Effect of an electrolyte salt dissolving in polysiloxane-based electrolyte on passive film formation on a graphite electrode

Science.gov (United States)

Nakahara, Hiroshi; Nutt, Steven

Electrochemical impedance spectroscopy (EIS) was performed during the first charge of a graphite/lithium metal test cell to determine the effect of an electrolyte salt on passive film formation in a polysiloxane-based electrolyte. The graphite electrode was separated from the lithium metal electrode by a porous polyethylene membrane immersed in a polysiloxane-based electrolyte with the dissolved lithium bis(oxalato) borate (LiBOB) or lithium bis(trifluoromethanesulfonyl) imide (LiTFSI). In case of LiTFSI, the conductivity of system decreased at 1.2 V. In contrast, for the case of LiBOB, the conductivity decreased at 1.7 V. The magnitudes of charge transfer resistance and film resistance for LiTFSI were smaller than that for LiBOB. Passive films on highly oriented pyrolytic graphite (HOPG) after charging (lithiating) in polysiloxane-based electrolyte were inspected microscopically. Gel-like film and island-like films were observed for LiBOB [H. Nakahara, A. Masias, S.Y. Yoon, T. Koike, K. Takeya, Proceedings of the 41st Power Sources Conference, vol. 165, Philadelphia, June 14-17, 2004; H. Nakahara, S.Y. Yoon, T. Piao, S. Nutt, F. Mansfeld, J. Power Sources, in press; H. Nakahara, S.Y. Yoon, S. Nutt, J. Power Sources, in press]. However, for LiTFSI, there was sludge accumulation on the HOPG surface. Compositional analysis revealed the presence of silicon on both HOPG specimens with LiBOB and with LiTFSI. The electrolyte salt dissolved in the polysiloxane-based electrolyte changed the electrochemical and morphological nature of passive films on graphite electrode.

PC based electrolytes with LiDFOB as an alternative salt for lithium-ion batteries

Science.gov (United States)

Knight, Brandon M.

Lithium-ion batteries (LIBs) have been greatly sought after as a source of renewable energy storage. LIBs have a wide range of applications including but not limited portable electronic devices, electric vehicles, and power tools. As a direct result of their commercial viability an insatiable hunger for knowledge, advancement within the field of LIBs has been omnipresent for the last two decades. However, there are set backs evident within the LIB field; most notably the limitations of standard electrolyte formulations and LiPF6 lithium salt. The standard primary carbonate of ethylene carbonate (EC) has a very limited operating range due to its innate physical properties, and the LiPF6 salt is known to readily decompose to form HF which can further degrade LIB longevity. The goal of our research is to explore the use of a new primary salt LiDFOB in conjunction with a propylene carbonate based electrolyte to establish a more flexible electrolyte formulation by constructing coin cells and cycling them under various conditions to give a clear understanding of each formulation inherent performance capabilities. Our studies show that 1.2M LiDFOB in 3:7 PC/EMC + 1.5% VC is capable of performing comparably to the standard 1.2M LiPF6 in 3:7 EC/EMC at 25°C and the PC electrolyte also illustrates performance superior to the standard at 55°C. The degradation of lithium manganese spinel electrodes, including LiNi 0.5Mn1.5O4, is an area of great concern within the field of lithium ion batteries (LIBs). Manganese containing cathode materials frequently have problems associated with Mn dissolution which significantly reduces the cycle life of LIB. Thus the stability of the cathode material is paramount to the performance of Mn spinel cathode materials in LIBs. In an effort to gain a better understanding of the stability of LiNi0.5 Mn1.5O4 in common LiPF6/carbonate electrolytes, samples were stored at elevated temperature in the presence of electrolyte. Then after storage both

Polymer electrolytes: an investigation of some poly (n-propylaziridine)/lithium salt compositions. Technical report

Energy Technology Data Exchange (ETDEWEB)

Baldwin, K R; Golder, A J; Knight, J

1984-04-01

Some poly(N-propylaziridine)/lithium salt compositions have been synthesized and their electrical conductivities have been measured in order to assess their suitability as electrolytes in safe, leakproof, high energy-density lithium batteries operating at ambient temperature. The effects on conductivity of temperature, and the nature and concentration of the salt have also been studied. The presence of the salts markedly improved the conductivity of the compositions over that of the undoped polymer but they were insufficiently conducting to be considered as battery electrolytes, due possibly to ion-pairing. Their creep resistance was also low. It was concluded that less fluid compositions containing higher molecular weight polymers better able to promote ion separation would be more suitable.

Enhanced cycling performance of a Li metal anode in a dimethylsulfoxide-based electrolyte using highly concentrated lithium salt for a lithium-oxygen battery

Science.gov (United States)

Togasaki, Norihiro; Momma, Toshiyuki; Osaka, Tetsuya

2016-03-01

Stable charge-discharge cycling behavior for a lithium metal anode in a dimethylsulfoxide (DMSO)-based electrolyte is strongly desired of lithium-oxygen batteries, because the Li anode is rapidly exhausted as a result of side reactions during cycling in the DMSO solution. Herein, we report a novel electrolyte design for enhancing the cycling performance of Li anodes by using a highly concentrated DMSO-based electrolyte with a specific Li salt. Lithium nitrate (LiNO3), which forms an inorganic compound (Li2O) instead of a soluble product (Li2S) on a lithium surface, exhibits a >20% higher coulombic efficiency than lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, and lithium perchlorate, regardless of the loading current density. Moreover, the stable cycling of Li anodes in DMSO-based electrolytes depends critically on the salt concentration. The highly concentrated electrolyte 4.0 M LiNO3/DMSO displays enhanced and stable cycling performance comparable to that of carbonate-based electrolytes, which had not previously been achieved. We suppose this enhancement is due to the absence of free DMSO solvent in the electrolyte and the promotion of the desolvation of Li ions on the solid electrolyte interphase surface, both being consequences of the unique structure of the electrolyte.

Electrochemical behavior and stability of a commercial activated carbon in various organic electrolyte combinations containing Li-salts

International Nuclear Information System (INIS)

Zhang, Tong; Fuchs, Bettina; Secchiaroli, Marco; Wohlfahrt-Mehrens, Margret; Dsoke, Sonia

2016-01-01

Highlights: • 1 M LiPF 6 in PC displays the widest electrochemical stability window among others couples electrolyte/activated carbon. • Electrolytes based on EC-DMC show lower impedance than electrolytes containing PC. • 1 M LiPF 6 in PC has the highest cycling stability with 75% of capacitance retention after 20 000 cycles. - Abstract: The fast development of Li-ion capacitor (LIC) technologies requires the use of low resistance and stable electrolytes. An electrolyte for a LIC not only has to provide Li for the intercalation/deintercalation of the battery-type materials, but it also needs to be compatible with the supercapacitor material. Before designing a hybrid Li-ion capacitor device containing Li-insertion and double layer-type materials, it is necessary to understand and separate the contribution of each electrode material to the resistance, capacity and stability in the chosen electrolyte. Due to the intensive research on Li-ion batteries, the interactions of Li-salt containing electrolytes combined with Li insertion materials have been extensively investigated, and a lot of literature is available on this field. In contrast, there is only little knowledge about the exclusive interaction and compatibility of Li containing electrolytes with supercapacitor-type electrode materials (in absence of battery materials). With this purpose, this paper explores the electrochemical performance of electrodes based on commercial activated carbon (AC) in various lithium salt-containing electrolytes. A standard electrolyte for Li-ion batteries (1 M LiPF 6 in EC:DMC, 1:1) is evaluated and compared with an electrolyte prepared with the same salt dissolved in propylene carbonate (1 M LiPF 6 in PC) which is a solvent typically used in commercial supercapacitors. Furthermore, two new electrolyte solutions are proposed, based on a blend of salts 0.8 M LiPF 6 + 0.2 M NEt 4 BF 4 in EC:DMC (1:1) as well as in pure PC. The effect of the electrolyte composition is evaluated

Investigations on PVdF- HFP - PEMA polymer blend electrolytes doped with different lithium salts

Science.gov (United States)

Manojkumar Ubarhande, Radha; Bhattacharya, Shreya; Usha Rani, M.; Shanker Babu, Ravi; Krishnaveni, S.

2017-11-01

Plasticized polymer blend electrolytes were prepared by incorporating poly (vinylidenefluoride-co-hexafluoropropylene)(PVdF-HFP) and poly(ethylmethacrylate) (PEMA) complexed with plasticizer (PC) and different lithium salts such as LiClO4, LiBF4, LiCF3SO3 and LiN (CF3SO2)2) using solution-casting technique. X-ray diffraction and Fourier transform infra-red techniques confirms the structural characters and complex formation of the polymer electrolytes respectively. AC impedance analysis was carried out for all the samples in the range303-373K. The results suggest that among the various lithium salts, LiN (CF3SO2)2) based electrolytes exhibited the highest ionic conductivity (3.17 × 10-3 Scm-1).

Effects of Imide–Orthoborate Dual-Salt Mixtures in Organic Carbonate Electrolytes on the Stability of Lithium Metal Batteries

Energy Technology Data Exchange (ETDEWEB)

Li, Xing [Energy and Environment; School of Materials Science and Engineering, Southwest Petroleum University, Chengdu, Sichuan 610500, China; Zheng, Jianming [Energy and Environment; Engelhard, Mark H. [Environmental Molecular; Mei, Donghai [Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Li, Qiuyan [Energy and Environment; Jiao, Shuhong [Energy and Environment; Liu, Ning [Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99354, United States; State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing, 100029, China; Zhao, Wengao [Energy and Environment; School of Energy Research, Xiamen University, Xiamen, Fujian 361102, China; Zhang, Ji-Guang [Energy and Environment; Xu, Wu [Energy and Environment

2018-01-09

The effects of lithium imide and lithium orthoborate dual-salt electrolytes of different salt chemistries in carbonate solvents on the cycling stability of Li metal batteries were systematically and comparatively investigated. Two imide salts (LiTFSI and LiFSI) and two orthoborate salts (LiBOB and LiDFOB) were chosen for this study and compared with the conventional LiPF6 salt. The cycling stability of the Li metal cells with the electrolytes follows the order from good to poor as LiTFSI-LiBOB > LiTFSI-LiDFOB > LiPF6 > LiFSI-LiBOB > LiFSI-LiDFOB, indicating that LiTFSI behaves better than LiFSI and LiBOB over LiDFOB in these four dual-salt mixtures. The LiTFSI-LiBOB can effectively protect the Al substrate and form a more robust surface film on Li metal anode, while the LiFSI-LiBOB results in serious corrosion to the stainless steel cell case and a thicker and looser surface film on Li anode. Computational calculations indicate that the chemical and electrochemical stabilities also follow the order of LiTFSI-LiBOB > LiTFSI-LiDFOB > LiFSI-LiBOB > LiFSI-LiDFOB. The key findings of this work emphasize that the salt chemistry is critically important for enhancing the interfacial stability of Li metal anode and should be carefully manipulated in the development of high performance Li metal batteries.

Solid electrolytes

Science.gov (United States)

Abraham, Kuzhikalail M.; Alamgir, Mohamed

1993-06-15

This invention pertains to Li ion (Li.sup.+) conductive solid polymer electrolytes composed of solvates of Li salts immobilized (encapsulated) in a solid organic polymer matrix. In particular, this invention relates to solid polymer electrolytes derived by immobilizing complexes (solvates) formed between a Li salt such as LiAsF.sub.6, LiCF.sub.3 SO.sub.3 or LiClO.sub.4 and a mixture of aprotic organic solvents having high dielectric constants such as ethylene carbonate (EC) (dielectric constant=89.6) and propylene carbonate (PC) (dielectric constant=64.4) in a polymer matrix such as polyacrylonitrile, poly(tetraethylene glycol diacrylate), or poly(vinyl pyrrolidinone).

Evaluation of a molten salt electrolyte for direct reduction of actinides

International Nuclear Information System (INIS)

Alangi, Nagaraj; Anupama, P.; Mukherjee, Jaya; Gantayet, L.M.

2011-01-01

Use of molten fluoride salt towards direct reduction of actinides and lanthanides by molten salt electrolysis is of interest for problems related to metallic nuclear fuels. The performance of the molten salt bath is dependent on the pre-conditioning of the molten salt. A procedure for conditioning of LiF-BaF 2 salt mixtures has been developed based on systematic electrochemical experimental investigations using voltammetry with graphite and platinum as electrode materials. We utilize the linear sweep voltammetry (LSV) as a diagnostic tool for assessment of the electrolyte condition. This technique is fast and offers the advantage of in-situ/online measurement eliminating the need for sampling. The conditioning procedure that was developed was tried on LiF-CaF 2

Effect of lithium salt concentrations on blended 49% poly(methyl methacrylate) grafted natural rubber and poly(methyl methacrylate) based solid polymer electrolyte

International Nuclear Information System (INIS)

Su’ait, M.S.; Ahmad, A.; Hamzah, H.; Rahman, M.Y.A.

2011-01-01

The effect of lithium salts (lithium tetrafluoroborate, LiBF 4 and lithium perchlorate, LiClO 4 ) as doping salts in rubber-polymer blends, 49% poly(methyl methacrylate) grafted natural rubber (MG49) and poly(methyl methacrylate) (PMMA) in solid polymer electrolyte (SPE) film for electrochemical devices application was investigated. The electrolyte films were prepared via the solution casting technique using 0–25 wt.% lithium salt. The effect of the lithium salts on chemical interaction, ionic conductivity and structural and morphological studies of (70:30) MG49-PMMA films was analyzed using Fourier Transform Infrared (FT-IR) Spectroscopy, Electrochemical Impedance Spectroscopy (EIS), X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). Infrared analysis showed that the interactions between lithium ions and oxygen atoms occur at the ether group (C–O–C) (1500–1100 cm −1 ) on the MMA structure in both MG49 and PMMA. The oxygen atoms in the structure of the polymer host act as electron donor atoms and form a coordinate bond with the lithium ions from the doping salt to form polymer–salt complexes. The ionic conductivity was investigated at room temperature as well as at a temperature range from 303 K to 373 K. The ionic conductivity without the addition of salt was 1.1 × 10 −12 S cm −1 . The highest conductivity at room temperature for (70:30) MG49-PMMA–LiBF 4 was 8.6 × 10 −6 S cm −1 at 25 wt.% of LiBF 4 . The ionic conductivity of (70:30) MG49-PMMA–LiClO 4 was 1.5 × 10 −8 S cm −1 at 25 wt.% of LiClO 4 . However, both electrolyte systems do not exhibit Arrhenius-like behavior. Systems with LiBF 4 salt have higher ionic conductivity than those with LiClO 4 salt because of the differences in anionic size and lattice energy of the appropriate salt. The observations from structural and morphology studies showed that complexation and re-crystallization occur in the system. The XRD studies showed a reduction of the MMA peak

Electrolytic experiments of gadolinium and neodymium ions in the fluoride molten salt

International Nuclear Information System (INIS)

Sim, J. B.; Hwang, S. C.; Kim, W. H.; Kang, Y. H.; Lee, B. J.; Yoo, J. H.

2002-01-01

Electrolytic reductions of Gd 3+ and Nd 3+ ions were carried out to prepare bismuth alloys including Gd and Nd solutes using a molten liquid Bi cathode in the LiF-NaF-KF fluoride salt. It was considered that selective separation of Gd from bismuth alloy is possible by controlling the addition amount of an oxidation agent to a salt phase. Cyclic voltammetry measurements are useful tools not only for in-situ detection of solutes in salt phase in the course of back extraction experiments but also for elucidation of electrochemical reactions of Gd and Nd in the FLINAK molten salt

Effect of salt species on electrochemical properties of gel-type polymer electrolyte based on chemically crosslinking rubber

Energy Technology Data Exchange (ETDEWEB)

Lee, Kab Youl; Jo, Nam Ju [Pusan National Univ., Busan (Korea). Dept. of Polymer Science and Engineering; Chung, Won Sub [Pusan National Univ., Busan (Korea). School of Materials Science and Engineering

2004-11-30

In our study, for ion-polymer interaction in gel-type polymer electrolyte (GPE), two kinds of ions were used. GPE systems were composed of Mg or Li salt, organic solvent ({gamma}-BL), and polymer matrix prepared by chemical crosslinking of NBR with poly(ethylene glycol) methylethermethacrylate (PEGMEM) having polar group (--CH{sub 2}--CH{sub 2}--O--) in the side chain of monomer. GPE consisting of Li{sup +} ion had higher ionic conductivity than that of Mg{sup 2+} ion at below 100 wt.% of electrolyte content (1 M salt/{gamma}-BL). On the other hand, GPE consisting of Mg{sup 2+} ion had higher ionic conductivity than that consisting of Li{sup +} ion at over 120 wt.% of electrolyte content (1 M salt/{gamma}-BL). The maximum liquid electrolyte content was 200 wt.% for all GPE systems. And the highest ionic conductivity of 3.3 x 10{sup -2} S cm{sup -1} was achieved for the case of Mg{sup 2+}-GPE with 200 wt.% of liquid electrolyte contents at 20 C. The interaction between ionic species and polymer matrix in GPE was investigated by using Fourier transform infrared spectroscopy (FT-IR). Also, cyclic voltammogram of Mg{sup 2+}-GPE confirmed the electrochemical property of divalent cation with two electron-transfer reactions.

Influence of the lithium salt electrolyte on the electrochemical performance of copper/LiFePO4 composites

International Nuclear Information System (INIS)

Trócoli, Rafael; Morales, Julián; Franger, Sylvain; Santos-Peña, Jesús

2012-01-01

In this work, we studied the influence of the electrolyte salt, LiPF 6 or LiClO 4 , on the electrochemical properties of copper/LiFePO 4 composites. We found a different stability voltage window for the two electrolytes that was remarkably wide for LiPF 6 . Also, copper addition is commonly accepted to increase electrode conductivity, which is beneficial for electrochemical purposes. However, copper is always oxidised to a variable extent depending on the particular electrolyte during the charge phase. Oxidation of the electrolyte solvent (especially with LiClO 4 ) was also observed during the first charge. In the first cycle, copper was more or less efficiently removed from the electrode surface. In subsequent cycles, however, these phenomena failed to occur (LiPF 6 ) or were weaker (LiClO 4 ). In all these configurations, iron is partially dissolved, to an extent dependent on the amount of copper present in the composite and differing with the particular electrolyte used. Electrochemical impedance spectroscopy allowed us to identify the process taking place close to 3.6 V in LiPF 6 configuration: Fe(II) from the composites are oxidised and irreversibly complexed by the joint action of HF formed from LiPF 6 and water traces and Cu(I) formed upon charging. Our hypothesis accurately explains the results observed in terms of charge/discharge profiles, capacities provided and capacities evolution upon cycling. Also, our test results testify to the importance of using low contents of copper in the composites and the good properties of LiPF 6 as electrolyte solvent.

Ionic conductivity of ternary electrolyte containing sodium salt and ionic liquid

International Nuclear Information System (INIS)

Egashira, Minato; Asai, Takahito; Yoshimoto, Nobuko; Morita, Masayuki

2011-01-01

Highlights: ► Ternary electrolyte containing NaBF 4 , polyether and ionic liquid has been prepared. ► The conductivity of the electrolytes has been evaluated toward content of ionic liquid. ► The conductivity shows maximum 1.2 mS cm −1 and is varied in relation to solution structure. - Abstract: For the development of novel non-aqueous sodium ion conductor with safety of sodium secondary cell, non-flammable ionic liquid is attractive as electrolyte component. A preliminary study has been carried out for the purpose of constructing sodium ion conducting electrolyte based on ionic liquid. The solubility of sodium salt such as NaBF 4 in ionic liquid is poor, thus the ternary electrolyte has been prepared where NaBF 4 with poly(ethylene glycol) dimethyl ether (PEGDME) as coordination former is dissolved with ionic liquid diethyl methoxyethyl ammonium tetrafluoroborate (DEMEBF 4 ). The maximum conductivity among the prepared solutions, ca. 1.2 mS cm −1 at 25 °C, was obtained when the molar ratio (ethylene oxide unit in PEGDME):NaBF 4 :DEMEBF 4 was 8:1:2. The relationship between the conductivity of the ternary electrolyte and its solution structure has been discussed.

Ionic relaxation in PEO/PVDF-HFP-LiClO4 blend polymer electrolytes: dependence on salt concentration

Science.gov (United States)

Das, S.; Ghosh, A.

2016-06-01

In this paper, we have studied the effect of LiClO4 salt concentration on the ionic conduction and relaxation in poly ethylene oxide (PEO) and poly (vinylidene fluoride hexafluoropropylene) (PVDF-HFP) blend polymer electrolytes, in which the molar ratio of ethylene oxide segments to lithium ions (R  =  EO: Li) has been varied between 3 and 35. We have observed two phases in the samples containing low salt concentrations (R  >  9) and single phase in the samples containing high salt concentrations (R  ⩽  9). The scanning electron microscopic images indicate that there exists no phase separation in the blend polymer electrolytes. The temperature dependence of the ionic conductivity shows two slopes corresponding to high and low temperatures and follows Arrhenius relation for the samples containing low salt concentrations (R  >  9). The conductivity relaxation as well as the structural relaxation has been clearly observed at around 104 Hz and 106 Hz for these concentrations of the blended electrolytes. However, a single conductivity relaxation peak has been observed for the compositions with R  ⩽  9. The scaling of the conductivity spectra shows that the relaxation mechanism is independent of temperature, but depends on salt concentration.

Advancing Polymer-Supported Ionogel Electrolytes Formed via Radical Polymerization

Science.gov (United States)

Visentin, Adam F.

Applications ranging from consumer electronics to the electric grid have placed demands on current energy storage technologies. There is a drive for devices that store more energy for rapid consumption in the case of electric cars and the power grid, and safer, versatile design options for consumer electronics. Electrochemical double-layer capacitors (EDLCs) are an option that has garnered attention as a means to address these varied energy storage demands. EDLCs utilize charge separation in electrolytes to store energy. This energy storage mechanism allows for greater power density (W kg -1) than batteries and higher energy density (Wh kg-1) than conventional capacitors - along with a robust lifetime in the range of thousands to millions of charge-discharge cycles. Safety and working voltage windows of EDLCs currently on the market are limited by the organic solvents utilized in the electrolyte. A potential solution lies in the replacement of the organic solvents with ionic liquids, or room-temperature molten salts. Ionic liquids possess many superior properties in comparison to conventional solvents: wide electrochemical window, low volatility, nonflammability, and favorable ionic conductivity. It has been an endeavor of this work to exploit these advantages while altering the liquid form factor into a gel. An ionic liquid/solid support scaffold composite electrolyte, or ionogel, adds additional benefits: flexible device design, lower encapsulation weight, and elimination of electrolyte leakage. This work has focused on investigations of a UV-polymerizable monomer, poly(ethylene glycol) diacrylate, as a precursor for forming ionogels in situ. The trade-off between gaining mechanical stability at the cost of ionic conductivity has been investigated for numerous ionogel systems. While gaining a greater understanding of the interactions between the gel scaffold and ionic liquid, an ionogel with the highest known ionic conductivity to date (13.1 mS cm-1) was

Polymer Electrolytes

Science.gov (United States)

Hallinan, Daniel T.; Balsara, Nitash P.

2013-07-01

This review article covers applications in which polymer electrolytes are used: lithium batteries, fuel cells, and water desalination. The ideas of electrochemical potential, salt activity, and ion transport are presented in the context of these applications. Potential is defined, and we show how a cell potential measurement can be used to ascertain salt activity. The transport parameters needed to fully specify a binary electrolyte (salt + solvent) are presented. We define five fundamentally different types of homogeneous electrolytes: type I (classical liquid electrolytes), type II (gel electrolytes), type III (dry polymer electrolytes), type IV (dry single-ion-conducting polymer electrolytes), and type V (solvated single-ion-conducting polymer electrolytes). Typical values of transport parameters are provided for all types of electrolytes. Comparison among the values provides insight into the transport mechanisms occurring in polymer electrolytes. It is desirable to decouple the mechanical properties of polymer electrolyte membranes from the ionic conductivity. One way to accomplish this is through the development of microphase-separated polymers, wherein one of the microphases conducts ions while the other enhances the mechanical rigidity of the heterogeneous polymer electrolyte. We cover all three types of conducting polymer electrolyte phases (types III, IV, and V). We present a simple framework that relates the transport parameters of heterogeneous electrolytes to homogeneous analogs. We conclude by discussing electrochemical stability of electrolytes and the effects of water contamination because of their relevance to applications such as lithium ion batteries.

Electrochemical investigation of electrochromic devices based on NiO and WO3 films using different lithium salts electrolytes

International Nuclear Information System (INIS)

Wei, Youxiu; Chen, Mu; Liu, Weiming; Li, Lei; Yan, Yue

2017-01-01

Highlights: •ECDs based on NiO and WO 3 films using different electrolytes were fabricated. •Effect of different electrolytes on films and ECDs was investigated. •Applied voltage distribution on NiO and WO 3 electrodes in an ECD was studied. •Voltage distribution on films was unbalanced and associated with electrolyte. •Films have different impedance behavior in different states and electrolytes. -- Abstract: Electrochromic devices (ECDs) with different liquid electrolytes were fabricated using NiO film as counter electrode, WO 3 film as working electrode. The effect of liquid electrolytes containing different lithium salts (LiClO 4 , LiPF 6 , LiTFSI) on films and ECDs was investigated, such as transmittance change, charge density, memory effect and cyclic stability. Films or ECDs using LiPF 6 electrolyte have excellent electrochromic properties but low cyclic stability, compared with LiClO 4 and LiTFSI electrolytes. In order to deeply understand the effect of electrolyte on films and devices, the voltage distribution of films based on an analog cell and electrochemical impedance spectroscopy (EIS) were measured and analyzed in different lithium salts electrolytes. Results show that voltage distribution and EIS characteristics of films have obvious difference in liquid LiClO 4 , LiPF 6 and LiTFSI electrolytes. Voltage distribution on NiO and WO 3 films is unbalanced and the impedance of films in bleached and colored states is different in the same electrolyte.

Polyfluorinated boron cluster based salts: A new electrolyte for application in nonaqueous asymmetric AC/Li{sub 4}Ti{sub 5}O{sub 12} supercapacitors

Energy Technology Data Exchange (ETDEWEB)

Ionica-Bousquet, C.M.; Munoz-Rojas, D.; Palacin, M.R. [Institut de Ciencia de Materials de Barcelona, CSIC, Campus UAB, E-08193 Bellaterra (Spain); Casteel, W.J. Jr.; Pearlstein, R.M.; Kumar, G. Girish; Pez, G.P. [Air Products and Chemicals, Inc., 7201 Hamilton Blvd., Allentown, PA 18195 (United States)

2011-02-01

Solutions of novel fluorinated lithium dodecaborate (Li{sub 2}B{sub 12}F{sub x}H{sub 12-x}) salts have been evaluated as electrolytes in nonaqueous asymmetric supercapacitors with Li{sub 4}Ti{sub 5}O{sub 12} as negative electrode, and activated carbon (AC) as positive electrode. The results obtained with these new electrolytes were compared with those obtained with cells built using standard 1 M LiPF{sub 6} dissolved in ethylene carbonate and dimethyl carbonate (EC:DMC; 1:1, v/v) as electrolyte. The specific energy, rate capability, and cycling performances of nonaqueous asymmetric cells based on these new electrolyte salts were studied. Cells assembled using the new fluoroborate salts show excellent reversibility, coulombic efficiency, rate capability and improved cyclability when compared with the standard electrolyte. These features confirm the suitability of lithium-fluoro-borate based salts to be used in nonaqueous asymmetric supercapacitors. (author)

Nanoscale Organic Hybrid Electrolytes

KAUST Repository

Nugent, Jennifer L.

2010-08-20

Nanoscale organic hybrid electrolytes are composed of organic-inorganic hybrid nanostructures, each with a metal oxide or metallic nanoparticle core densely grafted with an ion-conducting polyethylene glycol corona - doped with lithium salt. These materials form novel solvent-free hybrid electrolytes that are particle-rich, soft glasses at room temperature; yet manifest high ionic conductivity and good electrochemical stability above 5V. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoscale Organic Hybrid Electrolytes

KAUST Repository

Nugent, Jennifer L.; Moganty, Surya S.; Archer, Lynden A.

2010-01-01

Nanoscale organic hybrid electrolytes are composed of organic-inorganic hybrid nanostructures, each with a metal oxide or metallic nanoparticle core densely grafted with an ion-conducting polyethylene glycol corona - doped with lithium salt. These materials form novel solvent-free hybrid electrolytes that are particle-rich, soft glasses at room temperature; yet manifest high ionic conductivity and good electrochemical stability above 5V. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Distillation of LiCl from the LiCl-Li2O molten salt of the electrolytic reduction process

International Nuclear Information System (INIS)

Kim, I.S.; Oh, S.C.; Im, H.S.; Hur, J.M.; Lee, H.S.

2013-01-01

Electrolytic reduction of the uranium oxide in LiCl-Li 2 O molten salt for the treatment of spent nuclear fuel requires the separation of the residual salt from the reduced metal product, which contains about 20 wt% salt. In order to separate the residual salt and reuse it in the electrolytic reduction, a vacuum distillation process was developed. Lab-scale distillation equipment was designed and installed in an argon atmosphere glove box. The equipment consisted of an evaporator in which the reduced metal product was contained and exposed to a high temperature and reduced pressure; a receiver; and a vertically oriented condenser that operated at a temperature below the melting point of lithium chloride. We performed experiments with LiCl-Li 2 O salt to evaluate the evaporation rate of LiCl salt and varied the operating temperature to discern its effect on the behavior of salt evaporation. Complete removal of the LiCl salt from the evaporator was accomplished by reducing the internal pressure to <100 mTorr and heating to 900 deg C. We achieved evaporation efficiency as high as 100 %. (author)

Production of uranium metal via electrolytic reduction of uranium oxide in molten LiCl and salt distillation

International Nuclear Information System (INIS)

Eun-Young Choi; Chan Yeon Won; Dae-Seung Kang; Sung-Wook Kim; Ju-Sun Cha; Sung-Jai Lee; Wooshin Park; Hun Suk Im; Jin-Mok Hur

2015-01-01

Recovery of metallic uranium has been achieved by electrolytic reduction of uranium oxide in a molten LiCl-Li 2 O electrolyte at 650 deg C, followed by the removal of the residual salt by vacuum distillation at 850 deg C. Four types of stainless steel mesh baskets, with various mesh sizes (325, 1,400 and 2,300 meshes) and either three or five ply layers, were used both as cathodes and to contain the reduced product in the distillation stage. The recovered uranium had a metal fraction greater than 98.8 % and contained no residual salt. (author)

Reoxidation of uranium in electrolytically reduced simulated oxide fuel during residual salt distillation

International Nuclear Information System (INIS)

Eun-Young Choi; Jin-Mok Hur; Min Ku Jeon; University of Science and Technology, Yuseong-gu, Daejeon

2017-01-01

We report that residual salt removal by high-temperature distillation causes partial reoxidation of uranium metal to uranium oxide in electrolytically reduced simulated oxide fuel. Specifically, the content of uranium metal in the above product decreases with increasing distillation temperatures, which can be attributed to reoxidation by Li 2 O contained in residual salt (LiCl). Additionally, we estimate the fractions of Li 2 O reacted with uranium metal under these conditions, showing that they decrease with decreasing temperature, and calculate some thermodynamic parameters of the above reoxidation. (author)

Cation effect on small phosphonium based ionic liquid electrolytes with high concentrations of lithium salt

Science.gov (United States)

Chen, Fangfang; Kerr, Robert; Forsyth, Maria

2018-05-01

Ionic liquid electrolytes with high alkali salt concentrations have displayed some excellent electrochemical properties, thus opening up the field for further improvements to liquid electrolytes for lithium or sodium batteries. Fundamental computational investigations into these high concentration systems are required in order to gain a better understanding of these systems, yet they remain lacking. Small phosphonium-based ionic liquids with high concentrations of alkali metal ions have recently shown many promising results in experimental studies, thereby prompting us to conduct further theoretical exploration of these materials. Here, we conducted a molecular dynamics simulation on four small phosphonium-based ionic liquids with 50 mol. % LiFSI salt, focusing on the effect of cation structure on local structuring and ion diffusional and rotational dynamics—which are closely related to the electrochemical properties of these materials.

Reoxidation of uranium metal immersed in a Li2O-LiCl molten salt after electrolytic reduction of uranium oxide

Science.gov (United States)

Choi, Eun-Young; Jeon, Min Ku; Lee, Jeong; Kim, Sung-Wook; Lee, Sang Kwon; Lee, Sung-Jai; Heo, Dong Hyun; Kang, Hyun Woo; Jeon, Sang-Chae; Hur, Jin-Mok

2017-03-01

We present our findings that uranium (U) metal prepared by using the electrolytic reduction process for U oxide (UO2) in a Li2O-LiCl salt can be reoxidized into UO2 through the reaction between the U metal and Li2O in LiCl. Two salt types were used for immersion of the U metal: one was the salt used for electrolytic reduction, and the other was applied to the unused LiCl salts with various concentrations of Li2O and Li metal. Our results revealed that the degree of reoxidation increases with the increasing Li2O concentration in LiCl and that the presence of the Li metal in LiCl suppresses the reoxidation of the U metal.

Lithium-Ion Electrolytes Containing Flame Retardant Additives for Increased Safety Characteristics

Science.gov (United States)

Smart, Marshall C. (Inventor); Smith, Kiah A. (Inventor); Bugga, Ratnakumar V. (Inventor); Prakash, Surya G. (Inventor); Krause, Frederick Charles (Inventor)

2014-01-01

The invention discloses various embodiments of Li-ion electrolytes containing flame retardant additives that have delivered good performance over a wide temperature range, good cycle life characteristics, and improved safety characteristics, namely, reduced flammability. In one embodiment of the invention there is provided an electrolyte for use in a lithium-ion electrochemical cell, the electrolyte comprising a mixture of an ethylene carbonate (EC), an ethyl methyl carbonate (EMC), a fluorinated co-solvent, a flame retardant additive, and a lithium salt. In another embodiment of the invention there is provided an electrolyte for use in a lithium-ion electrochemical cell, the electrolyte comprising a mixture of an ethylene carbonate (EC), an ethyl methyl carbonate (EMC), a flame retardant additive, a solid electrolyte interface (SEI) film forming agent, and a lithium salt.

Role of electrolyte composition on structural, morphological and in-vitro biological properties of plasma electrolytic oxidation films formed on zirconium

International Nuclear Information System (INIS)

M, Sandhyarani; T, Prasadrao; N, Rameshbabu

2014-01-01

Highlights: • Uniform oxide films were formed on zirconium by plasma electrolytic oxidation. • Silicate in electrolyte alter the growth of m-ZrO 2 from (1 ¯ 11) to (2 0 0) orientation. • Addition of KOH to electrolyte improved the corrosion resistance of oxide films. • Silicon incorporated oxide films showed higher surface roughness and wettability. • Human osteosarcoma cells were strongly adhered and spreaded on all the oxide films. - Abstract: Development of oxide films on metallic implants with a good combination of corrosion resistance, bioactivity and cell adhesion can greatly improve its biocompatibility and functionality. Thus, the present work is aimed to fabricate oxide films on metallic Zr by plasma electrolytic oxidation (PEO) in methodically varied concentrations of phosphate, silicate and KOH based electrolyte systems using a pulsed DC power source. The oxide films fabricated on Zr are characterized for its phase composition, surface morphology, chemical composition, roughness, wettability, surface energy, corrosion resistance, apatite forming ability and osteoblast cell adhesion. Uniform films with thickness varying from 6 to 11 μm are formed. XRD patterns of all the PEO films showed the predominance of monoclinic zirconia phase. The film formed in phosphate + KOH electrolyte showed superior corrosion resistance, which can be ascribed to its pore free morphology. The films formed in silicate electrolyte showed higher apatite forming ability with good cell adhesion and spreading over its surface which is attributed to its superior surface roughness and wettability characteristics. Among the five different electrolyte systems employed in the present study, the PEO film formed in an electrolyte system with phosphate + silicate + KOH showed optimum corrosion resistance, apatite forming ability and biocompatibility

All-Organic Rechargeable Battery with Reversibility Supported by "Water-in-Salt" Electrolyte.

Science.gov (United States)

Dong, Xiaoli; Yu, Hongchuan; Ma, Yuanyuan; Bao, Junwei Lucas; Truhlar, Donald G; Wang, Yonggang; Xia, Yongyao

2017-02-21

Rechargeable batteries with organic electrodes are preferred to those with transition-metal-containing electrodes for their environmental friendliness, and resource availability, but all such batteries reported to date are based on organic electrolytes, which raise concerns of safety and performance. Here an aqueous-electrolyte all-organic rechargeable battery is reported, with a maximum operating voltage of 2.1 V, in which polytriphenylamine (PTPAn) and 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTCDA)-derived polyimide (PNTCDA) serve as cathode and anode material, respectively. A key feature of the design is use of a "water-in-salt" electrolyte to bind "free" water; this impedes the side reaction of water oxidation, thereby enabling excellent reversibility in aqueous solution. The battery can deliver a maximum energy density of 52.8 Wh kg -1 , which is close to most of the all-organic batteries with organic electrolytes. The battery exhibits a supercapacitor-like high power of 32 000 W kg -1 and a long cycle life (700 cycles with capacity retention of 85 %), due to the kinetics not being limited by ion diffusion at either electrode. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optimization of hybrid polymer electrolytes with the effect of lithium salt concentration in PEO/PVdF-HFP blends

Energy Technology Data Exchange (ETDEWEB)

Pradeepa, P.; Edwin raj, S.; Sowmya, G.; Kalaiselvimary, J.; Ramesh Prabhu, M., E-mail: mkram83@gmail.com

2016-03-15

Highlights: • Polymer blends based on PVdF-HFP/PEO were prepared for Li-ion battery applications. • Structural and electrochemical studies were carried out on prepared electrolytes. • The electrolytes can be used as electrolyte in the possible device fabrications. - Abstract: Poly(ethylene oxide) (PEO) 6.25 wt%/poly(vinylidene fluoride-co-hexafluoropropylene) [P(VdF-HFP)] 18.75 wt% blend based electrolyte films containing different concentrations (2–10) wt% of lithium salt were prepared. The miscibility studies have been performed by using X-ray diffraction and Fourier transform infrared spectroscopy. The role of interaction between polymer hosts on conductivity is discussed using the results of a.c. impedance studies. A room temperature conductivity of 2.3912 × 10{sup −4} S cm{sup −1} has been obtained for PEO (6.25)–PVdF-HFP (18.75)–LiClO{sub 4} (8)–PC (67) polymer complex. The temperature dependence of the conductivity of polymer electrolyte seems to obey VTF relation. Electrochemical stability (3.3 V) was observed in the prepared polymer electrolyte. Reduction process and oxidation process of the prepared electrolyte system have also been evaluated by means of cyclic voltammetry. Thermogravimetric analysis results indicate thermal stability of PEO/PVdF-HFP lithium salt complexes. Roughness parameter of the sample having maximum ionic conductivity was studied by AFM. The morphology of the polymer complex is investigated by using SEM.

Microhardness of anodic aluminum oxide formed in an alkaline electrolyte

Science.gov (United States)

Kanygina, O. N.; Filyak, M. M.

2017-04-01

The microhardness of anodic aluminum oxide formed by anodizing of aluminum sheet in electrolyte on the basis of sodium hydroxide has been determined experimentally. The microhardness of the hard film/soft substrate system has been estimated by three approaches: indentation geometry (length of diagonals) in film surfaces, the sum of the hardnesses of the film and the surface with allowance for the indentation surface area and geometry, and with allowance for the indentation depth. It is demonstrated that the approach accounting for the indentation depth makes it possible to eliminate the influence of the substrate. It is established that the microhardness of the films formed in alkaline electrolytes is comparable with that formed in acid electrolytes.

Electrochemical separation of actinides and fission products in molten salt electrolyte

Energy Technology Data Exchange (ETDEWEB)

Gay, R.L.; Grantham, L.F.; Fusselman, S.P. [Rockwell International/Rocketdyne Division, Canoga Park, CA (United States)] [and others

1995-10-01

Molten salt electrochemical separation may be applied to accelerator-based conversion (ABC) and transmutation systems by dissolving the fluoride transport salt in LiCl-KCl eutectic solvent. The resulting fluoride-chloride mixture will contain small concentrations of fission product rare earths (La, Nd, Gd, Pr, Ce, Eu, Sm, and Y) and actinides (U, Np, Pu, Am, and Cm). The Gibbs free energies of formation of the metal chlorides are grouped advantageously such that the actinides can be deposited on a solid cathode with the majority of the rare earths remaining in the electrolyte. Thus, the actinides are recycled for further transmutation. Rockwell and its partners have measured the thermodynamic properties of the metal chlorides of interest (rare earths and actinides) and demonstrated separation of actinides from rare earths in laboratory studies. A model is being developed to predict the performance of a commercial electrochemical cell for separations starting with PUREX compositions. This model predicts excellent separation of plutonium and other actinides from the rare earths in metal-salt systems.

Electrolytic method to make alkali alcoholates using ion conducting alkali electrolyte/separator

Science.gov (United States)

Joshi, Ashok V [Salt Lake City, UT; Balagopal, Shekar [Sandy, UT; Pendelton, Justin [Salt Lake City, UT

2011-12-13

Alkali alcoholates, also called alkali alkoxides, are produced from alkali metal salt solutions and alcohol using a three-compartment electrolytic cell. The electrolytic cell includes an anolyte compartment configured with an anode, a buffer compartment, and a catholyte compartment configured with a cathode. An alkali ion conducting solid electrolyte configured to selectively transport alkali ions is positioned between the anolyte compartment and the buffer compartment. An alkali ion permeable separator is positioned between the buffer compartment and the catholyte compartment. The catholyte solution may include an alkali alcoholate and alcohol. The anolyte solution may include at least one alkali salt. The buffer compartment solution may include a soluble alkali salt and an alkali alcoholate in alcohol.

Separation of Electrolytic Reduction Product from Stainless Steel Wire Mesh Cathode Basket via Salt Draining and Reuse of the Cathode Basket

OpenAIRE

Choi, Eun-Young; Lee, Jeong; Heo, Dong Hyun; Hur, Jin-Mok

2017-01-01

We demonstrated that the metallic product obtained after electrolytic reduction (also called oxide reduction (OR)) can be simply separated from a stainless steel wire mesh cathode basket only by using a salt drain. First, the OR run of a simulated oxide fuel (0.6 kg/batch) was conducted in a molten Li2O–LiCl salt electrolyte at 650°C. The simulated oxide fuel of the porous cylindrical pellets was used as a cathode by loading a stainless steel wire mesh cathode basket. Platinum was employed as...

The role of the salt electrolyt on the electrical conductive properties of a polymeric bipolar membrane

NARCIS (Netherlands)

Alcaraz, Antonio; Wilhelm, F.G.; Wessling, Matthias; Ramirez, Patricio

2001-01-01

We have studied the contribution of the salt electrolyte to the electrical conductive characteristics of a bipolar membrane. We present first a critical analysis of previous theoretical approaches, and discuss the limits of validity. Experimental current-voltage curves of several commercial bipolar

Enhanced electrocatalysis performance of amorphous electrolytic carbon from CO2 for oxygen reduction by surface modification in molten salt

International Nuclear Information System (INIS)

Chen, Zhigang; Gu, Yuxing; Du, Kaifa; Wang, Xu; Xiao, Wei; Mao, Xuhui; Wang, Dihua

2017-01-01

Highlights: •The potential of electrolytic carbon as catalyst for oxygen reduction was evaluated. •A molten salt method for electrolytic-carbon modification was demonstrated. •The electrolytic carbon was activated for the ORR by the molten salt sulfidation. •Sulfur and cobalt dual modification further improved the ORR activity of the carbon. -- Abstract: The electrolytic carbon (E-carbon) derived from greenhouse gas CO 2 in molten carbonates at mild temperature possesses high electrical conductivity and suitable specific surface area. In this work, its potential as catalyst is investigated towards oxygen reduction reaction (ORR). It is revealed that the pristine E-carbon has no electrocatalytic activity for the ORR due to its high surface content of carboxyl group. The carbon was then treated in a Li 2 SO 4 containing Li 2 CO 3 -Na 2 CO 3 -K 2 CO 3 molten salt at 550 °C. Sulfur modified E-carbon was obtained in the melt via a galvanic sulfidation reaction, in which Li 2 SO 4 served as a nontoxic sulfur source and an oxidant. The sulfur modified E-carbon showed a significantly improved electrocatalytic activity. Subsequently, a sulfur/cobalt dual modified carbon with much higher catalysis activity was successfully prepared by treating an E-carbon/CoSO 4 composite in the same melt. The dual modified E-carbon showed excellent catalytic performance with activity close to the commercial Pt/C catalyst but a high tolerance towards methanol.

Novel thixotropic gel electrolytes based on dicationic bis-imidazolium salts for quasi-solid-state dye-sensitized solar cells

Science.gov (United States)

Kim, Jun Young; Kim, Tae Ho; Kim, Dong Young; Park, Nam-Gyu; Ahn, Kwang-Duk

Novel thixotropic gel electrolytes have been successfully prepared by utilizing oligomeric poly(ethylene oxide) (PEO)-based bis-imidazolium diiodide salts and hydrophilic silica nanoparticles for application in quasi-solid-state dye-sensitized solar cells (DSSCs). The thixotropic gel-state of the ionic liquid-based composite electrolytes is confirmed by observing the typical hysteresis loop and temporary hydrogen bonding. On using the PEO-based composite electrolyte, a quasi-solid-state DSSC exhibited highly improved properties such as easy penetration of the electrolyte into the cell without leakage, long-term stability, high open-circuit voltage without the use of 4- tert-butylpyridine, and a high energy-conversion efficiency of 5.25% under AM 1.5 illumination (100 mW cm -2).

Converting hcp Mg-Al-Zn alloy into bcc Mg-Li-Al-Zn alloy by electrolytic deposition and diffusion of reduced lithium atoms in a molten salt electrolyte LiCl-KCl

International Nuclear Information System (INIS)

Lin, M.C.; Tsai, C.Y.; Uan, J.Y.

2007-01-01

A body-centered cubic (bcc) Mg-12Li-9Al-1Zn (wt.%) alloy was fabricated in air by electrolysis from LiCl-KCl molten salt at 500 deg. C. Electrolytic deposition of Li atoms on cathode (Mg-Al-Zn alloy) and diffusion of the Li atoms formed the bcc Mg-Li-Al-Zn alloy with 12 wt.% Li and only 0.264 wt.% K. Low K concentration in the bcc Mg alloy strip after the electrolysis process resulted from 47% atomic size misfit between K and Mg atoms and low solubility of K in Mg matrix

High cation transport polymer electrolyte

Science.gov (United States)

Gerald, II, Rex E.; Rathke, Jerome W [Homer Glen, IL; Klingler, Robert J [Westmont, IL

2007-06-05

A solid state ion conducting electrolyte and a battery incorporating same. The electrolyte includes a polymer matrix with an alkali metal salt dissolved therein, the salt having an anion with a long or branched chain having not less than 5 carbon or silicon atoms therein. The polymer is preferably a polyether and the salt anion is preferably an alkyl or silyl moiety of from 5 to about 150 carbon/silicon atoms.

Novel thixotropic gel electrolytes based on dicationic bis-imidazolium salts for quasi-solid-state dye-sensitized solar cells

Energy Technology Data Exchange (ETDEWEB)

Kim, Jun Young [Department of Polymer Science and Engineering, SungKyunKwan University, Suwon, Kyunggi-do 440-746 (Korea); Functional Polymer Lab., Korea Institute of Science and Technology, Seoul 136-791 (Korea); Kim, Tae Ho [Department of Polymer Science and Engineering, SungKyunKwan University, Suwon, Kyunggi-do 440-746 (Korea); Kim, Dong Young; Park, Nam-Gyu [Energy Materials Research Center, Korea Institute of Science and Technology, Seoul 136-791 (Korea); Ahn, Kwang-Duk [Functional Polymer Lab., Korea Institute of Science and Technology, Seoul 136-791 (Korea)

2008-01-03

Novel thixotropic gel electrolytes have been successfully prepared by utilizing oligomeric poly(ethylene oxide) (PEO)-based bis-imidazolium diiodide salts and hydrophilic silica nanoparticles for application in quasi-solid-state dye-sensitized solar cells (DSSCs). The thixotropic gel-state of the ionic liquid-based composite electrolytes is confirmed by observing the typical hysteresis loop and temporary hydrogen bonding. On using the PEO-based composite electrolyte, a quasi-solid-state DSSC exhibited highly improved properties such as easy penetration of the electrolyte into the cell without leakage, long-term stability, high open-circuit voltage without the use of 4-tert-butylpyridine, and a high energy-conversion efficiency of 5.25% under AM 1.5 illumination (100 mW cm{sup -2}). (author)

Development of electrolytic process in molten salt media for light rare-earth metals production. The metallic cerium electrodeposition

International Nuclear Information System (INIS)

Restivo, T.A.G.

1994-01-01

The development of molten salt process and the respective equipment aiming rare-earth metals recovery was described. In the present case, the liquid cerium metal electrodeposition in a molten electrolytes of cerium chloride and an equimolar mixture of sodium and potassium chlorides in temperatures near 800 C was studied. Due the high chemical reactivity of the rare-earth metals in the liquid state and their molten halides, an electrolytic cell was constructed with controlled atmosphere, graphite crucibles and anodes and a tungsten cathode. The electrolytic process variables and characteristics were evaluated upon the current efficiency and metallic product purity. Based on this evaluations, were suggested some alterations on the electrolytic reactor design and upon the process parameters. (author). 90 refs, 37 figs, 20 tabs

A study on the electrolytic reduction of uranium oxide in a LiCl-Li2O molten salt

International Nuclear Information System (INIS)

Su, J. S.; Hu, J. M.; Hong, S. S.; Jang, D. S.; Park, S. W.

2003-01-01

New electrolytic reduction technology was proposed that is based on the integration of metallization of uranium oxide and Li 2 O electrowinning. In this electrolytic reduction reaction, electrolytically reduced Li deposits on cathode and simultaneously reacts with uranium oxides to produce uranium metal showing more than 99% conversion. For the verification of process feasibility, the experiments to obtain basic data on the metallization of uranium oxide, investigation of reaction mechanism, the characteristics of closed recycle of Li 2 O and mass transfer were carried out. This evolutionary electrolytic reduction technology would give benefits over the conventional Li-reduction process improving economic viability such as: avoidance of handling of chemically active Li-LiCl molten salt, increase of metallization yield, and simplification of process

Stability of pharmaceutical salts in solid oral dosage forms.

Science.gov (United States)

Nie, Haichen; Byrn, Stephen R; Zhou, Qi Tony

2017-08-01

Using pharmaceutical salts in solid dosage forms can raise stability concerns, especially salt dissociation which can adversely affect the product performance. Therefore, a thorough understanding of the salt instability encountered in solid-state formulations is imperative to ensure the product quality. The present article uses the fundamental theory of acid base, ionic equilibrium, relationship of pH and solubility as a starting point to illustrate and interpret the salt formation and salt disproportionation in pharmaceutical systems. The criteria of selecting the optimal salt form and the underlying theory of salt formation and disproportionation are reviewed in detail. Factors influencing salt stability in solid dosage forms are scrutinized and discussed with the case studies. In addition, both commonly used and innovative strategies for preventing salt dissociations in formulation, on storage and during manufacturing will be suggested herein. This article will provide formulation scientists and manufacturing engineers an insight into the mechanisms of salt disproportionation and salt formation, which can help them to avoid and solve the instability issues of pharmaceutical salts in the product design.

Conductivity studies of PEG based polymer electrolyte for applications as electrolyte in ion batteries

Science.gov (United States)

Patil, Ravikumar V.; Praveen, D.; Damle, R.

2018-05-01

Development of lithium ion batteries employing solid polymer electrolytes as electrolyte material has led to efficient energy storage and usage in many portable devices. However, due to a few drawbacks like lower ionic conductivity of solid polymer electrolytes (SPEs), studies on SPEs for improvement in conductivity still have a good scope. In the present paper, we report the conductivity studies of a new SPE with low molecular weight poly ethylene glycol (PEG) as host polymer in which a salt with larger anion Lithium trifluro methane sulphonate (LTMS). XRD studies have revealed that the salt completely dissociates in the polymer giving a good stable electrolyte at lower salt concentration. Conductivity of the SPEs has been studied as a function of temperature and we reiterate that the conductivity is a thermally activated process and follows Arrhenius type behavior.

Electrolytic production of metals using a resistant anode

Science.gov (United States)

Tarcy, G.P.; Gavasto, T.M.; Ray, S.P.

1986-11-04

An electrolytic process is described comprising evolving oxygen on an anode in a molten salt, the anode comprising an alloy comprising a first metal and a second metal, both metals forming oxides, the oxide of the first metal being more resistant than the second metal to attack by the molten salt, the oxide of the second metal being more resistant than the first metal to the diffusion of oxygen. The electrode may also be formed of CuAlO[sub 2] and/or Cu[sub 2]O. 2 figs.

Synthesis and properties of new carboxyborate lithium salts as electrolytes for lithium-ion batteries

International Nuclear Information System (INIS)

Gładka, Dorota; Krajewski, Mariusz; Młynarska, Sandra; Galińska, Justyna; Zygadło-Monikowska, Ewa

2017-01-01

Bis(carboxytrifluoroborate lithium) salts [R(CH 2 COOBF 3 Li) 2 ] with oxyethylene groups R of oligomeric molar masses [R = O(CH 2 CH 2 O) n , where n = 3 or 11, BCB3 and BCB11, respectively] were synthesized via reaction of carboxylates salts with boron fluoride. The new salts were characterized by spectroscopic analysis. The physical properties of the salts were determined by oxyethylene chain length. For n = 3 the salt was crystalline with m p = 197 °C and for n = 11 it showed properties of an ionic liquid at ambient temperature. Their thermal stability was at least 250 °C. The values of lithium-ion transference numbers (T + ) of the solutions in polar aprotic solvents, determined by a well established steady-state technique, were in the range of 0.2–0.6. Electrochemical impedance spectroscopy analysis of solid polymer electrolytes (SPEs) based on PEO and studied salts with different concentration (from 24 to 94 wt %) was carried out. The ionic conductivity of SPEs was in the order of 10 −8 –10 −7 S cm −1 at room temperature and 10 −4 S cm −1 at 80 °C. A distinguishing feature of SPEs with the studied new salts is the high immobilization of anions, which causes almost a monoconducting character of charge transport. Lithium transference numbers (T + ) exceed 0.9.

Ionic Salt Effect on the Phase Transition of PS-b-P2VP Copolymers

Science.gov (United States)

Kim, Bokyung; An, Hyungju; Ryu, Du Yeol; Kim, Jehan

2009-03-01

Solid-state electrolytes have long been considered as suitable candidates owing to the simple and easy processes for rechargeable battery manufactures, compared to conventional liquid electrolyte counterparts. Especially, polymer/salt systems involving PMMA and PVP complex forms have been studied since they provide stable electrochemical characteristics as well as mechanical properties. We studied the phase behavior of PS-b-P2VP upon the salt addition by small angle x-ray scattering (SAXS) and depolarized light scattering. Transition temperatures of block copolymer were significantly influenced by the salt addition in addition to the changes of d-spacings, which is caused by the effective coordinative interaction between P2VP block and salt. This study suggests a simple approach to solid-state block copolymer electrolytes.

Electrochemical corrosion behaviour of plasma electrolytic oxidation coatings on AM50 magnesium alloy formed in silicate and phosphate based electrolytes

International Nuclear Information System (INIS)

Liang, J.; Srinivasan, P. Bala; Blawert, C.; Stoermer, M.; Dietzel, W.

2009-01-01

PEO coatings were produced on AM50 magnesium alloy by plasma electrolytic oxidation process in silicate and phosphate based electrolytes using a pulsed DC power source. The microstructure and composition of the PEO coatings were analyzed by scanning electron microscopy (SEM) and X-ray Diffraction (XRD). The corrosion resistance of the PEO coatings was evaluated using open circuit potential (OCP) measurements, potentiodynamic polarisation tests and electrochemical impedance spectroscopy (EIS) in 0.1 M NaCl solution. It was found that the electrolyte composition has a significant effect on the coating evolution and on the resulting coating characteristics, such as microstructure, composition, coating thickness, roughness and thus on the corrosion behaviour. The corrosion resistance of the PEO coating formed in silicate electrolyte was found to be superior to that formed in phosphate electrolyte in both the short-term and long-term electrochemical corrosion tests.

Mixtures of lecithin and bile salt can form highly viscous wormlike micellar solutions in water.

Science.gov (United States)

Cheng, Chih-Yang; Oh, Hyuntaek; Wang, Ting-Yu; Raghavan, Srinivasa R; Tung, Shih-Huang

2014-09-02

The self-assembly of biological surfactants in water is an important topic for study because of its relevance to physiological processes. Two common types of biosurfactants are lecithin (phosphatidylcholine) and bile salts, which are both present in bile and involved in digestion. Previous studies on lecithin-bile salt mixtures have reported the formation of short, rodlike micelles. Here, we show that lecithin-bile salt micelles can be further induced to grow into long, flexible wormlike structures. The formation of long worms and their resultant entanglement into transient networks is reflected in the rheology: the fluids become viscoelastic and exhibit Maxwellian behavior, and their zero-shear viscosity can be up to a 1000-fold higher than that of water. The presence of worms is further confirmed by data from small-angle neutron and X-ray scattering and from cryo-transmission electron microscopy (cryo-TEM). We find that micellar growth peaks at a specific molar ratio (near equimolar) of bile salt:lecithin, which suggests a strong binding interaction between the two species. In addition, micellar growth also requires a sufficient concentration of background electrolyte such as NaCl or sodium citrate that serves to screen the electrostatic repulsion of the amphiphiles and to "salt out" the amphiphiles. We postulate a mechanism based on changes in the molecular geometry caused by bile salts and electrolytes to explain the micellar growth.

"Water-in-salt" electrolytes enable the use of cost-effective aluminum current collectors for aqueous high-voltage batteries.

Science.gov (United States)

Kühnel, R-S; Reber, D; Remhof, A; Figi, R; Bleiner, D; Battaglia, C

2016-08-16

The extended electrochemical stability window offered by highly concentrated electrolytes allows the operation of aqueous batteries at voltages significantly above the thermodynamic stability limit of water, at which the stability of the current collector potentially limits the cell voltage. Here we report the observation of suppressed anodic dissolution of aluminum in "water-in-salt" electrolytes enabling roll-to-roll electrode fabrication for high-voltage aqueous lithium-ion batteries on cost-effective light-weight aluminum current collectors using established lithium-ion battery technology.

Electrolyte chemistry control in electrodialysis processing

Science.gov (United States)

Hayes, Thomas D.; Severin, Blaine F.

2017-12-26

Methods for controlling electrolyte chemistry in electrodialysis units having an anode and a cathode each in an electrolyte of a selected concentration and a membrane stack disposed therebetween. The membrane stack includes pairs of cationic selective and anionic membranes to segregate increasingly dilute salts streams from concentrated salts stream. Electrolyte chemistry control is via use of at least one of following techniques: a single calcium exclusionary cationic selective membrane at a cathode cell boundary, an exclusionary membrane configured as a hydraulically isolated scavenger cell, a multivalent scavenger co-electrolyte and combinations thereof.

A Study on the Electrolytic Reduction Mechanism of Uranium Oxide in a LiCl-Li2O Molten Salt

International Nuclear Information System (INIS)

Oh, Seung Chul; Hur, Jin Mok; Seo, Chung Seok; Park, Seong Won

2003-01-01

This study proposed a new electrolytic reduction technology that is based on the integration of simultaneous uranium oxide metallization and Li 2 O electrowinning. In this electrolytic reduction reaction, electrolytically reduced Li deposits on cathode and simultaneously reacts with uranium oxides to produce uranium metal showing more than 99% conversion. For the verification of process feasibility, the experiments to obtain basic data on the metallization of uranium oxide, investigation of reaction mechanism, the characteristics of closed recycle of Li 2 O and mass transfer were carried out. This evolutionary electrolytic reduction technology would give benefits over the conventional Li-reduction process improving economic viability such as: avoidance of handling of chemically active Li-LiCl molten salt increase of metallization yield, and simplification of process.

Crystal forms of the hydrogen oxalate salt of o-desmethylvenlafaxine.

Science.gov (United States)

Dichiarante, Elena; Curzi, Marco; Giaffreda, Stefano L; Grepioni, Fabrizia; Maini, Lucia; Braga, Dario

2015-06-01

To prepare new crystalline forms of the antidepressant o-desmethylvenlafaxine salt as potential new commercial forms and evaluate their physicochemical properties, in particular the dissolution rate. A new hydrogen oxalate salt of o-desmethylvenlafaxine hydrogen oxalate (ODV-OX) was synthesized, and a polymorph screening was performed using different solvents and crystallization conditions. Crystalline forms were characterized by a combination of solid-state techniques: X-ray powder diffraction, differential scanning calorimetry, thermogravimetric analysis, FT-IR spectroscopy and single crystal X-ray diffraction. The stability of all crystalline phases was tested under International Conference on Harmonisation (ICH) conditions (40°C and 75% Relative Humidity (RH)) for 1 week. Dissolution tests were performed on the hydrogen oxalate salt ODV-OX Form 1 and compared with dissolution test on the commercial form of the succinate salt of o-desmethylvenlafaxine. Five crystalline forms of ODV-OX were isolated, namely three hydrated forms (Form 1, Form 2, Form 3) and two anhydrous forms (Form 4 and Form 5). Comparative solubility tests on ODV-OX Form 1 and o-desmethylvenlafaxine succinate evidenced a significant increase in solubility for the hydrogen oxalate salt (142 g/l) with respect to the succinate salt (70 g/l). © 2015 Royal Pharmaceutical Society.

Chemical stability of {gamma}-butyrolactone-based electrolytes for aluminium electrolytic capacitors

Energy Technology Data Exchange (ETDEWEB)

Ue, Makoto [Mitsubishi Chemical Corp., Tsukuba Research Center, Ibaraki (Japan); Takeda, Masayuki [Mitsubishi Chemical Corp., Tsukuba Research Center, Ibaraki (Japan); Suzuki, Yoko [Mitsubishi Chemical Corp., Tsukuba Research Center, Ibaraki (Japan); Mori, Shoichiro [Mitsubishi Chemical Corp., Tsukuba Research Center, Ibaraki (Japan)

1996-06-01

{gamma}-Butyrolactone-based electrolytes have been used as the operating electrolytes for aluminum electrolytic capacitors. The chemical stability of these electrolytes at elevated temperatures has been examined by monitoring the decrease in their electrolytic conductivities. The deteriorated electrolytes were analyzed by gas and liquid chromatography and the conductivity decrease was directly correlated with the loss of acid components. In quaternary ammonium hydrogen maleate/{gamma}-butyrolactone electrolytes, the maleate anion decomposed by decarboxylation resulting in a complex polymer containing polyester and polyacrylate structures. Quaternary ammonium benzoate/{gamma}-butyrolactone electrolytes decomposed by SN2 reactions giving alkyl benzoates and trialkylamines. The deterioration of the carboxylate salt/{gamma}-butyrolactone electrolytes was accelerated by electrolysis. (orig.)

Electrolytes including fluorinated solvents for use in electrochemical cells

Science.gov (United States)

Tikhonov, Konstantin; Yip, Ka Ki; Lin, Tzu-Yuan

2015-07-07

Provided are electrochemical cells and electrolytes used to build such cells. The electrolytes include ion-supplying salts and fluorinated solvents capable of maintaining single phase solutions with the salts at between about -30.degree. C. to about 80.degree. C. The fluorinated solvents, such as fluorinated carbonates, fluorinated esters, and fluorinated esters, are less flammable than their non-fluorinated counterparts and increase safety characteristics of cells containing these solvents. The amount of fluorinated solvents in electrolytes may be between about 30% and 80% by weight not accounting weight of the salts. Fluorinated salts, such as fluoroalkyl-substituted LiPF.sub.6, fluoroalkyl-substituted LiBF.sub.4 salts, linear and cyclic imide salts as well as methide salts including fluorinated alkyl groups, may be used due to their solubility in the fluorinated solvents. In some embodiments, the electrolyte may also include a flame retardant, such as a phosphazene or, more specifically, a cyclic phosphazene and/or one or more ionic liquids.

Extended UNIQUAC Model for Correlation and Prediction of Vapor-Liquid-Liquid-Solid Equilibria in Aqueous Salt Systems Containing Non-Electrolytes. Part B. Alcohol (Ethanol, Propanols, Butanols) - Water-salt systems

DEFF Research Database (Denmark)

Thomsen, Kaj; Iliuta, Maria Cornelia; Rasmussen, Peter

2004-01-01

The Extended UNIQUAC model for electrolyte solutions is an excess Gibbs energy function consisting of a Debye-Huckel term and a term corresponding to the UNIQUAC equation. For vapor-liquid equilibrium calculations, the fugacities of gas-phase components are calculated with the Soave-Redlich-Kwong......The Extended UNIQUAC model for electrolyte solutions is an excess Gibbs energy function consisting of a Debye-Huckel term and a term corresponding to the UNIQUAC equation. For vapor-liquid equilibrium calculations, the fugacities of gas-phase components are calculated with the Soave...... solid-liquid-vapor equilibrium and thermal property data for strongly non-ideal systems. In this work, the model is extended to aqueous salt systems containing higher alcohols. The calculations are based on an extensive database consisting of salt solubility data, vapor liquid equilibrium data...

Characterization of reaction products in sodium-oxygen batteries : An electrolyte concentration study

OpenAIRE

Hedman, Jonas

2017-01-01

In this thesis, the discharge products formed at the cathode and the performance and cell chemistry of sodium-oxygen batteries have been studied. This was carried out using different NaOTf salt concentrations. The influence of different salt concentrations on sodium-oxygen batteries was investigated since it has been shown that increasing the salt concentration beyond conventional concentrations could result in advantages such as increased stability of the electrolytes towards decomposition, ...

Analysis of cell performance and thermal regeneration of a lithium-tin cell having an immobilized fused-salt electrolyte

Science.gov (United States)

Cairns, E. J.; Shimotake, H.

1969-01-01

Cell performance and thermal regeneration of a thermally regenerative cell uses lithium and tin and a fused-salt electrolyte. The emf of the Li-Sn cell, as a function of cathode-alloy composition, is shown to resemble that of the Na-Bi cell.

The effect of salt on the morphologies of compositionally asymmetric block copolymer electrolytes

Science.gov (United States)

Loo, Whitney; Maslyn, Jacqueline; Oh, Hee Jeung; Balsara, Nitash

Block copolymer electrolytes are promising for applications in lithium metal solid-state batteries. Due to their ability to microphase separate into distinct morphologies, their ion transport and mechanical properties can be decoupled. The addition of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt to poly(styrene)-block-poly(ethylene oxide) (SEO) has been shown to increase microphase separation in symmetric block copolymer systems due to an increase in the effective interaction parameter (χeff) ; however the effect of block copolymer compositional asymmetry is not well-understood. The effect of compositional asymmetry on polymer morphology was investigated through small and wide angle X-ray scattering (SAXS/WAXS). The effective Flory-Huggins interaction parameter was extracted from the scattering profiles in order to construct a phase diagram to demonstrate the effect of salt and compositional asymmetry on block copolymer morphology.

Zinc sorption in two vertisol and one aridisol series as affected by electrolyte concentration and sodium adsorption ratio

International Nuclear Information System (INIS)

Hussein, A. A.; Elamin, E. A.; El Mahi, Y. E.

2002-01-01

The effects of electrolyte concentration (C) and sodium adsorption ratio (SAR) on zinc sorption was studied. Top soil samples (0-30 cm) were taken from soils representing three arid-zon smectitc sites in the Gezira Scheme (Sudan). The orders of these soils are vertisol (El-Hosh (now Wad El Ataya) and El-Suleimi) and aridisol (El-Laota). These soils had no previous history of zinc application, and were previously equilibrated with mixed NaCl-CaCl 2 solutions to render different levels of SAR and salt concentration. Zinc retention decreased as electrolyte concentration increased, where maximum sorption occurred at low electrolyte concentration soils having high pH and high negative charge. Sodium adsorption ratio had little effect on Zn sorption as precipitation prevailed at high pH. It was also found that the sorption capacity of three soils were similar despite the variation in CaCO 3 and clay contents, hence cation exchange capacity and surface area. The results indicated that Zn was more soluble in the saline phases of Gezira soils, whereas sodicity had little effect.(Author)

Modeling Electrolytically Top-Gated Graphene

Directory of Open Access Journals (Sweden)

Mišković ZL

2010-01-01

Full Text Available Abstract We investigate doping of a single-layer graphene in the presence of electrolytic top gating. The interfacial phenomenon is modeled using a modified Poisson–Boltzmann equation for an aqueous solution of simple salt. We demonstrate both the sensitivity of graphene’s doping levels to the salt concentration and the importance of quantum capacitance that arises due to the smallness of the Debye screening length in the electrolyte.

Solid polymer electrolytes

Science.gov (United States)

Abraham, Kuzhikalail M.; Alamgir, Mohamed; Choe, Hyoun S.

1995-01-01

This invention relates to Li ion (Li.sup.+) conductive solid polymer electrolytes composed of poly(vinyl sulfone) and lithium salts, and their use in all-solid-state rechargeable lithium ion batteries. The lithium salts comprise low lattice energy lithium salts such as LiN(CF.sub.3 SO.sub.2).sub.2, LiAsF.sub.6, and LiClO.sub.4.

Separation of Electrolytic Reduction Product from Stainless Steel Wire Mesh Cathode Basket via Salt Draining and Reuse of the Cathode Basket

Directory of Open Access Journals (Sweden)

Eun-Young Choi

2017-01-01

Full Text Available We demonstrated that the metallic product obtained after electrolytic reduction (also called oxide reduction (OR can be simply separated from a stainless steel wire mesh cathode basket only by using a salt drain. First, the OR run of a simulated oxide fuel (0.6 kg/batch was conducted in a molten Li2O–LiCl salt electrolyte at 650°C. The simulated oxide fuel of the porous cylindrical pellets was used as a cathode by loading a stainless steel wire mesh cathode basket. Platinum was employed as an anode. After the electrolysis, the residual salt of the cathode basket containing the reduction product was drained by placing it at gas phase above the molten salt using a holder. Then, at a room temperature, the complete separation of the reduction product from the cathode basket was achieved by inverting it without damaging or deforming the basket. Finally, the emptied cathode basket obtained after the separation was reused for the second OR run by loading a fresh simulated oxide fuel. We also succeeded in the separation of the metallic product from the reused cathode basket for the second OR run.

Reoxidation of uranium metal immersed in a Li{sub 2}O-LiCl molten salt after electrolytic reduction of uranium oxide

Energy Technology Data Exchange (ETDEWEB)

Choi, Eun-Young, E-mail: eychoi@kaeri.re.kr [Korea Atomic Energy Research Institute, Daedoek-daero 989-111, Yuseong-gu, Daejeon 34057 (Korea, Republic of); Jeon, Min Ku [Korea Atomic Energy Research Institute, Daedoek-daero 989-111, Yuseong-gu, Daejeon 34057 (Korea, Republic of); Department of Quantum Energy Chemical Engineering, University of Science and Technology, Gajeong-ro 217, Yuseong-gu, Daejeon 34113 (Korea, Republic of); Lee, Jeong [Korea Atomic Energy Research Institute, Daedoek-daero 989-111, Yuseong-gu, Daejeon 34057 (Korea, Republic of); Kim, Sung-Wook [Korea Atomic Energy Research Institute, Daedoek-daero 989-111, Yuseong-gu, Daejeon 34057 (Korea, Republic of); Department of Quantum Energy Chemical Engineering, University of Science and Technology, Gajeong-ro 217, Yuseong-gu, Daejeon 34113 (Korea, Republic of); Lee, Sang Kwon [Korea Atomic Energy Research Institute, Daedoek-daero 989-111, Yuseong-gu, Daejeon 34057 (Korea, Republic of); Lee, Sung-Jai [Korea Atomic Energy Research Institute, Daedoek-daero 989-111, Yuseong-gu, Daejeon 34057 (Korea, Republic of); Department of Quantum Energy Chemical Engineering, University of Science and Technology, Gajeong-ro 217, Yuseong-gu, Daejeon 34113 (Korea, Republic of); Heo, Dong Hyun; Kang, Hyun Woo; Jeon, Sang-Chae; Hur, Jin-Mok [Korea Atomic Energy Research Institute, Daedoek-daero 989-111, Yuseong-gu, Daejeon 34057 (Korea, Republic of)

2017-03-15

We present our findings that uranium (U) metal prepared by using the electrolytic reduction process for U oxide (UO{sub 2}) in a Li{sub 2}O–LiCl salt can be reoxidized into UO{sub 2} through the reaction between the U metal and Li{sub 2}O in LiCl. Two salt types were used for immersion of the U metal: one was the salt used for electrolytic reduction, and the other was applied to the unused LiCl salts with various concentrations of Li{sub 2}O and Li metal. Our results revealed that the degree of reoxidation increases with the increasing Li{sub 2}O concentration in LiCl and that the presence of the Li metal in LiCl suppresses the reoxidation of the U metal. - Highlights: • Uranium (U) metal can be reoxidized into UO{sub 2} through the reaction between the U metal and Li{sub 2}O in LiCl. • The degree of reoxidation increases with the Li{sub 2}O concentration in LiCl. • The presence of the Li metal in LiCl suppresses the reoxidation of the U metal.

Stable lithium electrodeposition in liquid and nanoporous solid electrolytes

KAUST Repository

Lu, Yingying

2014-08-10

Rechargeable lithium, sodium and aluminium metal-based batteries are among the most versatile platforms for high-energy, cost-effective electrochemical energy storage. Non-uniform metal deposition and dendrite formation on the negative electrode during repeated cycles of charge and discharge are major hurdles to commercialization of energy-storage devices based on each of these chemistries. A long-held view is that unstable electrodeposition is a consequence of inherent characteristics of these metals and their inability to form uniform electrodeposits on surfaces with inevitable defects. We report on electrodeposition of lithium in simple liquid electrolytes and in nanoporous solids infused with liquid electrolytes. We find that simple liquid electrolytes reinforced with halogenated salt blends exhibit stable long-term cycling at room temperature, often with no signs of deposition instabilities over hundreds of cycles of charge and discharge and thousands of operating hours. We rationalize these observations with the help of surface energy data for the electrolyte/lithium interface and impedance analysis of the interface during different stages of cell operation. Our findings provide support for an important recent theoretical prediction that the surface mobility of lithium is significantly enhanced in the presence of lithium halide salts. Our results also show that a high electrolyte modulus is unnecessary for stable electrodeposition of lithium.

Extended UNIQUAC model for correlation and prediction of vapour-liquid-solid equilibria in aqueous salt systems containing non-electrolytes

DEFF Research Database (Denmark)

Iliuta, Maria C.; Thomsen, Kaj; Rasmussen, Peter

2000-01-01

to aqueous salt systems containing non-electrolytes in order to demonstrate its ability in representing solid-liquid-vapour (SLV) equilibrium and thermal property data for these strongly non-ideal systems. The model requires only pure component and binary temperature-dependent interaction parameters....... The calculations are based on an extensive database consisting of salt solubility data in pure and mixed solvents, VLE data for solvent mixtures and mixed solvent-electrolyte systems and thermal properties for mixed solvent solutions. Application of the model to the methanol-water system in the presence of several...... ions (Na+, K+, NH4+, Cl-, NO3-, SO42-, CO2- and HCO3-) shows that the Extended UNIQUAC model is able to give an accurate description of VLE and SLE in ternary add quaternary mixtures, using the name set of binary interaction parameters. The capability of the model to predict accurately the phase...

Performance of electrical double layer capacitors fabricated with gel polymer electrolytes containing Li+ and K+-salts: A comparison

International Nuclear Information System (INIS)

Singh, Manoj K.; Hashmi, S. A.

2015-01-01

The comparative performance of the solid-state electrical double layer capacitors (EDLCs) based on the multiwalled carbon nanotube (MWCNT) electrodes and poly (vinaylidinefluoride-co-hexafluoropropyline) (PVdF-HFP) based gel polymer electrolytes (GPEs) containing potassium and lithium salts have been studied. The room temperature ionic conductivity of the GPEs have been found to be ∼3.8×10 −3 and 5.9×10 −3 S cm −1 for lithium and potassium based systems. The performance of EDLC cells studied by impedance spectroscopy, cyclic voltammetry and constant current charge-discharge techniques, indicate that the EDLC with potassium salt containing GPE shows excellent performance almost equivalent to the EDLC with Li-salt-based GPE

Developing New Electrolytes for Advanced Li-ion Batteries

Science.gov (United States)

McOwen, Dennis Wayne

The use of renewable energy sources is on the rise, as new energy generating technologies continue to become more efficient and economical. Furthermore, the advantages of an energy infrastructure which relies more on sustainable and renewable energy sources are becoming increasingly apparent. The most readily available of these renewable energy sources, wind and solar energy in particular, are naturally intermittent. Thus, to enable the continued expansion and widespread adoption of renewable energy generating technology, a cost-effective energy storage system is essential. Additionally, the market for electric/hybrid electric vehicles, which both require efficient energy storage, continues to grow as more consumers seek to reduce their consumption of gasoline. These vehicles, however, remain quite expensive, due primarily to costs associated with storing the electrical energy. High-voltage and thermally stable Li-ion battery technology is a promising solution for both grid-level and electric vehicle energy storage. Current limitations in materials, however, limit the energy density and safe operating temperature window of the battery. Specifically, the state-of-the-art electrolyte used in Li-ion batteries is not compatible with recently developed high-voltage positive electrodes, which are one of the most effectual ways of increasing the energy density. The electrolyte is also thermally unstable above 50 °C, and prone to thermal runaway reaction if exposed to prolonged heating. The lithium salt used in such electrolytes, LiPF6, is a primary contributor to both of these issues. Unfortunately, an improved lithium salt which meets the myriad property requirements for Li-ion battery electrolytes has eluded researchers for decades. In this study, a renewed effort to find such a lithium salt was begun, using a recently developed methodology to rapidly screen for desirable properties. Four new lithium salts and one relatively new but uncharacterized lithium salt were

Properties of ENR-50 Based Electrolyte System

International Nuclear Information System (INIS)

Zainal, N.; Mohamed, N.S.; Zainal, N.; Idris, R.

2013-01-01

In this work, epoxidized natural rubber 50 (ENR-50) has been used as a host polymer for the preparation of electrolyte system. Attenuated total reflection-fourier transform infrared spectroscopic analyses showed the presence of lithium salt-ENR interactions. The glass transition temperature displayed an increasing trend with the increase in salt concentration indicating that the ionic conductivity was not influenced by segmental motion of the ENR-50 chains. The increase in glass transition temperature with the addition of salt was due to the formation of transient cross-linking between ENR-50 chains via the coordinated interaction between ENR-50 chains and salt. The highest room temperature ionic conductivity obtained was in the order of 10 -5 S cm -1 for the film containing 50 wt % of lithium salt. The ionic conductivity of this electrolyte system increased with increasing temperature and obeyed the Vogel-Tamman-Fulcher behavior. The increase in ionic conductivity of the electrolyte system with salt concentration could also be correlated to the charge carriers concentration and/ or migration rate of charge carriers. (author)

Electrolyte materials - Issues and challenges

International Nuclear Information System (INIS)

Balbuena, Perla B.

2014-01-01

Electrolytes are vital components of an electrochemical energy storage device. They are usually composed of a solvent or mixture of solvents and a salt or a mixture of salts which provide the appropriate environment for ionic conduction. One of the main issues associated with the selection of a proper electrolyte is that its electronic properties have to be such that allow a wide electrochemical window - defined as the voltage range in which the electrolyte is not oxidized or reduced - suitable to the battery operating voltage. In addition, electrolytes must have high ionic conductivity and negligible electronic conductivity, be chemically stable with respect to the other battery components, have low flammability, and low cost. Weak stability of the electrolyte against oxidation or reduction leads to the formation of a solid-electrolyte interphase (SEI) layer at the surface of the cathode and anode respectively. Depending on the materials of the electrolyte and those of the electrode, the SEI layer may be composed by combinations of organic and inorganic species, and it may exert a passivating role. In this paper we discuss the current status of knowledge about electrolyte materials, including non-aqueous liquids, ionic liquids, solid ceramic and polymer electrolytes. We also review the basic knowledge about the SEI layer formation, and challenges for a rational design of stable electrolytes

Novel polymeric systems for lithium-ion batteries gel electrolytes

International Nuclear Information System (INIS)

Appetecchi, G.B.; Alessandrini, F.; Passerini, S.; Caporiccio, G.; Boutevin, B.; Guida-Pietrasanta, F.

2004-01-01

The investigation of chemically cross-linked, self-supporting gel-type electrolyte membranes, based on hybrid polyfluorosilicone polymers reinforced with nanosized silica, for lithium-ion battery systems is reported. The polyfluorosilicone materials were selected on the basis of their high chemical and thermal stabilities. The precursors were synthesized with functional groups capable to form inter-molecular cross-linking, thus obtaining three-dimensional polymer matrices. The latter were undergone to swelling processes in (non-aqueous, lithium salt containing) electrolytic solutions to obtain gel-type polymer electrolytes. Several kinds of membranes, based on different types of polyfluorosilicone precursor, were prepared and characterized in terms of swelling behavior, ionic conductivity and electrochemical stability. The properties of the swelled matrices were evaluated as a function of dipping time, temperature, kind of electrolytic solution and cross-linking initiator content

LiCl-LiI molten salt electrolyte with bismuth-lead positive electrode for liquid metal battery

Science.gov (United States)

Kim, Junsoo; Shin, Donghyeok; Jung, Youngjae; Hwang, Soo Min; Song, Taeseup; Kim, Youngsik; Paik, Ungyu

2018-02-01

Liquid metal batteries (LMBs) are attractive energy storage device for large-scale energy storage system (ESS) due to the simple cell configuration and their high rate capability. The high operation temperature caused by high melting temperature of both the molten salt electrolyte and metal electrodes can induce the critical issues related to the maintenance cost and degradation of electrochemical properties resulting from the thermal corrosion of materials. Here, we report a new chemistry of LiCl-LiI electrolyte and Bi-Pb positive electrode to lower the operation temperature of Li-based LMBs and achieve the long-term stability. The cell (Li|LiCl-LiI|Bi-Pb) is operated at 410 °C by employing the LiCl-LiI (LiCl:LiI = 36:64 mol %) electrolyte and Bi-Pb alloy (Bi:Pb = 55.5:44.5 mol %) positive electrode. The cell shows excellent capacity retention (86.5%) and high Coulombic efficiencies over 99.3% at a high current density of 52 mA cm-2 during 1000th cycles.

High Lithium Transference Number Electrolytes via Creation of 3-Dimensional, Charged, Nanoporous Networks from Dense Functionalized Nanoparticle Composites

KAUST Repository

Schaefer, Jennifer L.

2013-03-26

High lithium transference number, tLi+, electrolytes are desired for use in both lithium-ion and lithium metal rechargeable battery technologies. Historically, low tLi+ electrolytes have hindered device performance by allowing ion concentration gradients within the cell, leading to high internal resistances that ultimately limit cell lifetime, charging rates, and energy density. Herein, we report on the synthesis and electrochemical features of electrolytes based on nanoparticle salts designed to provide high tLi+. The salts are created by cofunctionalization of metal oxide nanoparticles with neutral organic ligands and tethered lithium salts. When dispersed in a conducting fluid such as tetraglyme, they spontaneously form a charged, nanoporous network of particles at moderate nanoparticle loadings. Modification of the tethered anion chemistry from -SO3 - to -SO3BF3 - is shown to enhance ionic conductivity of the electrolytes by facilitating ion pair dissociation. At a particle volume fraction of 0.15, the electrolyte exists as a self-supported, nanoporous gel with an optimum ionic conductivity of 10 -4 S/cm at room temperature. Galvanostatic polarization measurements on symmetric lithium metal cells containing the electrolyte show that the cell short circuit time, tSC, is inversely proportional to the square of the applied current density tSC ∼ J-2, consistent with previously predicted results for traditional polymer-in-salt electrolytes with low tLi+. Our findings suggest that electrolytes with tLi+ ≈ 1 and good ion-pair dissociation delay lithium dendrite nucleation and may lead to improved lithium plating in rechargeable batteries with metallic lithium anodes. © 2013 American Chemical Society.

A study on the electrolytic reduction of U3O8 to uranium metal in LiCl-Li2O molten salt

International Nuclear Information System (INIS)

Seo, J. S.; Heo, J. M.; Hong, S. S.; Kang, D. S.; Park, S. W.

2002-01-01

New electrolytic reduction technology was proposed that is based on the intregration of metallization of U 3 O 8 and Li 2 O electrowinning. In this electrolytic reduction reaction, electrolytically reduced Li deposits on cathode and simultaneously reacts with uranium oxide to produce uranium metal showing more than 99% conversion. For the verification of process feasibility, the experiments to obtain basic data on the metallization of uranium oxide, materials for cathode and anode electrode, the characteristics of closed recycle of Li 2 O and mass transfer were carried out. This evolutionary electrolytic reduction technology would give benefits over the conventional Li-reduction process improving economic viability such as: avoidance of handling of chemically active Li-LiCl molten salt, increase of metallization yield, and simplification of process

Effects of heating on salt-occluded zeolite

International Nuclear Information System (INIS)

Lewis, M.A.; Hash, M.C.; Pereira, C.; Ackerman, J.P.

1996-01-01

The electrometallurgical treatment of spent nuclear fuel generates a waste stream of fission products in the electrolyte, LiCl-KCl eutectic salt. Argonne National Laboratory is developing a mineral waste form for this waste stream. The waste form consists of a composite formed by hot pressing salt-occluded zeolite and a glass binder. Pressing conditions must be judiciously chosen. For a given pressure, increasing temperatures and hold times give denser products but the zeolite is frequently converted to sodalite. Reducing the temperature or hold time leads to a porous zeolite composite. Therefore, conditions that affect the thermal stability of salt-occluded zeolite both with and without glass are being investigated in an ongoing study. The parameters varied in this stage of the work were heating time, temperature, salt loading, and glass content. The heat-treated samples were examined primarily by X-ray diffraction. Large variations were found in the rate at which salt-occluded zeolite converted to other phases such as nepheline, salt, and sodalite. The products depended on the initial salt loading. Heating times required for these transitions depended on the procedure and temperature used to prepare the salt-occluded zeolite. Mixtures of glass and zeolite reacted much faster than the pure salt-occluded zeolite and were almost always converted to sodalite

Metal Production by Molten Salt Electrolysis

DEFF Research Database (Denmark)

Grjotheim, K.; Kvande, H.; Qingfeng, Li

Chemistry and electrochemistry of molten salts are reviewed. Technological aspects of electrolytic production of aluminium, magnesium, and other metals are comprehensively surveyed.......Chemistry and electrochemistry of molten salts are reviewed. Technological aspects of electrolytic production of aluminium, magnesium, and other metals are comprehensively surveyed....

Fundamental Properties of Salts

Energy Technology Data Exchange (ETDEWEB)

Toni Y Gutknecht; Guy L Fredrickson

2012-11-01

Thermal properties of molten salt systems are of interest to electrorefining operations, pertaining to both the Fuel Cycle Research & Development Program (FCR&D) and Spent Fuel Treatment Mission, currently being pursued by the Department of Energy (DOE). The phase stability of molten salts in an electrorefiner may be adversely impacted by the build-up of fission products in the electrolyte. Potential situations that need to be avoided, during electrorefining operations, include (i) fissile elements build up in the salt that might approach the criticality limits specified for the vessel, (ii) electrolyte freezing at the operating temperature of the electrorefiner due to changes in the liquidus temperature, and (iii) phase separation (non-homogenous solution). The stability (and homogeneity) of the phases can be monitored by studying the thermal characteristics of the molten salts as a function of impurity concentration. Simulated salt compositions consisting of the selected rare earth and alkaline earth chlorides, with a eutectic mixture of LiCl-KCl as the carrier electrolyte, were studied to determine the melting points (thermal characteristics) using a Differential Scanning Calorimeter (DSC). The experimental data were used to model the liquidus temperature. On the basis of the this data, it became possible to predict a spent fuel treatment processing scenario under which electrorefining could no longer be performed as a result of increasing liquidus temperatures of the electrolyte.

Process to remove rare earth from IFR electrolyte

International Nuclear Information System (INIS)

Ackerman, J.P.; Johnson, T.R.

1994-01-01

The invention is a process for the removal of rare earths from molten chloride electrolyte salts used in the reprocessing of integrated fast reactor fuel (IFR). The process can be used either continuously during normal operation of the electrorefiner or as a batch process. The process consists of first separating the actinide values from the salt before purification by removal of the rare earths. After replacement of the actinides removed in the first step, the now-purified salt electrolyte has the same uranium and plutonium concentration and ratio as when the salt was removed from the electrorefiner. 1 fig

A study of integrated cathode assembly for electrolytic reduction of uranium oxide in LiCl-Li2O molten salt

International Nuclear Information System (INIS)

Park, Sung Bin; Seo, Jung Seok; Kang, Dae Seung; Kwon, Sun Kil; Park, Seong Won

2004-01-01

Interest of electrolytic reduction of uranium oxide is increasing in treatment of spent metal fuels. Argonne National Laboratory (ANL) has reported the experimental results of electrochemical reduction of uranium oxide fuel in bench-scale apparatus with cyclic voltammetry, and has designed high-capacity reduction (HCR) cells and conducted three kg-scale UO 2 reduction runs. From the cyclic voltammograms, the mechanism of electrolytic reduction of metal oxides is analyzed. The uranium oxide in LiCl-Li 2 O is converted to uranium metal according to the two mechanism; direct and indirect electrolytic reduction. In this study, cyclic voltammograms for LiCl-3wt% Li 2 O system and U 3 O 8 -LiCl-3wt% Li 2 O system using the 325-mesh stainless steel screen in cathode assembly have been obtained. Direct electrolytic reduction of uranium oxide in LiCl-3wt% Li 2 O molten salt has been conducted

Designing Advanced Ceramic Waste Forms for Electrochemical Processing Salt Waste

International Nuclear Information System (INIS)

Ebert, W. L.; Snyder, C. T.; Frank, Steven; Riley, Brian

2016-01-01

This report describes the scientific basis underlying the approach being followed to design and develop ''advanced'' glass-bonded sodalite ceramic waste form (ACWF) materials that can (1) accommodate higher salt waste loadings than the waste form developed in the 1990s for EBR-II waste salt and (2) provide greater flexibility for immobilizing extreme waste salt compositions. This is accomplished by using a binder glass having a much higher Na_2O content than glass compositions used previously to provide enough Na+ to react with all of the Cl- in the waste salt and generate the maximum amount of sodalite. The phase compositions and degradation behaviors of prototype ACWF products that were made using five new binder glass formulations and with 11-14 mass% representative LiCl/KCl-based salt waste were evaluated and compared with results of similar tests run with CWF products made using the original binder glass with 8 mass% of the same salt to demonstrate the approach and select a composition for further studies. About twice the amount of sodalite was generated in all ACWF materials and the microstructures and degradation behaviors confirmed our understanding of the reactions occurring during waste form production and the efficacy of the approach. However, the porosities of the resulting ACWF materials were higher than is desired. These results indicate the capacity of these ACWF waste forms to accommodate LiCl/KCl-based salt wastes becomes limited by porosity due to the low glass-to-sodalite volume ratio. Three of the new binder glass compositions were acceptable and there is no benefit to further increasing the Na content as initially planned. Instead, further studies are needed to develop and evaluate alternative production methods to decrease the porosity, such as by increasing the amount of binder glass in the formulation or by processing waste forms in a hot isostatic press. Increasing the amount of binder glass to eliminate porosity will decrease the waste

Designing Advanced Ceramic Waste Forms for Electrochemical Processing Salt Waste

Energy Technology Data Exchange (ETDEWEB)

Ebert, W. L. [Argonne National Lab. (ANL), Argonne, IL (United States); Snyder, C. T. [Argonne National Lab. (ANL), Argonne, IL (United States); Frank, Steven [Argonne National Lab. (ANL), Argonne, IL (United States); Riley, Brian [Argonne National Lab. (ANL), Argonne, IL (United States)

2016-03-01

This report describes the scientific basis underlying the approach being followed to design and develop “advanced” glass-bonded sodalite ceramic waste form (ACWF) materials that can (1) accommodate higher salt waste loadings than the waste form developed in the 1990s for EBR-II waste salt and (2) provide greater flexibility for immobilizing extreme waste salt compositions. This is accomplished by using a binder glass having a much higher Na₂O content than glass compositions used previously to provide enough Na+ to react with all of the Cl– in the waste salt and generate the maximum amount of sodalite. The phase compositions and degradation behaviors of prototype ACWF products that were made using five new binder glass formulations and with 11-14 mass% representative LiCl/KCl-based salt waste were evaluated and compared with results of similar tests run with CWF products made using the original binder glass with 8 mass% of the same salt to demonstrate the approach and select a composition for further studies. About twice the amount of sodalite was generated in all ACWF materials and the microstructures and degradation behaviors confirmed our understanding of the reactions occurring during waste form production and the efficacy of the approach. However, the porosities of the resulting ACWF materials were higher than is desired. These results indicate the capacity of these ACWF waste forms to accommodate LiCl/KCl-based salt wastes becomes limited by porosity due to the low glass-to-sodalite volume ratio. Three of the new binder glass compositions were acceptable and there is no benefit to further increasing the Na content as initially planned. Instead, further studies are needed to develop and evaluate alternative production methods to decrease the porosity, such as by increasing the amount of binder glass in the formulation or by processing waste forms in a hot isostatic press. Increasing the amount of binder glass to eliminate porosity will decrease

Gamma ray degradation of electrolytes containing alkylcarbonate solvents and a lithium salt

Energy Technology Data Exchange (ETDEWEB)

Caillon-Caravanier, Magaly; Jones, Jennifer; Anouti, Meriem; Lemordant, Daniel [Laboratoire CIME/PCMB (EA4244), Universite F. Rabelais, Faculte des Sciences et Techniques, Parc de Grandmont, 37200 Tours (France); Montigny, Frederic [Plateau d' Analyse Chimique, Universite F. Rabelais, Faculte de Pharmacie, 31 avenue Monge 37200 Tours (France); Willmann, Patrick [CNES, 18 avenue E. Belin, 31055 Toulouse (France); David, Jean-Pierre; Soonckindt, Sabine [Departement Environnement Spatial DSEP/ONERA, 2, avenue E. Belin, 31055 Toulouse (France)

2010-01-15

Lithium-ion batteries for space applications, such as satellites, are subjected to cosmic radiations, in particular, {gamma}-irradiation. In this study, the effects of this radiation on electrolytes and their components used in the lithium-ion batteries are investigated. The conductivity and viscosity of the samples have been measured before and after the irradiation. The modifications are evaluated by spectral analyses such as Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy ({sup 1}H and {sup 13}C NMR), solid phase microextraction-gas chromatography (SPME-GC) and gas chromatography-mass spectroscopy (GC-MS). The experimental results show that only the samples containing vinylene carbonate and/or the lithium salt LiPF{sub 6} are degraded by {gamma}-radiation. (author)

Novel concepts in electrochemical solar cells. Second quarterly progress report, August 15, 1979-October 15, 1979. [Molten salt electrolytes

Energy Technology Data Exchange (ETDEWEB)

DuBow, J.; Job, R.; Krishnan, R.; Gale, B.

1979-01-01

It is considered that the short term stability of n-GaAs PEC's in a ferrocene-based, ambient temperature molten salt electrolyte is reasonably good. However, longer term evaluation is required to determine the extent and significance of corrosion, stability, etc. Extremely few fundamental studies have been made of the semiconductor/molten salt interphase and experiments in this area would be most useful. Indeed, even the design parameters for PECs of any kind have not been quantitatively delineated and present consideration will be given to models for PEC solar cells and limitations caused by ion transport in the electrolyte. The MoSe/sub 2/ and MoS/sub 2/ electrodes appear to have substrate reproducibility and transport limitations that make them unsuitable candidates for efficient PEC's at this time. Similarly, the lack of availability of high quality CuInSe/sub 2/ and CuInS/sub 2/ substrates limits the quantitative experimental evaluation of their utility for PEC applications. We are presently focusing attention on CdSe/CdTe mixtures and CdS as electrodes as well as Si and GaAs in molten salt and polyelectrolyte solutions. The system for solar cell evaluation and network analysis of substrates and cells was mode operational. Preliminary work on economic and theoretical modelling was begun. Progress is reported. (WHK)

Sustainable Carbon/Carbon Supercapacitors Operating Down to -40 °C in Aqueous Electrolyte Made with Cholinium Salt.

Science.gov (United States)

Abbas, Qamar; Béguin, François

2018-03-09

Cholinium chloride at a concentration of 5 mol kg -1 in water is proposed as a low-cost and environmentally friendly aqueous electrolyte, enabling extension of the operating range of carbon/carbon supercapacitors (SCs) down to -40 °C. This solution has a pH close to neutrality (pH 6.1) and high conductivity of 88 mS cm -1 at 24 °C. The supercapacitors demonstrate a high capacitance of 126 F g -1 (per mass of one electrode) and long life span at voltages up to 1.5 V. At -40 °C, the carbon/carbon SCs display excellent electrochemical characteristics with only slightly reduced capacitance of 106 F g -1 and negligible ohmic losses. As compared to previous works, where antifreezing additives were introduced in traditional neutral electrolytes, the low solubility of the salt and related poor conductivity of the solution is no longer an issue, which makes cholinium salt aqueous solutions very promising for SCs operating at sub-ambient temperature conditions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

An Evaluation of Four Electrolyte Models for the Prediction of Thermodynamic Properties of Aqueous Electrolyte Solutions

Directory of Open Access Journals (Sweden)

Kamalodin Momeni

2017-04-01

Full Text Available In this work, the performance of four electrolyte models for prediction the osmotic and activity coefficients of different aqueous salt solutions at 298 K, atmospheric pressure and in a wide range of concentrations are evaluated. In two of these models, (electrolyte Non-Random Two-Liquid e-NRTL and Mean Spherical Approximation-Non-Random Two-Liquid MSA-NRTL, association between ions of opposite charges for simplification purposes is ignored and in the other two ones, (Associative Mean Spherical Approximation-Non-Random Two-Liquid AMSA-NRTL and Binding Mean Spherical Approximation BiMSA association and solvation effects are considered. The predictions of these four models for the osmotic and activity coefficients of electrolyte solutions at 298 K and atmospheric pressure are compared with the experimental data reported in the literature. This comparison includes, 28 different aqueous salt solutions including thio-cyanates, perchlorates, nitrates, hydroxides, quaternary ammonium salts and others. The results show, the performance of models that consider association effects are better than others especially for higher salt concentrations. However, the best performance belongs to BiMSA model which has some parameters with physical meaning.

Preparation and corrosion resistance of a nanocomposite plasma electrolytic oxidation coating on Mg-1%Ca alloy formed in aluminate electrolyte containing titania nano-additives

DEFF Research Database (Denmark)

Daroonparvar, Mohammadreza; Yajid, M. A. M.; Yusof, N. M.

2016-01-01

Titania nanoparticles were utilized as suspension in alkaline aluminate electrolyte to form nanocomposite coatings on magnesium alloy containing 1 wt% calcium by plasma electrolytic oxidation process. Microhardness, wettability, potentiodynamic polarization, wettability, electrochemical impedance...

Effect of Salt Forms of Chitosan on In Vitro Permeability ...

African Journals Online (AJOL)

Purpose: To investigate the effect of chitosan (CS) salt forms and pH condition on the transepithelial electrical resistance (TEER) of Caco-2 cell monolayer for enhanced permeability. Methods: Solutions (2 %w/v) of four different salt forms of CS-aspartate (CS-A), CS-ethylene diamine tetraacetate (CS-EDTA), ...

Study of the Electrolytic Reduction of Uranium Oxide in LiCl-Li2O Molten Salts with an Integrated Cathode Assembly

International Nuclear Information System (INIS)

Park, Sung Bin; Seo, Chung Seok; Kang, Dae Seung; Kwon, Seon Gil; Park, Seong Won

2005-01-01

The electrolytic reduction of uranium oxide in a LiCl-Li 2 O molten salt system has been studied in a 10 g U 3 O 3 /batch-scale experimental apparatus with an integrated cathode assembly at 650 .deg. C. The integrated cathode assembly consists of an electric conductor, the uranium oxide to be reduced and the membrane for loading the uranium oxide. From the cyclic voltammograms for the LiCl-3 wt% Li 3 O system and the U 3 O 3 -LiCl-3 wt% Li 2 O system according to the materials of the membrane in the cathode assembly, the mechanisms of the predominant reduction reactions in the electrolytic reactor cell were to be understood; direct and indirect electrolytic reduction of uranium oxide. Direct and indirect electrolytic reductions have been performed with the integrated cathode assembly. Using the 325-mesh stainless steel screen the uranium oxide failed to be reduced to uranium metal by a direct and indirect electrolytic reduction because of a low current efficiency and with the porous magnesia membrane the uranium oxide was reduced successfully to uranium metal by an indirect electrolytic reduction because of a high current efficiency.

Ion transport mechanisms in lamellar phases of salt-doped PS–PEO block copolymer electrolytes

KAUST Repository

Sethuraman, Vaidyanathan; Mogurampelly, Santosh; Ganesan, Venkat

2017-01-01

We use a multiscale simulation strategy to elucidate, at an atomistic level, the mechanisms underlying ion transport in the lamellar phase of polystyrene–polyethylene oxide (PS–PEO) block copolymer (BCP) electrolytes doped with LiPF6 salts. Explicitly, we compare the results obtained for ion transport in the microphase separated block copolymer melts to those for salt-doped PEO homopolymer melts. In addition, we also present results for dynamics of the ions individually in the PEO and PS domains of the BCP melt, and locally as a function of the distance from the lamellar interfaces. When compared to the PEO homopolymer melt, ions were found to exhibit slower dynamics in both the block copolymer (overall) and in the PEO phase of the BCP melt. Such results are shown to arise from the effects of slower polymer segmental dynamics in the BCP melt and the coordination characteristics of the ions. Polymer backbone-ion residence times analyzed as a function of distance from the interface indicate that ions have a larger residence time near the interface compared to that near the bulk of lamella, and demonstrates the influence of the glassy PS blocks and microphase segregation on the ion transport properties. Ion transport mechanisms in BCP melts reveal that there exist five distinct mechanisms for ion transport along the backbone of the chain and exhibit qualitative differences from the behavior in homopolymer melts. We also present results as a function of salt concentration which show that the mean-squared displacements of the ions decrease with increasing salt concentration, and that the ion residence times near the polymer backbone increase with increasing salt concentration.

Ion transport mechanisms in lamellar phases of salt-doped PS–PEO block copolymer electrolytes

KAUST Repository

Sethuraman, Vaidyanathan

2017-10-23

We use a multiscale simulation strategy to elucidate, at an atomistic level, the mechanisms underlying ion transport in the lamellar phase of polystyrene–polyethylene oxide (PS–PEO) block copolymer (BCP) electrolytes doped with LiPF6 salts. Explicitly, we compare the results obtained for ion transport in the microphase separated block copolymer melts to those for salt-doped PEO homopolymer melts. In addition, we also present results for dynamics of the ions individually in the PEO and PS domains of the BCP melt, and locally as a function of the distance from the lamellar interfaces. When compared to the PEO homopolymer melt, ions were found to exhibit slower dynamics in both the block copolymer (overall) and in the PEO phase of the BCP melt. Such results are shown to arise from the effects of slower polymer segmental dynamics in the BCP melt and the coordination characteristics of the ions. Polymer backbone-ion residence times analyzed as a function of distance from the interface indicate that ions have a larger residence time near the interface compared to that near the bulk of lamella, and demonstrates the influence of the glassy PS blocks and microphase segregation on the ion transport properties. Ion transport mechanisms in BCP melts reveal that there exist five distinct mechanisms for ion transport along the backbone of the chain and exhibit qualitative differences from the behavior in homopolymer melts. We also present results as a function of salt concentration which show that the mean-squared displacements of the ions decrease with increasing salt concentration, and that the ion residence times near the polymer backbone increase with increasing salt concentration.

Studies on the Properties of Plasticizer and Lithium Salt on PMMA-based Solid Polymer Electrolytes

International Nuclear Information System (INIS)

Chew, K. W.; Tan, C. G.; Osman, Z.

2010-01-01

The effects of plasticizer and lithium salt on PMMA-based solid polymer electrolyte have been investigated. In current project, three system samples consisted of pure poly(methyl methacrylate (PMMA) system, plasticized poly(methyl methacrylate)(PMMA-EC) system and the LiCF 3 SO 3 salted-poly(methyl methacrylate) containing a fixed amount of plasticizer ([PMMA-EC]-LiCF 3 SO 3 ) system have been prepared using solution casting technique. The conductivities of the films from each system are characterized by impedance spectroscopy and infrared spectrum. With the addition of plasticizer, results show improvement on the ionic conductivity value where the value of 6.25x10 -10 Scm -1 is obtained. This may be due to the nature of plasticizer that softens the polymer and hence enhanced the ionic transportation across the polymer. The room temperature conductivity for the highest conducting sample in the ([PMMA-EC]-LiCF 3 SO 3 ) system is 1.36x10 -5 Scm -1 . Fourier Transform Infrared Spectroscopy (FTIR) indicates complexation between the polymer and the plasticizer and the polymer, the plasticizer and the salts, and the result of XRD further supports the observation.

Synthesis and characterization of PVA blended LiClO4 as electrolyte material for battery Li-ion

Science.gov (United States)

Gunawan, I.; Deswita; Sugeng, B.; Sudaryanto

2017-07-01

It have been synthesized the materials for Li ion battery electrolytes, namely PVA with the addition of LiClO4 salt were varied 0, 5, 10, 15 and 20% by weight respectively. The objective of this study is to control the ionic conductivity in traditional polymer electrolytes, to improve ionic conductivity with the addition of lithium perchlorat (LiClO4). These electrolyte materials prepared by PVA powder was dissolved into distilled water and added LiClO4 salt were varied. After drying the solution, PVA sheet blended LiClO4 salt as electrolyte material for Li ion battery obtained. PVA blended LiClO4 salt crystallite form was confirmed using X-Ray Difraction (XRD) equipment. Observation of the morphology done by using Scanning Electron Microscope (SEM). While the electrical conductivity of the material is measured using LCR meter. The results of XRD pattern of LiClO4 shows intense peaks at angles 2θ = 23.2, 32.99, and 36.58°, which represent the crystalline nature of the salt. Particles morphology of the sample revealed by scanning electron microscopy are irregular in shape and agglomerated, with mean size 200-300 nm. It can be concluded that polycrystalline particles are composed of large number of crystallites. The study of conductivity by using LCR meter shows that all the graphs represent the DC and AC conductivity phenomena.

Recent results on aqueous electrolyte cells

Science.gov (United States)

Wessells, Colin; Huggins, Robert A.; Cui, Yi

2011-03-01

The improved safety of aqueous electrolytes makes aqueous lithium-ion batteries an attractive alternative to commercial cells utilizing flammable and expensive organic electrolytes. Two important issues relating to their use have been addressed in this work. One is the extension of the usable voltage range by the incorporation of lithium salts, and the other is the investigation of a useful negative electrode reactant, LiTi2(PO4)3. The electrochemical stability of aqueous lithium salt solutions containing two lithium salts, LiNO3 and Li2SO4, has been characterized using a constant current technique. In both cases, concentrated solutions had effective electrolyte stability windows substantially greater than that of pure water under standard conditions. At an electrolyte leakage current of 10 μA cm-2 between two platinum electrodes in 5 M LiNO3 the cell voltage can reach 2.0 V, whereas with a leakage current of 50 μA cm-2 it can reach 2.3 V. LiTi2(PO4)3 was synthesized using a Pechini method and cycled in pH-neutral Li2SO4. At a reaction potential near the lower limit of electrolyte stability, an initial discharge capacity of 118 mAh g-1 was measured at a C/5 rate, while about 90% of this discharge capacity was retained after 100 cycles. This work demonstrates that it is possible to have useful aqueous electrolyte lithium-ion batteries using the LiTi2(PO4)3 anode with cell voltages of 2 V and above.

Fire-extinguishing organic electrolytes for safe batteries

Science.gov (United States)

Wang, Jianhui; Yamada, Yuki; Sodeyama, Keitaro; Watanabe, Eriko; Takada, Koji; Tateyama, Yoshitaka; Yamada, Atsuo

2018-01-01

Severe safety concerns are impeding the large-scale employment of lithium/sodium batteries. Conventional electrolytes are highly flammable and volatile, which may cause catastrophic fires or explosions. Efforts to introduce flame-retardant solvents into the electrolytes have generally resulted in compromised battery performance because those solvents do not suitably passivate carbonaceous anodes. Here we report a salt-concentrated electrolyte design to resolve this dilemma via the spontaneous formation of a robust inorganic passivation film on the anode. We demonstrate that a concentrated electrolyte using a salt and a popular flame-retardant solvent (trimethyl phosphate), without any additives or soft binders, allows stable charge-discharge cycling of both hard-carbon and graphite anodes for more than 1,000 cycles (over one year) with negligible degradation; this performance is comparable or superior to that of conventional flammable carbonate electrolytes. The unusual passivation character of the concentrated electrolyte coupled with its fire-extinguishing property contributes to developing safe and long-lasting batteries, unlocking the limit toward development of much higher energy-density batteries.

Novel Nonflammable Electrolytes for Secondary Magnesium Batteries and High Voltage Electrolytes for Electrochemcial Supercapacitors

Energy Technology Data Exchange (ETDEWEB)

Dixon, Brian

2008-12-30

Magnesium has been used successfully in primary batteries, but its use in rechargeable cells has been stymied by the lack of suitable non-aqueous electrolyte that can conduct Mg+2 species, combined with poor stripping and plating properties. The development of a suitable cathode material for rechargeable magnesium batteries has also been a roadblock, but a nonflammable electrolyte is key. Likewise, the development of safe high voltage electrochemical supercapaitors has been stymied by the use of flammable solvents in the liquid electrolyte; to wit, acetonitrile. The purpose of the research conducted in this effort was to identify useful compositions of magnesium salts and polyphosphate solvents that would enable magnesium ions to be cycled within a secondary battery design. The polyphosphate solvents would provide the solvent for the magnesium salts while preventing the electrolyte from being flammable. This would enable these novel electrolytes to be considered as an alternative to THF-based electrolytes. In addition, we explored several of these solvents together with lithium slats for use as high voltage electrolytes for carbon-based electrochemical supercapacitors. The research was successful in that: 1) Magnesium imide dissolved in a phosphate ester solvent that contains a halogented phosphate ester appears to be the preferred electrolyte for a rechargeable Mg cell. 2) A combination of B-doped CNTs and vanadium phosphate appear to be the cathode of choice for a rechargeable Mg cell by virtue of higher voltage and better reversibility. 3) Magnesium alloys appear to perform better than pure magnesium when used in combination with the novel polyphosphate electrolytes. Also, this effort has established that Phoenix Innovation's family of phosphonate/phosphate electrolytes together with specific lithium slats can be used in supercapacitor systems at voltages of greater than 10V.

Electrolytes for magnesium electrochemical cells

Science.gov (United States)

Burrell, Anthony K.; Sa, Niya; Proffit, Danielle Lee; Lipson, Albert; Liao, Chen; Vaughey, John T.; Ingram, Brian J.

2017-07-04

An electrochemical cell includes a high voltage cathode configured to operate at 1.5 volts or greater; an anode including Mg.sup.0; and an electrolyte including an ether solvent and a magnesium salt; wherein: a concentration of the magnesium salt in the ether is 1 M or greater.

Thermal Aging of Anions in Ionic Liquids containing Lithium Salts by IC/ESI-MS

International Nuclear Information System (INIS)

Pyschik, Marcelina; Kraft, Vadim; Passerini, Stefano; Winter, Martin; Nowak, Sascha

2014-01-01

Highlights: • Thermal aging investigation of TFSI- and FSI- based ionic liquids and their mixtures with Li salts. • PYR 13 FSI shows thermal decomposition when mixed with LiPF 6 and LiClO 4 . • PYR 13 TFSI does not show any decomposition products with the electrolyte salts. • LiPF 6 dissolved in ionic liquids suffers of thermal aging as in conventional Li-ion battery electrolytes. - Abstract: The stability of 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR 13 TFSI) and 1-methyl-1-propylpyrrolidinium bis(fluorosulfonyl)imide (PYR 13 FSI) ionic liquids at elevated temperatures (60 °C) is investigated by ion chromatography. Additionally, the influence of the electrolyte salts, lithium hexafluorophosphate (LiPF 6 ), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium perchlorate (LiClO 4 ), on the decomposition of both the ionic liquids was analysed over a long term stability study. It has been found out that TFSI has a much higher thermal stability than FSI. The addition of LiTFSI did not show any effect on the aging of both ionic liquid anions. However, PYR 13 FSI degraded when mixed with the electrolyte salts LiPF 6 and LiClO 4 , while PYR 13 TFSI did not. Finally, LiPF 6 forms the same hydrolysis products in the investigated ionic liquids as in the commonly used electrolytes based on organic solvents in lithium-ion batteries

Preparation and characterization of Jatropha oil-based Polyurethane as non-aqueous solid polymer electrolyte for electrochemical devices

International Nuclear Information System (INIS)

Mustapa, Siti Rosnah; Aung, Min Min; Ahmad, Azizan; Mansor, Ahmad; TianKhoon, Lee

2016-01-01

Jatropha-oil based polyurethane is one of the initiative for replacing conventional petroleum based polyurethane. The vegetable oil-based polyurethane is more cost-effective and synthesize from renewable resources. Polyurethane was synthesized through prepolymerization method between jatropha oil-based polyol and diphenylmethane 4, 4’diisocyanate, (MDI) in inert condition. Then, lithium perchloride ion (LiClO 4 ) was added to the polyurethane system to form electrolyte film via solution casting technique. The polymer electrolytes were prepared by varying the amount of LiClO 4 ion 10 wt.% to 30 wt. %. The highest conductivity is achieved at 25 wt.% of LiClO 4 salt content, which is 1.29 × 10 −4 S/cm at room temperature 30 °C. The FTIR results showed the shifting of carbonyl group (C=O) (1750 cm −1 – 1730 cm −1 ), ether and ester group (C-O-C) (1300 cm −1 –1000 cm −1 ) and amine functional groups (N-H) (1650 cm −1 –1500 cm −1 ) in polyurethane electrolytes from the blank polyurethane shows that oxygen and nitrogen atom acts as electron donor in the electrolytes system. It also confirmed that the intermolecular reaction had occurred in the electrolytes system. While, the XRD analysis showed the semi-crystalline properties of polyurethane have been reduced to amorphous phase upon the increasing addition of lithium ion. SEM results revealed the morphology analysis of the polyurethane electrolytes. There is homogenous and smooth surface in polyurethane and the dissociation of salt was observed after the addition of salt indicates there was interaction between salt and the polymer host.

Dynamics and relaxation of charge carriers in poly(methylmethacrylate)-lithium salt based polymer electrolytes plasticized with ethylene carbonate

Science.gov (United States)

Pal, P.; Ghosh, A.

2016-07-01

In this paper, we have studied the dynamics and relaxation of charge carriers in poly(methylmethacrylate)-lithium salt based polymer electrolytes plasticized with ethylene carbonate. Structural and thermal properties have been examined using X-ray diffraction and differential scanning calorimetry, respectively. We have analyzed the complex conductivity spectra by using power law model coupled with the contribution of electrode polarization at low frequencies and high temperatures. The temperature dependence of the ionic conductivity and crossover frequency exhibits Vogel-Tammann-Fulcher type behavior indicating a strong coupling between the ionic and the polymer chain segmental motions. The scaling of the ac conductivity indicates that relaxation dynamics of charge carriers follows a common mechanism for all temperatures and ethylene carbonate concentrations. The analysis of the ac conductivity also shows the existence of a nearly constant loss in these polymer electrolytes at low temperatures and high frequencies. The fraction of free anions and ion pairs in polymer electrolyte have been obtained from the analysis of Fourier transform infrared spectra. It is observed that these quantities influence the behavior of the composition dependence of the ionic conductivity.

Dynamics and relaxation of charge carriers in poly(methylmethacrylate)-lithium salt based polymer electrolytes plasticized with ethylene carbonate

Energy Technology Data Exchange (ETDEWEB)

Pal, P.; Ghosh, A., E-mail: sspag@iacs.res.in [Department of Solid State Physics, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032 (India)

2016-07-28

In this paper, we have studied the dynamics and relaxation of charge carriers in poly(methylmethacrylate)-lithium salt based polymer electrolytes plasticized with ethylene carbonate. Structural and thermal properties have been examined using X-ray diffraction and differential scanning calorimetry, respectively. We have analyzed the complex conductivity spectra by using power law model coupled with the contribution of electrode polarization at low frequencies and high temperatures. The temperature dependence of the ionic conductivity and crossover frequency exhibits Vogel-Tammann-Fulcher type behavior indicating a strong coupling between the ionic and the polymer chain segmental motions. The scaling of the ac conductivity indicates that relaxation dynamics of charge carriers follows a common mechanism for all temperatures and ethylene carbonate concentrations. The analysis of the ac conductivity also shows the existence of a nearly constant loss in these polymer electrolytes at low temperatures and high frequencies. The fraction of free anions and ion pairs in polymer electrolyte have been obtained from the analysis of Fourier transform infrared spectra. It is observed that these quantities influence the behavior of the composition dependence of the ionic conductivity.

Novel polymeric systems for lithium ion batteries gel electrolytes

International Nuclear Information System (INIS)

Appetecchi, G.B.; Alessandrini, F.; Passerini, S.; Caporiccio, G.; Boutevin, B.; Guida-PietraSanta, F.

2005-01-01

Cross-linked, self-supporting, membranes for lithium ion battery gel electrolytes were obtained by cross-linking a mixture of polyfluorosilicone (PFSi) and polysilicone containing ethylene oxide (EO) units [P(Si-EO)]. The membranes were also reinforced with nanosized silica. The two polymer precursors were synthesized with functional groups capable to form inter-molecular cross-linking, thus obtaining three-dimensional, polymer matrices. The precursors were dissolved in a common solvent and cross-linked to obtain free-standing PFSi/P(Si-EO):SiO 2 composite films. The latter were undergone to swelling processes in (non-aqueous, aprotic, lithium salt containing) electrolytic solutions to obtain gel-type polymer electrolytes. The properties of the swelled PFSi/P(Si-EO):SiO 2 samples were evaluated as a function of the electrolytic solutions and the dipping time. The PFSi/P(Si-EO):SiO 2 membranes exhibited large swelling properties, high ionic conductivity and good electrochemical stability

Improvement of N-phthaloylchitosan based gel polymer electrolyte in dye-sensitized solar cells using a binary salt system.

Science.gov (United States)

Yusuf, S N F; Azzahari, A D; Selvanathan, V; Yahya, R; Careem, M A; Arof, A K

2017-02-10

A binary salt system utilizing lithium iodide (LiI) as the auxiliary component has been introduced to the N-phthaloylchitosan (PhCh) based gel polymer electrolyte consisting of ethylene carbonate (EC), dimethylformamide (DMF), tetrapropylammonium iodide (TPAI), and iodine (I 2 ) in order to improve the performance of dye-sensitized solar cell (DSSC) with efficiency of 6.36%, photocurrent density, J SC of 17.29mAcm -2 , open circuit voltage, V OC of 0.59V and fill factor, FF of 0.62. This efficiency value is an improvement from the 5.00% performance obtained by the DSSC consisting of only TPAI single salt system. The presence of the LiI in addition to the TPAI improves the charge injection rates and increases the iodide contribution to the total conductivity and both factors contribute to the increase in efficiency of the DSSC. The interaction behavior between polymer-plasticizer-salt was thoroughly investigated using EIS, FTIR spectroscopy and XRD. Copyright © 2016 Elsevier Ltd. All rights reserved.

Quadrupole terms in the Maxwell equations: Debye-Hückel theory in quadrupolarizable solvent and self-salting-out of electrolytes.

Science.gov (United States)

Slavchov, Radomir I

2014-04-28

If the molecules of a given solvent possess significant quadrupolar moment, the macroscopic Maxwell equations must involve the contribution of the density of the quadrupolar moment to the electric displacement field. This modifies the Poisson-Boltzmann equation and all consequences from it. In this work, the structure of the diffuse atmosphere around an ion dissolved in quadrupolarizable medium is analyzed by solving the quadrupolar variant of the Coulomb-Ampere's law of electrostatics. The results are compared to the classical Debye-Hückel theory. The quadrupolar version of the Debye-Hückel potential of a point charge is finite even in r = 0. The ion-quadrupole interaction yields a significant expansion of the diffuse atmosphere of the ion and, thus, it decreases the Debye-Hückel energy. In addition, since the dielectric permittivity of the electrolyte solutions depends strongly on concentration, the Born energy of the dissolved ions alters with concentration, which has a considerable contribution to the activity coefficient γ± known as the self-salting-out effect. The quadrupolarizability of the medium damps strongly the self-salting-out of the electrolyte, and thus it affects additionally γ±. Comparison with experimental data for γ± for various electrolytes allows for the estimation of the quadrupolar length of water: LQ ≈ 2 Å, in good agreement with previous assessments. The effect of quadrupolarizability is especially important in non-aqueous solutions. Data for the activity of NaBr in methanol is used to determine the quadrupolarizability of methanol with good accuracy.

Ionic-Liquid-Based Polymer Electrolytes for Battery Applications.

Science.gov (United States)

Osada, Irene; de Vries, Henrik; Scrosati, Bruno; Passerini, Stefano

2016-01-11

The advent of solid-state polymer electrolytes for application in lithium batteries took place more than four decades ago when the ability of polyethylene oxide (PEO) to dissolve suitable lithium salts was demonstrated. Since then, many modifications of this basic system have been proposed and tested, involving the addition of conventional, carbonate-based electrolytes, low molecular weight polymers, ceramic fillers, and others. This Review focuses on ternary polymer electrolytes, that is, ion-conducting systems consisting of a polymer incorporating two salts, one bearing the lithium cation and the other introducing additional anions capable of plasticizing the polymer chains. Assessing the state of the research field of solid-state, ternary polymer electrolytes, while giving background on the whole field of polymer electrolytes, this Review is expected to stimulate new thoughts and ideas on the challenges and opportunities of lithium-metal batteries. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrolytes for lithium and lithium-ion batteries

CERN Document Server

Jow, T Richard; Borodin, Oleg; Ue, Makoto

2014-01-01

Electrolytes for Lithium and Lithium-ion Batteries provides a comprehensive overview of the scientific understanding and technological development of electrolyte materials in the last?several years. This book covers key electrolytes such as LiPF6 salt in mixed-carbonate solvents with additives for the state-of-the-art Li-ion batteries as well as new electrolyte materials developed recently that lay the foundation for future advances.?This book also reviews the characterization of electrolyte materials for their transport properties, structures, phase relationships, stabilities, and impurities.

Ionic liquids as electrolytes

International Nuclear Information System (INIS)

Galinski, Maciej; Lewandowski, Andrzej; Stepniak, Izabela

2006-01-01

Salts having a low melting point are liquid at room temperature, or even below, and form a new class of liquids usually called room temperature ionic liquids (RTIL). Information about RTILs can be found in the literature with such key words as: room temperature molten salt, low-temperature molten salt, ambient-temperature molten salt, liquid organic salt or simply ionic liquid. Their physicochemical properties are the same as high temperature ionic liquids, but the practical aspects of their maintenance or handling are different enough to merit a distinction. The class of ionic liquids, based on tetraalkylammonium cation and chloroaluminate anion, has been extensively studied since late 1970s of the XX century, following the works of Osteryoung. Systematic research on the application of chloroaluminate ionic liquids as solvents was performed in 1980s. However, ionic liquids based on aluminium halides are moisture sensitive. During the last decade an increasing number of new ionic liquids have been prepared and used as solvents. The general aim of this paper was to review the physical and chemical properties of RTILs from the point of view of their possible application as electrolytes in electrochemical processes and devices. The following points are discussed: melting and freezing, conductivity, viscosity, temperature dependence of conductivity, transport and transference numbers, electrochemical stability, possible application in aluminium electroplating, lithium batteries and in electrochemical capacitors

Electrolyte for stable cycling of high-energy lithium sulfur redox flow batteries

Science.gov (United States)

Xiao, Jie; Liu, Jun; Pan, Huilin; Henderson, Wesley A.

2018-04-24

A device comprising: a lithium sulfur redox flow battery comprising an electrolyte composition comprising: (i) a dissolved Li2Sx electroactive salt, wherein x.gtoreq.4; (ii) a solvent selected from dimethyl sulfoxide, tetrahydrofuran, or a mixture thereof; and (iii) a supporting salt at a concentration of at least 2 M, as measured by moles of supporting salt divided by the volume of the solvent without considering the volume change of the electrolyte after dissolving the supporting salt.

Recent results on aqueous electrolyte cells

KAUST Repository

Wessells, Colin

2011-03-01

The improved safety of aqueous electrolytes makes aqueous lithium-ion batteries an attractive alternative to commercial cells utilizing flammable and expensive organic electrolytes. Two important issues relating to their use have been addressed in this work. One is the extension of the usable voltage range by the incorporation of lithium salts, and the other is the investigation of a useful negative electrode reactant, LiTi 2(PO 4) 3. The electrochemical stability of aqueous lithium salt solutions containing two lithium salts, LiNO 3 and Li 2SO 4, has been characterized using a constant current technique. In both cases, concentrated solutions had effective electrolyte stability windows substantially greater than that of pure water under standard conditions. At an electrolyte leakage current of 10 μA cm -2 between two platinum electrodes in 5 M LiNO 3 the cell voltage can reach 2.0 V, whereas with a leakage current of 50 μA cm -2 it can reach 2.3 V. LiTi 2(PO 4) 3 was synthesized using a Pechini method and cycled in pH-neutral Li 2SO 4. At a reaction potential near the lower limit of electrolyte stability, an initial discharge capacity of 118 mAh g -1 was measured at a C/5 rate, while about 90% of this discharge capacity was retained after 100 cycles. This work demonstrates that it is possible to have useful aqueous electrolyte lithium-ion batteries using the LiTi 2(PO 4) 3 anode with cell voltages of 2 V and above. © 2010 Elsevier B.V. All rights reserved.

Method for treating electrolyte to remove Li.sub.2 O

Science.gov (United States)

Tomczuk, Zygmunt; Miller, William E.; Johnson, Gerald K.; Willit, James L.

1998-01-01

A method of removing Li.sub.2 O present in an electrolyte predominantly of LiCl and KCl. The electrolyte is heated to a temperature not less than about 500.degree. C. and then Al is introduced into the electrolyte in an amount in excess of the stoichiometric amount needed to convert the Li.sub.2 O to a Li-Al alloy and lithium aluminate salt. The salt and aluminum are maintained in contact with agitation for a time sufficient to convert the Li.sub.2 O.

Non-aqueous electrolytes for lithium ion batteries

Science.gov (United States)

Chen, Zonghai; Amine, Khalil

2015-11-12

The present invention is generally related to electrolytes containing anion receptor additives to enhance the power capability of lithium-ion batteries. The anion receptor of the present invention is a Lewis acid that can help to dissolve LiF in the passivation films of lithium-ion batteries. Accordingly, one aspect the invention provides electrolytes comprising a lithium salt; a polar aprotic solvent; and an anion receptor additive; and wherein the electrolyte solution is substantially non-aqueous. Further there are provided electrochemical devices employing the electrolyte and methods of making the electrolyte.

Electrolyte for stable cycling of high-energy lithium sulfur redox flow batteries

Energy Technology Data Exchange (ETDEWEB)

Xiao, Jie; Liu, Jun; Pan, Huilin; Henderson, Wesley A.

2018-04-24

A device comprising: a lithium sulfur redox flow battery comprising an electrolyte composition comprising: (i) a dissolved Li₂S_x electroactive salt, wherein x.gtoreq.4; (ii) a solvent selected from dimethyl sulfoxide, tetrahydrofuran, or a mixture thereof; and (iii) a supporting salt at a concentration of at least 2 M, as measured by moles of supporting salt divided by the volume of the solvent without considering the volume change of the electrolyte after dissolving the supporting salt.

Electrolytes for lithium ion batteries

Science.gov (United States)

Vaughey, John; Jansen, Andrew N.; Dees, Dennis W.

2014-08-05

A family of electrolytes for use in a lithium ion battery. The genus of electrolytes includes ketone-based solvents, such as, 2,4-dimethyl-3-pentanone; 3,3-dimethyl 2-butanone(pinacolone) and 2-butanone. These solvents can be used in combination with non-Lewis Acid salts, such as Li.sub.2[B.sub.12F.sub.12] and LiBOB.

Method for treating electrolyte to remove Li{sub 2}O

Science.gov (United States)

Tomczuk, Z.; Miller, W.E.; Johnson, G.K.; Willit, J.L.

1998-01-20

A method is described for removing Li{sub 2}O present in an electrolyte predominantly of LiCl and KCl. The electrolyte is heated to a temperature not less than about 500 C and then Al is introduced into the electrolyte in an amount in excess of the stoichiometric amount needed to convert the Li{sub 2}O to a Li-Al alloy and lithium aluminate salt. The salt and aluminum are maintained in contact with agitation for a time sufficient to convert the Li{sub 2}O.

Stabilization of Li Metal Anode in DMSO-Based Electrolytes via Optimization of Salt-Solvent Coordination for Li-O ₂ Batteries

Energy Technology Data Exchange (ETDEWEB)

Liu, Bin [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland WA 99354 USA; Xu, Wu [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland WA 99354 USA; Yan, Pengfei [Environmental and Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland WA 99354 USA; Kim, Sun Tai [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland WA 99354 USA; Department of Energy Engineering, School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology, Ulsan 689-798 South Korea; Engelhard, Mark H. [Environmental and Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland WA 99354 USA; Sun, Xiuliang [Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland WA 99354 USA; Mei, Donghai [Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland WA 99354 USA; Cho, Jaephil [Department of Energy Engineering, School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology, Ulsan 689-798 South Korea; Wang, Chong-Min [Environmental and Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland WA 99354 USA; Zhang, Ji-Guang [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland WA 99354 USA

2017-03-08

The conventional DMSO-based electrolyte (1 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in DMSO) is unstable against the Li metal anode and therefore cannot be used directly in practical Li-O2 batteries. Here, we demonstrate that a highly concentrated electrolyte based on LiTFSI in DMSO (with a molar ratio of 1:3) can greatly improve the stability of the Li metal anode against DMSO and significantly improve the cycling stability of Li-O2 batteries. This highly concentrated electrolyte contains no free DMSO solvent molecules, but only complexes of (TFSI–)a-Li+-(DMSO)b (where a + b = 4), and thus enhances their stability with Li metal anodes. In addition, such salt-solvent complexes have higher Gibbs activation energy barriers than the free DMSO solvent molecules, indicating improved stability of the electrolyte against the attack of superoxide radical anions. Therefore, the stability of this highly concentrated electrolyte at both Li metal anodes and carbon-based air electrodes has been greatly enhanced, resulting in improved cyclic stability of Li-O2 batteries. The fundamental stability of the electrolyte with free-solvent against the chemical and electrochemical reactions can also be used to enhance the stability of other electrochemical systems.

Computer simulation of aqueous Na-Cl electrolytes

Energy Technology Data Exchange (ETDEWEB)

Hummer, G. [Los Alamos National Lab., NM (United States); Soumpasis, D.M. [Max-Planck-Institut fuer Biophysikalische Chemie (Karl-Friedrich-Bonhoeffer-Institut), Goettingen (Germany); Neumann, M. [Vienna Univ. (Austria). Inst. fuer Experimentalphysik

1993-11-01

Equilibrium structure of aqueous Na-Cl electrolytes between 1 and 5 mol/l is studied by means of molecular dynamics computer simulation using interaction site descriptions of water and ionic components. Electrostatic interactions are treated both with the newly developed charged-clouds scheme and with Ewald summation. In the case of a 5 mol/l electrolyte, the results for pair correlations obtained by the two methods are in excellent agreement. However, the charged-clouds technique is much faster than Ewald summation and makes simulations at lower salt concentrations feasible. It is found that both ion-water and ion-ion correlation functions depend only weakly on the ionic concentration. Sodium and chloride ions exhibit only a negligible tendency to form contact pairs. In particular, no chloride ion pairs in contact are observed.

Computer simulation of aqueous Na-Cl electrolytes

International Nuclear Information System (INIS)

Hummer, G.; Soumpasis, D.M.; Neumann, M.

1993-01-01

Equilibrium structure of aqueous Na-Cl electrolytes between 1 and 5 mol/l is studied by means of molecular dynamics computer simulation using interaction site descriptions of water and ionic components. Electrostatic interactions are treated both with the newly developed charged-clouds scheme and with Ewald summation. In the case of a 5 mol/l electrolyte, the results for pair correlations obtained by the two methods are in excellent agreement. However, the charged-clouds technique is much faster than Ewald summation and makes simulations at lower salt concentrations feasible. It is found that both ion-water and ion-ion correlation functions depend only weakly on the ionic concentration. Sodium and chloride ions exhibit only a negligible tendency to form contact pairs. In particular, no chloride ion pairs in contact are observed

Electrolytes for Wide Operating Temperature Lithium-Ion Cells

Science.gov (United States)

Smart, Marshall C. (Inventor); Bugga, Ratnakumar V. (Inventor)

2016-01-01

Provided herein are electrolytes for lithium-ion electrochemical cells, electrochemical cells employing the electrolytes, methods of making the electrochemical cells and methods of using the electrochemical cells over a wide temperature range. Included are electrolyte compositions comprising a lithium salt, a cyclic carbonate, a non-cyclic carbonate, and a linear ester and optionally comprising one or more additives.

TRANSPORT MECHANISM STUDIES OF CHITOSAN ELECTROLYTE SYSTEMS

International Nuclear Information System (INIS)

Navaratnam, S.; Ramesh, K.; Ramesh, S.; Sanusi, A.; Basirun, W.J.; Arof, A.K.

2015-01-01

ABSTRACT: Knowledge of ion-conduction mechanisms in polymers is important for designing better polymer electrolytes for electrochemical devices. In this work, chitosan-ethylene carbonate/propylene carbonate (chitosan-EC/PC) system with lithium acetate (LiCH 3 COO) and lithium triflate (LiCF 3 SO 3 ) as salts were prepared and characterized using electrochemical impedance spectroscopy to study the ion-conduction mechanism. It was found that the electrolyte system using LiCF 3 SO 3 salt had a higher ionic conductivity, greater dielectric constant and dielectric loss value compared to system using LiCH 3 COO at room temperature. Hence, it may be inferred that the system incorporated with LiCF 3 SO 3 dissociated more readily than LiCH 3 COO. Conductivity mechanism for the systems, 42 wt.% chitosan- 28 wt.% LiCF 3 SO 3 -30 wt.% EC/PC (CLT) and 42 wt.% chitosan-28 wt.% LiCH 3 COO-30 wt.% EC/PC (CLA) follows the overlapping large polaron tunneling (OLPT) model. Results show that the nature of anion size influences the ionic conduction of chitosan based polymer electrolytes. The conductivity values of the CLA system are found to be higher than that of CLT system at higher temperatures. This may be due to the vibration of bigger triflate anions would have hindered the lithium ion movements. FTIR results show that lithium ions can form complexation with polymer host which would provide a platform for ion hopping

Transmission electron microscopy of coatings formed by plasma electrolytic oxidation of titanium.

Science.gov (United States)

Matykina, E; Arrabal, R; Skeldon, P; Thompson, G E

2009-05-01

Transmission electron microscopy and supporting film analyses are used to investigate the changes in composition, morphology and structure of coatings formed on titanium during DC plasma electrolytic oxidation in a calcium- and phosphorus-containing electrolyte. The coatings are of potential interest as bioactive surfaces. The initial barrier film, of mixed amorphous and nanocrystalline structure, formed below the sparking voltage of 180 V, incorporates small amounts of phosphorus and calcium species, with phosphorus confined to the outer approximately 63% of the coating thickness. On commencement of sparking, calcium- and phosphorus-rich amorphous material forms at the coating surface, with local heating promoting crystallization in underlying and adjacent anodic titania. The amorphous material thickens with increased treatment time, comprising almost the whole of the approximately 5.7-microm-thick coating formed at 340 V. At this stage, the coating is approximately 4.4 times thicker than the oxidized titanium, with a near-surface composition of about 12 at.% Ti, 58 at.% O, 19 at.% P and 11 at.% Ca. Further, the amount of titanium consumed in forming the coating is similar to that calculated from the anodizing charge, although there may be non-Faradaic contributions to the coating growth.

Corrosion behaviors and effects of corrosion products of plasma electrolytic oxidation coated AZ31 magnesium alloy under the salt spray corrosion test

International Nuclear Information System (INIS)

Wang, Yan; Huang, Zhiquan; Yan, Qin; Liu, Chen; Liu, Peng; Zhang, Yi; Guo, Changhong; Jiang, Guirong; Shen, Dejiu

2016-01-01

Highlights: • Corrosion behaviors of a PEO coating was investigated after the salt spray test. • Corrosion products have significant effects on corrosion behaviors of the coating. • An electrochemical corrosion model is proposed. - Abstract: The effects of corrosion products on corrosion behaviors of AZ31 magnesium alloy with a plasma electrolytic oxidation (PEO) coating were investigated under the salt spray corrosion test (SSCT). The surface morphology, cross-sectional microstructure, chemical and phase compositions of the PEO coating were determined using scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction analysis (XRD), respectively. Further, the corrosion process of the samples under the SSCT was examined in a non-aqueous electrolyte (methanol) using electrochemical impedance spectroscopy (EIS) coupled with equivalent circuit. The results show that the inner layer of the coating was destroyed firstly and the corrosion products have significant effects on the corrosion behaviors of the coating. The results above are discussed and an electrochemical corrosion model is proposed in the paper.

Corrosion behaviors and effects of corrosion products of plasma electrolytic oxidation coated AZ31 magnesium alloy under the salt spray corrosion test

Energy Technology Data Exchange (ETDEWEB)

Wang, Yan; Huang, Zhiquan; Yan, Qin; Liu, Chen; Liu, Peng; Zhang, Yi [State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004 (China); Guo, Changhong; Jiang, Guirong [College of Mechanical Engineering, Yanshan University, Qinhuangdao 066004 (China); Shen, Dejiu, E-mail: DejiuShen@163.com [State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004 (China)

2016-08-15

Highlights: • Corrosion behaviors of a PEO coating was investigated after the salt spray test. • Corrosion products have significant effects on corrosion behaviors of the coating. • An electrochemical corrosion model is proposed. - Abstract: The effects of corrosion products on corrosion behaviors of AZ31 magnesium alloy with a plasma electrolytic oxidation (PEO) coating were investigated under the salt spray corrosion test (SSCT). The surface morphology, cross-sectional microstructure, chemical and phase compositions of the PEO coating were determined using scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction analysis (XRD), respectively. Further, the corrosion process of the samples under the SSCT was examined in a non-aqueous electrolyte (methanol) using electrochemical impedance spectroscopy (EIS) coupled with equivalent circuit. The results show that the inner layer of the coating was destroyed firstly and the corrosion products have significant effects on the corrosion behaviors of the coating. The results above are discussed and an electrochemical corrosion model is proposed in the paper.

Structural and optical characterization of PVA:KMnO4 based solid polymer electrolyte

Directory of Open Access Journals (Sweden)

Omed Gh. Abdullah

Full Text Available Solid polymer electrolyte films of polyvinyl alcohol (PVA doped with a different weight percent of potassium permanganate (KMnO4 were prepared by standard solution cast method. XRD and FTIR techniques were performed for structural study. Complex formation between the PVA polymer and KMnO4 salt was confirmed by Fourier transform infrared (FTIR spectroscopy. The description of crystalline nature of the solid polymer electrolyte films has been confirmed by XRD analysis. The UV-Visible absorption spectra were analyzed in terms of absorption formula for non-crystalline materials. The fundamental optical parameters such as optical band gap energy, refractive index, optical conductivity, and dielectric constants have been investigated and showed a clear dependence on the KMnO4 concentration. The observed value of optical band gap energy for pure PVA is about 6.27 eV and decreases to a value 3.12 eV for the film sample formed with 4 wt% KMnO4 salt. The calculated values of refractive index and the dielectric constants of the polymer electrolyte films increase with increasing KMnO4 content. Keywords: Solid polymer electrolyte, XRD analysis, FTIR study, Optical band gap, Dielectric constant, Refractive index

A study for an electrolytic reduction of tantalum oxide in a LiCl-Li2O molten salt

International Nuclear Information System (INIS)

Park, Sung Bin; Park, Byung Heung; Seo, Chung Seok; Kang, Dae Seung; Kwon, Seon Gil; Park, Seong Won

2005-01-01

Korea Atomic Energy Research Institute (KAERI) has developed the Advanced Spent Fuel Conditioning Process (ACP) to be an innovative technology for handling the PWR spent fuel. As part of ACP, the electrolytic reduction process (ER process) is the electrochemical reduction process of uranium oxide to uranium metal in a molten salt. The ER process has advantages in a technical stability, an economic potential and a good proliferation resistance. KAERI has reported on the good experimental results of an electrochemical reduction of the uranium oxide in a 20 kg HM/batch lab-scale. The ER process can be applicable to the reduction of other metal oxides. Metal tantalum powder has attracted attention for a variety of applications. A tantalum capacitor made from superfine and pliable tantalum powders is very small in size and it has a higher-capacitance part, therefore it is useful for microelectronic devices. By the ER process the metal tantalum can be obtained from tantalum pentoxide. In this work, a 40 g Ta 2 O 5 /batch electrochemical reactor was used for the synthesis of the metal tantalum. From the results of the cyclic voltammograms for the Ta 2 O 5 -LiCl-Li 2 O system, the mechanism of the tantalum reduction in a molten LiCl-Li 2 O salt system was investigated. Tantalum pentoxide is chemically reduced to tantalum metal by the lithium metal which is electrochemically deposited into an integrated cathode assembly in the LiCl-Li 2 O molten salt. The experiments for the tantalum reduction were performed with a chronopotentiometry in the reactor cell, the reduced products were analyzed from an analysis of the X-ray diffraction (XRD), scanning electron microscope and energy dispersive X-ray (SEM-EDX). From the results, the electrolytic reduction process is applicable to the synthesis of metal tantalum

Zinc-based electrolyte compositions, and related electrochemical processes and articles

Science.gov (United States)

Kniajanski, Sergei; Soloveichik, Grigorii Lev

2018-02-20

An aqueous electrolyte composition is described, including a zinc salt based on zinc acetate or zinc glocolate. The saturation concentration of zinc in the electrolyte composition is in the range of about 2.5M to about 3.5M. The composition also contains at least one salt of a monovalent cation. The molar ratio of zinc to the monovalent cation is about 1:2. An aqueous zinc electroplating bath, containing the aqueous electrolyte composition, is also disclosed, along with a method for the electrochemical deposition of zinc onto a substrate surface, using the electroplating bath. Related flow batteries are also described, including a catholyte, as well as an anolyte based on the aqueous electrolyte composition, with a membrane between the catholyte and the anolyte.

An electrolyte CPA equation of state for mixed solvent electrolytes

DEFF Research Database (Denmark)

Maribo-Mogensen, Bjørn; Thomsen, Kaj; Kontogeorgis, Georgios M.

2015-01-01

Despite great efforts over the past decades, thermodynamic modeling of electrolytes in mixed solvents is still a challenge today. The existing modeling frameworks based on activity coefficient models are data-driven and require expert knowledge to be parameterized. It has been suggested...... using a self-consistent model for the static permittivity. A simple scheme for parameterization of salts with a limited number of parameters is proposed and model parameters for a range of salts are determined from experimental data of activity and osmotic coefficients as well as freezing point...

Unusual Passivation Ability of Superconcentrated Electrolytes toward Hard Carbon Negative Electrodes in Sodium-Ion Batteries.

Science.gov (United States)

Takada, Koji; Yamada, Yuki; Watanabe, Eriko; Wang, Jianhui; Sodeyama, Keitaro; Tateyama, Yoshitaka; Hirata, Kazuhisa; Kawase, Takeo; Yamada, Atsuo

2017-10-04

The passivation of negative electrodes is key to achieving prolonged charge-discharge cycling with Na-ion batteries. Here, we report the unusual passivation ability of superconcentrated Na-salt electrolytes. For example, a 50 mol % sodium bis(fluorosulfonyl)amide (NaFSA)/succinonitrile (SN) electrolyte enables highly reversible Na + insertion into a hard carbon negative electrode without any electrolyte additive, functional binder, or electrode pretreatment. Importantly, an anion-derived passivation film is formed via preferential reduction of the anion upon charging, which can effectively suppress further electrolyte reduction. As a structural characteristic of the electrolyte, most anions are coordinated to multiple Na + cations at high concentration, which shifts the lowest unoccupied molecular orbitals of the anions downward, resulting in preferential anion reduction. The present work provides a new understanding of the passivation mechanism with respect to the coordination state of the anion.

Lithium-conducting ionic melt electrolytes from polyether-functionalized fluorosulfonimide anions

International Nuclear Information System (INIS)

Hallac, B.B.; Geiculescu, O.E.; Rajagopal, R.V.; Creager, S.E.; DesMarteau, D.D.

2008-01-01

Solvent-free lithium-conducting ionic melt (IM) electrolytes were synthesized and characterized with respect to chemical structure, purity, and ion transport properties. The melts consist of lithium (perfluorovinylether)sulfonimide salts attached covalently to a lithium-solvating polyether chain. Ionic conductivities are relatively high which is a consequence of the favorable combination of the low lattice energy of the lithium fluorosulfonimide salt (low basicity of the fluorosulfonimide anion), the relatively low viscosity of the polyether matrix, and the relatively high salt content of the melts. Galvanostatic dc polarization experiments, using cells with non-blocking Li electrodes, indicate that salt concentration polarization does not occur in these electrolytes as dc current is passed through them

Stereoselectivity in the salt-cocrystal products formed by phenylglycinol or phenylglycine with their respective sodium or hydrochloride salts.

Science.gov (United States)

Brittain, Harry G

2013-01-01

The salt and stereoselective cocrystal phenomena associated with 2-phenylglycinol and 2-phenylglycine have been studied using X-ray powder diffraction and differential scanning calorimetry. The chiral identities of the free acids and their sodium salts, or the free bases and their chloride salts, were found to play a determining role as to whether a salt-cocrystal product could or could not be formed. In particular, when cocrystallization of an enantiomerically pure basic or zwitterionic substance with its enantiomerically pure acid addition salt was attempted, a salt-cocrystal was only obtained when the absolute configuration of the two reactants is opposite. On the other hand, it has been found that no stereoselectivity in salt-cocrystal formation existed in the cocrystallization of an enantiomerically pure acidic or zwitterionic substance with its enantiomerically pure base addition salt. Copyright © 2012 Wiley Periodicals, Inc.

Kinetic studies on the removal of fission products from molten salt using Zeolite-4A. Contributed Paper RD-15

International Nuclear Information System (INIS)

Shafi, Suheel; Prabhakara Reddy, B.; Perumal, S.V.; Nagarajan, K.

2014-01-01

Molten salt electrorefining process is one of the nonaqueous processes, being developed for reprocessing metallic spent fuel. This process uses liquid metals and molten salts and is operated at elevated temperatures. In the electro-refining process, the spent fuel is used as the anode of the electro-refiner and the actinide elements in the spent fuel are electrotransported from the anode through the molten salt electrolyte onto a suitable cathode where they are collected as metals in pure form. After some batches are processed, chlorides of fission products such as alkali, alkaline earth and rare earth metals accumulate in the electrolyte salt. The accumulated FPs in the salt will be removed by adsorption/ion-exchange by using zeolite columns. Hence, kinetic studies on the adsorption of Cs, Ba which are some of the major FP products in LiCI-KCI eutectic, have been carried out

Nonflammable perfluoropolyether-based electrolytes for lithium batteries

Science.gov (United States)

Wong, Dominica H. C.; Thelen, Jacob L.; Fu, Yanbao; Devaux, Didier; Pandya, Ashish A.; Battaglia, Vincent S.; Balsara, Nitash P.; DeSimone, Joseph M.

2014-01-01

The flammability of conventional alkyl carbonate electrolytes hinders the integration of large-scale lithium-ion batteries in transportation and grid storage applications. In this study, we have prepared a unique nonflammable electrolyte composed of low molecular weight perfluoropolyethers and bis(trifluoromethane)sulfonimide lithium salt. These electrolytes exhibit thermal stability beyond 200 °C and a remarkably high transference number of at least 0.91 (more than double that of conventional electrolytes). Li/LiNi1/3Co1/3Mn1/3O2 cells made with this electrolyte show good performance in galvanostatic cycling, confirming their potential as rechargeable lithium batteries with enhanced safety and longevity. PMID:24516123

Ion Transport and Structure in Polymer Electrolytes with Applications in Lithium Batteries

Science.gov (United States)

Chintapalli, Mahati

When mixed with lithium salts, polymers that contain more than one chemical group, such as block copolymers and endgroup-functionalized polymers, are promising electrolyte materials for next-generation lithium batteries. One chemical group can provide good ion solvation and transport properties, while the other chemical group can provide secondary properties that improve the performance characteristics of the battery. Secondary properties of interest include non-flammability for safer lithium ion batteries and high mechanical modulus for dendrite resistance in high energy density lithium metal batteries. Block copolymers and other materials with multiple chemical groups tend to exhibit nanoscale heterogeneity and can undergo microphase separation, which impacts the ion transport properties. In block copolymers that microphase separate, ordered self-assembled structures occur on longer length scales. Understanding the interplay between structure at different length scales, salt concentration, and ion transport is important for improving the performance of multifunctional polymer electrolytes. In this dissertation, two electrolyte materials are characterized: mixtures of endgroup-functionalized, short chain perfluoropolyethers (PFPEs) and lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) salt, and mixtures of polystyrene-block-poly(ethylene oxide) (PS- b-PEO; SEO) and LiTFSI. The PFPE/LiTFSI electrolytes are liquids in which the PFPE backbone provides non-flammability, and the endgroups resemble small molecules that solvate ions. In these electrolytes, the ion transport properties and nanoscale heterogeneity (length scale 1 nm) are characterized as a function of endgroup using electrochemical techniques, nuclear magnetic resonance spectroscopy, and wide angle X-ray scattering. Endgroups, especially those containing PEO segments, have a large impact on ionic conductivity, in part because the salt distribution is not homogenous; we find that salt partitions

Electrolyte for batteries with regenerative solid electrolyte interface

Science.gov (United States)

Xiao, Jie; Lu, Dongping; Shao, Yuyan; Bennett, Wendy D.; Graff, Gordon L.; Liu, Jun; Zhang, Ji-Guang

2017-08-01

An energy storage device comprising: an anode; and a solute-containing electrolyte composition wherein the solute concentration in the electrolyte composition is sufficiently high to form a regenerative solid electrolyte interface layer on a surface of the anode only during charging of the energy storage device, wherein the regenerative layer comprises at least one solute or solvated solute from the electrolyte composition.

Ion Dynamics Study of Potato Starch + Sodium Salts Electrolyte System

Directory of Open Access Journals (Sweden)

Tuhina Tiwari

2013-01-01

Full Text Available The effect of different anions, namely, SCN−, I−, and ClO4−, on the electrical properties of starch-based polymer electrolytes has been studied. Anion size and conductivity are having an inverse trend indicating systems to be predominantly anionic conductor. Impact of anion size and multiplet forming tendency is reflected in number of charge carriers and mobility, respectively. Ion dynamics study reveals the presence of different mechanisms in different frequency ranges. Interestingly, superlinear power law (SLPL is found to be present at <5 MHz frequency, which is further confirmed by dielectric data.

Superconcentrated electrolytes for a high-voltage lithium-ion battery

Science.gov (United States)

Wang, Jianhui; Yamada, Yuki; Sodeyama, Keitaro; Chiang, Ching Hua; Tateyama, Yoshitaka; Yamada, Atsuo

2016-01-01

Finding a viable electrolyte for next-generation 5 V-class lithium-ion batteries is of primary importance. A long-standing obstacle has been metal-ion dissolution at high voltages. The LiPF6 salt in conventional electrolytes is chemically unstable, which accelerates transition metal dissolution of the electrode material, yet beneficially suppresses oxidative dissolution of the aluminium current collector; replacing LiPF6 with more stable lithium salts may diminish transition metal dissolution but unfortunately encounters severe aluminium oxidation. Here we report an electrolyte design that can solve this dilemma. By mixing a stable lithium salt LiN(SO2F)2 with dimethyl carbonate solvent at extremely high concentrations, we obtain an unusual liquid showing a three-dimensional network of anions and solvent molecules that coordinate strongly to Li+ ions. This simple formulation of superconcentrated LiN(SO2F)2/dimethyl carbonate electrolyte inhibits the dissolution of both aluminium and transition metal at around 5 V, and realizes a high-voltage LiNi0.5Mn1.5O4/graphite battery that exhibits excellent cycling durability, high rate capability and enhanced safety. PMID:27354162

Continuous modification of AK11 silumin with multicomponent salt on base of NaCl

Directory of Open Access Journals (Sweden)

J. Pezda

2007-12-01

Full Text Available Sodium belongs to the most effective modifying agents. The sodium can be brought into metal bath in metallic form or in form of chemical compounds comprising sodium, the most often in form of NaF. In the both above mentioned cases action of sodium is of very short duration, (what constitutes its main disadvantage, as lasting for about 15-20 minutes, mainly due to its evaporation from metal bath.Prolongation of modifying agent’s action can be accomplished due to technology of continuous introduction of sodium to metal bath. That technology is based on continuous electrolysis of sodium salt, occurring directly in melting pot with liquid alloy. Application of solid electrolyte – conducting sodium ions (ionic conductance – and simultaneously maintaining solid state of aggregation in melting and superheating temperature of alloy, i.e. 600÷800°C is indispensable for such process. Suitable sodium salt which is placed in retort produced from solid electrolyte shall undergo dissociation, and next electrolysis, in result of applied direct current. Sodium ions arisen during the dissociation of sodium salts and electrolysis are “conveyed” through retort walls made from solid electrolyte. In contact with liquid alloy as cathode, sodium ions pass to atomic state, modifying the alloy. The paper discusses results of initial study concerning process of continuous modification of AK11 silumin with use of multicomponent sodium salt on base of NaCl, shows results of tensile strength Rm and measurement of voltage drop for the alloy in solid state. Values of those parameters have confirmed obtained modification effect of investigated alloys. Assurance of stable run of continuous modification process brings about necessity of a further research aimed at optimization of parameters of the process.

Actinide-Lanthanide separation by an electrolytic method in molten salt media: feasibility assessment of a renewed liquid cathode

International Nuclear Information System (INIS)

Huguet, A.

2009-12-01

This study is part of a research program concerning the assessment of pyrochemical methods for the nuclear waste processing. The An-Ln partitioning could be achieved by an electrolytic selective extraction in molten salt media. It has been decided to focus on liquid reactive cathode which better suits to a group actinides co-recycling. The aim of the study is to propose, define and initiate the development of an electrolytic pyro-process dedicated to the quantitative and selective recovery of the actinides. Quantitativeness is related to technology, whereas selectivity is governed by chemistry. The first step consisted in selecting the adequate operating conditions, which enables a sufficient An-Ln separation. The first step consisted, by means of thermodynamic calculi and electrochemical investigations, in selecting a promising combination between molten electrolyte and cathodic material, regarding the process constraints. To improve the recovery yield, it is necessary to develop a disruptive technology: here comes the concept of a dynamic electrodeposition carried out onto liquid metallic drops. The next step consisted in designing and manufacturing a lab-scale device which enables dropping flow studies. Since interfacial phenomena are of primary meaning in such a concept, it has been decided to focus on high temperature liquid-liquid interfacial measurements. (author)

Ionogel Electrolytes through Sol-Gel Processing

Science.gov (United States)

Horowitz, Ariel I.

Electrical energy needs have intensified due to the ubiquity of personal electronics, the decarbonization of energy services through electrification, and the use of intermittent renewable energy sources. Despite developments in mechanical and thermal methods, electrochemical technologies are the most convenient and effective means of storing electrical energy. These technologies include both electrochemical cells, commonly called batteries, and electrochemical double-layer capacitors, or "supercapacitors", which store energy electrostatically. Both device types require an ion-conducting electrolyte. Current devices use solutions of complex salts in organic solvents, leading to both toxicity and flammability concerns. These drawbacks can be avoided by replacing conventional electrolytes with room-temperature molten salts, known as ionic liquids (ILs). ILs are non-volatile, non-flammable, and offer high conductivity and good electrochemical stability. Device mass can be reduced by combining ILs with a solid scaffold material to form an "ionogel," further improving performance metrics. In this work, sol-gel chemistry is explored as a means of forming ionogel electrolytes. Sol-gel chemistry is a solution-based, industrially-relevant, well-studied technique by which solids such as silica can be formed in situ. Previous works used a simple acid-catalyzed sol-gel reaction to create brittle, glassy ionogels. Here, both the range of products that can be accomplished through sol-gel processing and the understanding of interactions between ILs and the sol-gel reaction network are greatly expanded. This work introduces novel ionogel materials, including soft and compliant silica-supported ionogels and PDMS-supported ionogels. The impacts of the reactive formulation, IL identity, and casting time are detailed. It is demonstrated that variations in formulation can lead to rapid gelation and open pore structures in the silica scaffold or slow gelation and more dense silica

Physiological Mechanism of Enhancing Salt Stress Tolerance of Perennial Ryegrass by 24-Epibrassinolide

Directory of Open Access Journals (Sweden)

Wenli Wu

2017-06-01

Full Text Available Brassinosteroids (BR regulate plant tolerance to salt stress but the mechanisms underlying are not fully understood. This study was to investigate physiological mechanisms of 24-epibrassinolide (EBR's impact on salt stress tolerance in perennial ryegrass (Lolium perenne L. The grass seedlings were treated with EBR at 0, 10, and 100 nM, and subjected to salt stress (250 mM NaCl. The grass irrigated with regular water without EBR served as the control. Salt stress increased leaf electrolyte leakage (EL, malondialdehyde (MDA, and reduced photosynthetic rate (Pn. Exogenous EBR reduced EL and MDA, increased Pn, chlorophyll content, and stomatal conductance (gs. The EBR applications also alleviated decline of superoxide dismutase (SOD and catalase (CAT and ascorbate peroxidase (APX activity when compared to salt treatment alone. Salt stress increased leaf abscisic acid (ABA and gibberellin A4 (GA4 content but reduced indole-3-acetic acid (IAA, zeatin riboside (ZR, isopentenyl adenosine (iPA, and salicylic acid (SA. Exogenous EBR at 10 nm and 100 nM increased ABA, and iPA content under salt stress. The EBR treatment at 100 nM also increased leaf IAA, ZR, JA, and SA. In addition, EBR treatments increased leaf proline and ions (K+, Mg2+, and Ca2+ content, and reduced Na+/K+ in leaf tissues. The results of this study suggest that EBR treatment may improve salt stress tolerance by increasing the level of selected hormones and antioxidant enzyme (SOD and CAT activity, promoting accumulation of proline and ions (K+, Ca2+, and Mg2+ in perennial ryegrass.

Synthesis, Characterization and Conductivity Study of Poly(vinyl 4-HYDROXY-3-METHOXY Benzal) and its Sodio Salt in Solid State

Science.gov (United States)

Borah, P.; Hussain, S.; Dutta, A.

Among the various ion-conducting materials, polymer salt complexes are of current interest due to their possible application as solid electrolyte as well as their physical nature in advanced high-energy electrochemical devices such as batteries, fuel cells, electrochromic display devices, photo electro-chemical solar cells52-55 etc. The main advantages of polymeric electrolytes are their mechanical properties, ease of fabrication of thin films of desired sizes and their ability to form proper electrode-electrolyte contact. Polymer electrolyte usually consists of a polymer and a salt and is considered to be solid solutions in which the polymer functions as solvent. In the present paper the synthesis, characterization and the conductivity study of the polymer poly (vinyl 4-hydroxy-3-methoxy benzal) (PV-HMB) and its sodio salt (PV-HMB-Na) have been reported. The polymer was prepared by carrying out homogenous acetalization between the prepolymer poly vinylalcohol (PVA) and 4-hydroxy-3-methoxy benzaldehyde (vanilline). PVA was dissolved in dimethyl formamide (DMF) and lithium chloride (LiCl) system i.e., in non-aqueous medium. The sodio salt was prepared by alkalization. The polymer and its salt were characterized by IR, 1H NMR and DSC. Frequency and temperature dependence of ac conductivity has been studied to learn about the electrical conduction behaviour in this material. The electrical conductivity of the new polymeric salt was found to be in the range 10-4 to 10-6 Scm-1. There is about 103 to 104 fold increase in the conductivity of the new polymer salt. Apparent activation energy of the polymer and its salt were found to be 0.139 and 0.08998 ev respectively.

A study of the potential interaction of valsartan with some electrolytes

African Journals Online (AJOL)

The effect of electrolytes (salts) on the partition coefficient of valsartan was studied at room temperature. The investigation was done by partitioning valsartan between 1-octanol and electrolyte solutions of varying concentrations. It was found that all the electrolytes increased the partition coefficient of the drug except sodium ...

Electrolytic method for the production of lithium using a lithium-amalgam electrode

Science.gov (United States)

Cooper, John F.; Krikorian, Oscar H.; Homsy, Robert V.

1979-01-01

A method for recovering lithium from its molten amalgam by electrolysis of the amalgam in an electrolytic cell containing as a molten electrolyte a fused-salt consisting essentially of a mixture of two or more alkali metal halides, preferably alkali metal halides selected from lithium iodide, lithium chloride, potassium iodide and potassium chloride. A particularly suitable molten electrolyte is a fused-salt consisting essentially of a mixture of at least three components obtained by modifying an eutectic mixture of LiI-KI by the addition of a minor amount of one or more alkali metal halides. The lithium-amalgam fused-salt cell may be used in an electrolytic system for recovering lithium from an aqueous solution of a lithium compound, wherein electrolysis of the aqueous solution in an aqueous cell in the presence of a mercury cathode produces a lithium amalgam. The present method is particularly useful for the regeneration of lithium from the aqueous reaction products of a lithium-water-air battery.

The impact of uni-univalent electrolytes on (water + acetic acid + toluene) equilibria: Representation with electrolyte-NRTL model

International Nuclear Information System (INIS)

Saien, Javad; Fattahi, Mahdi; Mozafarvandi, Maryam

2014-01-01

Highlights: • Experimental LLE data for water + acetic acid + toluene + NaCl or KCl were reported. • The salting-out effect was detected; indicating the stronger effect of NaCl. • The electrolyte-NRTL model was adequately used to correlate the phase equilibria. • A good agreement was observed between calculated and experimental tie-lines. - Abstract: The presence of salts can significantly alter the (liquid + liquid) equilibrium and extraction process. In this work, a study was conducted on the (liquid + liquid) equilibria of (water + acetic acid + toluene + sodium chloride or potassium chloride) at temperatures (288.2, 298.2 and 313.2) K. This chemical system, irrespective of salt, is frequently used in (liquid + liquid) extraction investigations. The selected salt concentrations in initial aqueous solutions were (0.9 and 1.7) mol · L −1 . The results show that salting-out effect of the salts was significant, so that an enhancement in the acetic acid distribution coefficient was achieved within (15.6 to 66.8)% with NaCl and within (2.5 to 37.6)% with KCl. Meantime, high separation factors were found at low temperatures and low solute concentrations. The electrolyte-NRTL model was satisfactorily used to correlate the phase equilibria. In this regard for each salt, the temperature dependent binary interaction parameters between components were calculated. The predicted tie-line mole fractions give root-mean square deviation (RMSD) values of only 0.0038 and 0.0045 for the systems containing NaCl and KCl, respectively

X-ray diffraction of slag-based sodium salt waste forms

Energy Technology Data Exchange (ETDEWEB)

Langton, C. A. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Missimer, D. M. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

2014-09-30

The attached report documents sample preparation and x-ray diffraction results for a series of cement and blended cement matrices prepared with either water or a 4.4 M Na salt solution. The objective of the study was to provide initial phase characterization for the Cementitious Barriers Partnership reference case cementitious salt waste form. This information can be used to: 1) generate a base line for the evolution of the waste form as a function of time and conditions, 2) potentially to design new binders based on mineralogy of the binder, 3) understand and predict anion and cation leaching behavior of contaminants of concern, and 4) predict performance of the waste forms for which phase solubility and thermodynamic data are available.

TS/EL ELECTRICAL WORK REQUEST FORM

CERN Multimedia

TS Department

2008-01-01

To facilitate the processing of requests for minor electrical installation work to be carried out by the TS/EL group, a new procedure designed to improve contacts and exchange of information with customers has been set up. The procedure comprises a check to determine whether the TS/EL or the TS/FM group is responsible for the area where the electrical work is to be done. If the work is to be performed by the EL group, an on-line request form must be completed. The following steps must be completed: On a web browser, use the link http://ts-dep.web.cern.ch/ts-dep/groups/el/el.htm In the left-hand menu choose ‘Demande de Travaux Electriques’ Enter the building number to check which group to contact and click ‘FIND’ If the area is: Under FM’s responsibility:\tCall 77777 Under EL’s responsibility:\tClick the link to the work form, complete it and send it (click ‘ENVOYER’) IMPORTANT This form is for minor electrical installation requests only. Please call 72201 in t...

Structure of tungsten electrodeposited from oxide chloride-fluoride molten salts

International Nuclear Information System (INIS)

Pavlovskij, V.A.; Reznichenko, V.A.

1998-01-01

Investigation results on the influence of electrolysis parameters and electrolyte composition on tungsten cathode deposit structure are presented. The electrolysis was performed in NaCl-NaF-WO 3 molten salts using tungsten and tungsten coated molybdenum cathodes. Morphological and metallographic studies of tungsten crystals were carrier out. Tungsten deposits were obtained in the form of crystalline conglomerates, sponge and high dispersity powder

Block Copolymer Electrolytes: Thermodynamics, Ion Transport, and Use in Solid- State Lithium/Sulfur Cells

Science.gov (United States)

Teran, Alexander Andrew

Nanostructured block copolymer electrolytes containing an ion-conducting block and a modulus-strengthening block are of interest for applications in solid-state lithium metal batteries. These materials can self-assemble into well-defined microstructures, creating conducting channels that facilitate ion transport. The overall objective of this dissertation is to gain a better understanding of the behavior of salt-containing block copolymers, and evaluate their potential for use in solid-state lithium/sulfur batteries. Anionically synthesized polystyrene-b-poly(ethylene oxide) (SEO) copolymers doped with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt were used as a model system. This thesis investigates the model system on several levels: from fundamental thermodynamic studies to bulk characterization and finally device assembly and testing. First, the thermodynamics of neat and salt-containing block copolymers was studied. The addition of salt to these materials is necessary to make them conductive, however even small amounts of salt can have significant effects on their phase behavior, and consequently their iontransport and mechanical properties. As a result, the effect of salt addition on block copolymer thermodynamics has been the subject of significant interest over the last decade. A comprehensive study of the thermodynamics of block copolymer/salt mixtures over a wide range of molecular weights, compositions, salt concentrations and temperatures was conducted. Next, the effect of molecular weight on ion transport in both homopolymer and copolymer electrolytes were studied over a wide range of chain lengths. Homopolymer electrolytes show an inverse relationship between conductivity and chain length, with a plateau in the infinite molecular weight limit. This is due to the presence of two mechanisms of ion conduction in homopolymers; the first mechanism is a result of the segmental motion of the chains surrounding the salt ions, 2 creating a liquid

New polysaccharide-based polymer electrolytes; Nouveaux electrolytes polymeres a base de polysaccharides

Energy Technology Data Exchange (ETDEWEB)

Velasquez-Morales, P.; Le Nest, J.F.; Gandini, A. [Ecole Francaise de Papeterie et des Industries Graphique, 38 - Saint Martin d`Heres (France)

1996-12-31

Polysaccharides like cellulose and chitosan are known for their filmic properties. This paper concerns the synthesis and the study of chitosan-based polymer electrolytes. A preliminary work concerns the study of glucosamine reactivity. The poly-condensation of chitosan ethers (obtained by reaction with ethylene oxide or propylene oxide) with bifunctional and monofunctional oligo-ethers leads to the formation of thin lattices (10 {mu}m) having excellent mechanical properties. The presence of grafted polyether chains along the polysaccharide skeleton allows to modify the vitreous transition temperature and the molecular disorder of the system. Two type of polymer electrolytes have been synthesized: electrolytes carrying a dissolved alkaline metal salt and ionomers. The analysis of their thermal, dynamical mechanical, nuclear magnetic relaxation, electrical, and electrochemical properties shows that this new class of polymer electrolytes has the same performances as ethylene poly-oxide based amorphous lattices plus the advantage of having good filmic properties. Abstract only. (J.S.)

New polysaccharide-based polymer electrolytes; Nouveaux electrolytes polymeres a base de polysaccharides

Energy Technology Data Exchange (ETDEWEB)

Velasquez-Morales, P; Le Nest, J F; Gandini, A [Ecole Francaise de Papeterie et des Industries Graphique, 38 - Saint Martin d` Heres (France)

1997-12-31

Polysaccharides like cellulose and chitosan are known for their filmic properties. This paper concerns the synthesis and the study of chitosan-based polymer electrolytes. A preliminary work concerns the study of glucosamine reactivity. The poly-condensation of chitosan ethers (obtained by reaction with ethylene oxide or propylene oxide) with bifunctional and monofunctional oligo-ethers leads to the formation of thin lattices (10 {mu}m) having excellent mechanical properties. The presence of grafted polyether chains along the polysaccharide skeleton allows to modify the vitreous transition temperature and the molecular disorder of the system. Two type of polymer electrolytes have been synthesized: electrolytes carrying a dissolved alkaline metal salt and ionomers. The analysis of their thermal, dynamical mechanical, nuclear magnetic relaxation, electrical, and electrochemical properties shows that this new class of polymer electrolytes has the same performances as ethylene poly-oxide based amorphous lattices plus the advantage of having good filmic properties. Abstract only. (J.S.)

Complex hydrides as room-temperature solid electrolytes for rechargeable batteries

DEFF Research Database (Denmark)

Jongh, P. E. de; Blanchard, D.; Matsuo, M.

2016-01-01

A central goal in current battery research is to increase the safety and energy density of Li-ion batteries. Electrolytes nowadays typically consist of lithium salts dissolved in organic solvents. Solid electrolytes could facilitate safer batteries with higher capacities, as they are compatible...... electrolytes, discussing in detail LiBH4, strategies towards for fast room-temperature ionic conductors, alternative compounds, and first explorations of implementation of these electrolytes in all-solid-state batteries....

Carboxymethyl Carrageenan Based Biopolymer Electrolytes

International Nuclear Information System (INIS)

Mobarak, N.N.; Jumaah, F.N.; Ghani, M.A.; Abdullah, M.P.; Ahmad, A.

2015-01-01

Highlights: • The paper highlights the potential of carboxymethyl carrageenan based on iota and kappa to be utilized as host polymer. • The highest conductivity were achieved up to ∼10 −3 S cm −1 by carboxymethyl carrageenan without the addition of plasticizer. • The electrochemical stability windows of the films were electrochemically stable up to 3.0 V. - Abstract: A series of biodegradable carboxymethyl carrageenan based polymer electrolytes, which are carboxymethyl kappa carrageenan (sulphate per disaccharide) and carboxymethyl iota carrageenan (two sulphates per disaccharide), have been prepared by a solution casting technique with different ratios of lithium nitrate (LiNO 3 ) salts. Interestingly, the lithium ions tended to interact with the carbonyl group in the different modes of symmetry, as observed from reflection Fourier transform infrared (ATR-FTIR) spectroscopy analysis. In the carboxymethyl kappa carrageenan electrolytes, as the concentration of LiNO 3 increased, the asymmetric stretching peak of the carbonyl bond became dominant because it can be observed clearly with the shifting of the peak from 1592 to 1602 cm −1 due to the interaction between the lithium ion and the carbonyl group, while the broad O-H stretching peak became sharp and intense. However, for the carboxymethyl iota carrageenan, the asymmetry stretching mode of the carbonyl group shifted from 1567 to 1599 cm −1 , as the salt concentration increased. The shifting of the C-O-C peak also occurred in the iota-based electrolytes. However, the changes in the peak that represented SO 4 2− symmetric stretching were only detected when the ion pair formation was observed. It was proposed that the peak shifting was due to the presence of the lithium ion pathway, forming a dative bond between the lithium and oxygen in the carbonyl group. Accordingly, as more peak shifting was observed, the number of the ion pathways also increased. This hypothesis was supported by the impedance

Polymer electrolytes based on aromatic lithium sulfonyl-imide compounds; Electrolytes polymeres a base de sulfonylimidures de lithium aromatiques

Energy Technology Data Exchange (ETDEWEB)

Reibel, L.; Bayoudh, S. [Centre National de la Recherche Scientifique (CNRS), 67 - Strasbourg (France). Institut Charles Sadron; Baudry, P. [Electricite de France, 77 - Moret sur Loing (France). Direction des Etudes et Recherches; Majastre, H. [Bollore Technologies, 29 - Quimper (France); Herlem, G. [UFR de Sciences et Techniques, L.E.S., 25 - Besancon (France)

1996-12-31

This paper presents ionic conductivity results obtained with polymer electrolytes and also with propylene carbonate solutions. The domain of electrochemical activity of this salt has been determined using cycle volt-amperometry in propylene carbonate. Preliminary experiments on the stability of the polymer electrolyte with respect to the lithium electrode have been carried out for a possible subsequent use in lithium batteries. (J.S.) 4 refs.

Polymer electrolytes based on aromatic lithium sulfonyl-imide compounds; Electrolytes polymeres a base de sulfonylimidures de lithium aromatiques

Energy Technology Data Exchange (ETDEWEB)

Reibel, L; Bayoudh, S [Centre National de la Recherche Scientifique (CNRS), 67 - Strasbourg (France). Institut Charles Sadron; Baudry, P [Electricite de France, 77 - Moret sur Loing (France). Direction des Etudes et Recherches; Majastre, H [Bollore Technologies, 29 - Quimper (France); Herlem, G [UFR de Sciences et Techniques, L.E.S., 25 - Besancon (France)

1997-12-31

This paper presents ionic conductivity results obtained with polymer electrolytes and also with propylene carbonate solutions. The domain of electrochemical activity of this salt has been determined using cycle volt-amperometry in propylene carbonate. Preliminary experiments on the stability of the polymer electrolyte with respect to the lithium electrode have been carried out for a possible subsequent use in lithium batteries. (J.S.) 4 refs.

Acemetacin cocrystals and salts: structure solution from powder X-ray data and form selection of the piperazine salt

Directory of Open Access Journals (Sweden)

Palash Sanphui

2014-03-01

Full Text Available Acemetacin (ACM is a non-steroidal anti-inflammatory drug (NSAID, which causes reduced gastric damage compared with indomethacin. However, acemetacin has a tendency to form a less soluble hydrate in the aqueous medium. We noted difficulties in the preparation of cocrystals and salts of acemetacin by mechanochemical methods, because this drug tends to form a hydrate during any kind of solution-based processing. With the objective to discover a solid form of acemetacin that is stable in the aqueous medium, binary adducts were prepared by the melt method to avoid hydration. The coformers/salt formers reported are pyridine carboxamides [nicotinamide (NAM, isonicotinamide (INA, and picolinamide (PAM], caprolactam (CPR, p-aminobenzoic acid (PABA, and piperazine (PPZ. The structures of an ACM–INA cocrystal and a binary adduct ACM–PABA were solved using single-crystal X-ray diffraction. Other ACM cocrystals, ACM–PAM and ACM–CPR, and the piperazine salt ACM–PPZ were solved from high-resolution powder X-ray diffraction data. The ACM–INA cocrystal is sustained by the acid...pyridine heterosynthon and N—H...O catemer hydrogen bonds involving the amide group. The acid...amide heterosynthon is present in the ACM–PAM cocrystal, while ACM–CPR contains carboxamide dimers of caprolactam along with acid–carbonyl (ACM hydrogen bonds. The cocrystals ACM–INA, ACM–PAM and ACM–CPR are three-dimensional isostructural. The carboxyl...carboxyl synthon in ACM–PABA posed difficulty in assigning the position of the H atom, which may indicate proton disorder. In terms of stability, the salts were found to be relatively stable in pH 7 buffer medium over 24 h, but the cocrystals dissociated to give ACM hydrate during the same time period. The ACM–PPZ salt and ACM–nicotinamide cocrystal dissolve five times faster than the stable hydrate form, whereas the ACM–PABA adduct has 2.5 times faster dissolution rate. The pharmaceutically acceptable

Acemetacin cocrystals and salts: structure solution from powder X-ray data and form selection of the piperazine salt.

Science.gov (United States)

Sanphui, Palash; Bolla, Geetha; Nangia, Ashwini; Chernyshev, Vladimir

2014-03-01

Acemetacin (ACM) is a non-steroidal anti-inflammatory drug (NSAID), which causes reduced gastric damage compared with indomethacin. However, acemetacin has a tendency to form a less soluble hydrate in the aqueous medium. We noted difficulties in the preparation of cocrystals and salts of acemetacin by mechanochemical methods, because this drug tends to form a hydrate during any kind of solution-based processing. With the objective to discover a solid form of acemetacin that is stable in the aqueous medium, binary adducts were prepared by the melt method to avoid hydration. The coformers/salt formers reported are pyridine carboxamides [nicotinamide (NAM), isonicotinamide (INA), and picolinamide (PAM)], caprolactam (CPR), p-aminobenzoic acid (PABA), and piperazine (PPZ). The structures of an ACM-INA cocrystal and a binary adduct ACM-PABA were solved using single-crystal X-ray diffraction. Other ACM cocrystals, ACM-PAM and ACM-CPR, and the piperazine salt ACM-PPZ were solved from high-resolution powder X-ray diffraction data. The ACM-INA cocrystal is sustained by the acid⋯pyridine heterosynthon and N-H⋯O catemer hydrogen bonds involving the amide group. The acid⋯amide heterosynthon is present in the ACM-PAM cocrystal, while ACM-CPR contains carboxamide dimers of caprolactam along with acid-carbonyl (ACM) hydrogen bonds. The cocrystals ACM-INA, ACM-PAM and ACM-CPR are three-dimensional isostructural. The carboxyl⋯carboxyl synthon in ACM-PABA posed difficulty in assigning the position of the H atom, which may indicate proton disorder. In terms of stability, the salts were found to be relatively stable in pH 7 buffer medium over 24 h, but the cocrystals dissociated to give ACM hydrate during the same time period. The ACM-PPZ salt and ACM-nicotinamide cocrystal dissolve five times faster than the stable hydrate form, whereas the ACM-PABA adduct has 2.5 times faster dissolution rate. The pharmaceutically acceptable piperazine salt of acemetacin exhibits superior

Measuring and modeling aqueous electrolyte/amino-acid solutions with ePC-SAFT

International Nuclear Information System (INIS)

Held, Christoph; Reschke, Thomas; Müller, Rainer; Kunz, Werner; Sadowski, Gabriele

2014-01-01

Highlights: • Amino-acid solubilities and osmotic coefficients in ternary solutions containing one amino acids and one salt measured. • Weak salt influence on amino-acid solubilities except for salts containing Mg [2+] or NO 3 [−] (salting-in behavior). • Osmotic coefficients dominated by the solute with the highest molality. • Amino-acid solubilities and osmotic coefficients predicted reasonably with ePC-SAFT with deviations of 3.7% and 9.3%. • Predictions based on pure-component parameters for ions and amino acids using no ion/amino-acid fitting parameters. -- Abstract: In this work thermodynamic properties of electrolyte/amino acid/water solutions were measured and modeled. Osmotic coefficients at 298.15 K were measured by means of vapor-pressure osmometry. Amino-acid solubility at 298.15 K was determined gravimetrically. Considered aqueous systems contained one of the four amino acids: glycine, L-/DL-alanine, L-/DL-valine, and L-proline up to the respective amino-acid solubility limit and one of 13 salts composed of the ions Li + , Na + , K + , NH 4 + , Cl − , Br − , I − , NO 3 − , and SO 4 2− at salt molalities of 0.5, 1.0, and 3.0 mol · kg −1 , respectively. The data show that the salt influence is more pronounced on osmotic coefficients than on amino-acid solubility. The electrolyte Perturbed-Chain Statistical Association Theory (ePC-SAFT) was applied to model thermodynamic properties in aqueous electrolyte/amino-acid solutions. In previous works, this model had been applied to binary salt/water and binary amino acid/water systems. Without fitting any additional parameters, osmotic coefficients and amino-acid solubility in the ternary electrolyte/amino acid/water systems could be predicted with overall deviations of 3.7% and 9.3%, respectively, compared to the experimental data

Feasibility of salt reduction in processed foods in Argentina Factibilidad de reducir el contenido de sal de los alimentos procesados en la Argentina

Directory of Open Access Journals (Sweden)

Daniel Ferrante

2011-02-01

Full Text Available OBJECTIVE: To assess an intervention to reduce salt intake based on an agreement with the food industry. METHODS: Salt content was measured in bakery products through a national survey and biochemical analyses. Low-salt bread was evaluated by a panel of taste testers to determine whether a reduced salt bread could remain undetected. French bread accounts for 25% of the total salt intake in Argentina; hence, reducing its salt concentration from 2% to 1.4% was proposed and tested. A crossover trial was conducted to evaluate the reduction in urinary sodium and blood pressure in participants during consumption of the low-salt bread compared with ordinary bread. RESULTS: Average salt content in bread was 2%. This study evaluated low-salt bread containing 1.4% salt. This reduction remained mostly undetected by the panels of taste testers. In the crossover trial, which included 58 participants, a reduction of 25 milliequivalents in 24hour urine sodium excretion, a reduction in systolic blood pressure of 1.66 mmHg, and a reduction in diastolic blood pressure of 0.76 mmHg were found during the low-salt bread intake. CONCLUSIONS: The study showed that dietary salt reduction was feasible and well accepted in the population studied through a reduction of salt content in bread. Although the effects on urinary sodium and blood pressure were moderate, a countrywide intervention could have a greater public health impact.OBJETIVO: Evaluar una intervención destinada a reducir el consumo de sal a partir de un convenio con la industria alimentaria. MÉTODOS: Se midió el contenido de sal de los productos de panadería por medio de una encuesta nacional y análisis bioquímicos. Un grupo de catadores evaluó el pan con bajo contenido de sal para determinar si la disminución pasaba inadvertida. Dado que el pan francés representa 25% del consumo total de sal en la Argentina, se propuso someter a prueba este tipo de pan con una disminución de la concentración de

Hot corrosion behavior of plasma-sprayed partially stabilized zirconia coatings in a lithium molten salt

International Nuclear Information System (INIS)

Cho, Soo Haeng; Hong, Sun Seok; Kang, Dae Seong; Park, Byung Heong; Hur, Jin Mok; Lee, Han Soo

2008-01-01

The electrolytic reduction of spent oxide fuel involves the liberation of oxygen in a molten LiCl electrolyte, which results in a chemically aggressive environment that is too corrosive for typical structural materials. It is essential to choose the optimum material for the process equipment handling molten salt. IN713LC is one of the candidate materials proposed for application in electrolytic reduction process. In this study, Yttria-Stabilized Zirconia (YSZ) top coat was applied to a surface of IN713LC with an aluminized metallic bond coat by an optimized plasma spray process, and were investigated the corrosion behavior at 675 .deg. C for 216 hours in the molten salt LiCl-Li 2 O under an oxidizing atmosphere. The as-coated and tested specimens were examined by OM, SEM/EDS and XRD, respectively. The bare superalloy reveals obvious weight loss, and the corrosion layer formed on the surface of the bare superalloy was spalled due to the rapid scale growth and thermal stress. The top coatings showed a much better hot-corrosion resistance in the presence of LiCl-Li 2 O molten salt when compared to those of the uncoated superalloy and the aluminized bond coatings. These coatings have been found to be beneficial for increasing to the hot-corrosion resistance of the structural materials for handling high temperature lithium molten salts

"Water-in-salt" electrolyte enables high-voltage aqueous lithium-ion chemistries.

Science.gov (United States)

Suo, Liumin; Borodin, Oleg; Gao, Tao; Olguin, Marco; Ho, Janet; Fan, Xiulin; Luo, Chao; Wang, Chunsheng; Xu, Kang

2015-11-20

Lithium-ion batteries raise safety, environmental, and cost concerns, which mostly arise from their nonaqueous electrolytes. The use of aqueous alternatives is limited by their narrow electrochemical stability window (1.23 volts), which sets an intrinsic limit on the practical voltage and energy output. We report a highly concentrated aqueous electrolyte whose window was expanded to ~3.0 volts with the formation of an electrode-electrolyte interphase. A full lithium-ion battery of 2.3 volts using such an aqueous electrolyte was demonstrated to cycle up to 1000 times, with nearly 100% coulombic efficiency at both low (0.15 coulomb) and high (4.5 coulombs) discharge and charge rates. Copyright © 2015, American Association for the Advancement of Science.

Equilibrium calculation for the electrolytic reduction process of the ACP

International Nuclear Information System (INIS)

Park, Byung Heung; Seo, Chung Seok; Yoon, Ji Sup

2006-01-01

The electrolytic reduction process is the most critical process of the advanced spent fuel conditioning process (ACP) since most of the chemical reactions take place during this reduction process in a molten salt bath. However, it is very difficult to observe the behavior of all the spent fuel elements by experiments. Therefore, a perspective calculation is required to predict how much the chemicals are distributed between the phases and which forms are stable in each phase. Chemical equilibria take place during the electrolytic reduction process. The reduction process uses a porous magnesia filter and the materials to be reduced are loaded into the filter, which means the filter, the cathode of the electrolytic reduction cell, acts as a packed-bed reactor. Lithium metal is produced by an electrolytic reaction in a molten Li 2 O-LiCl cell and the reaction is denoted as Eq. In this work, attention has been paid to the chemical reactions of Eq. since an electrochemical reaction is controlled easily by the supplied current and the extents of the chemical reactions are determined by considering many candidates species. Uranium oxides, for example, can be reduced to U 4 O 9 , UO 2 , and/or U when U 3 O 8 is fed to the electrolytic reduction process

Polymer-electrolyte-gated nanowire synaptic transistors for neuromorphic applications

Science.gov (United States)

Zou, Can; Sun, Jia; Gou, Guangyang; Kong, Ling-An; Qian, Chuan; Dai, Guozhang; Yang, Junliang; Guo, Guang-hua

2017-09-01

Polymer-electrolytes are formed by dissolving a salt in polymer instead of water, the conducting mechanism involves the segmental motion-assisted diffusion of ion in the polymer matrix. Here, we report on the fabrication of tin oxide (SnO2) nanowire synaptic transistors using polymer-electrolyte gating. A thin layer of poly(ethylene oxide) and lithium perchlorate (PEO/LiClO4) was deposited on top of the devices, which was used to boost device performances. A voltage spike applied on the in-plane gate attracts ions toward the polymer-electrolyte/SnO2 nanowire interface and the ions are gradually returned after the pulse is removed, which can induce a dynamic excitatory postsynaptic current in the nanowire channel. The SnO2 synaptic transistors exhibit the behavior of short-term plasticity like the paired-pulse facilitation and self-adaptation, which is related to the electric double-effect regulation. In addition, the synaptic logic functions and the logical function transformation are also discussed. Such single SnO2 nanowire-based synaptic transistors are of great importance for future neuromorphic devices.

Supercapacitor Electrolyte Solvents with Liquid Range Below -80 C

Science.gov (United States)

Brandon, Erik; Smart, Marshall; West, William

2010-01-01

A previous NASA Tech Brief ["Low-Temperature Supercapacitors" (NPO-44386) NASA Tech Briefs, Vol. 32, No 7 (July 2008), page 32] detailed ongoing efforts to develop non-aqueous supercapacitor electrolytes capable of supporting operation at temperatures below commercially available cells (which are typically limited to charging and discharging at > or equal to -40 C). These electrolyte systems may enable energy storage and power delivery for systems operating in extreme environments, such as those encountered in the Polar regions on Earth or in the exploration of space. Supercapacitors using these electrolytes may also offer improved power delivery performance at moderately low temperatures (e.g. -40 to 0 C) relative to currently available cells, offering improved cold-cranking and cold-weather acceleration capabilities for electrical or hybrid vehicles. Supercapacitors store charge at the electrochemical double-layer, formed at the interface between a high surface area electrode material and a liquid electrolyte. The current approach to extending the low-temperature limit of the electrolyte focuses on using binary solvent systems comprising a high-dielectric-constant component (such as acetonitrile) in conjunction with a low-melting-point co-solvent (such as organic formates, esters, and ethers) to depress the freezing point of the system, while maintaining sufficient solubility of the salt. Recent efforts in this area have led to the identification of an electrolyte solvent formulation with a freezing point of -85.7 C, which is achieved by using a 1:1 by volume ratio of acetonitrile to 1,3-dioxolane

The effect of Li2CO3 substitution on synthesis of LiBOB compounds as salt of electrolyte battery lithium ion

Science.gov (United States)

Lestariningsih, Titik; Wigayati, Etty Marty; Sabrina, Qolby; Prihandoko, Bambang; Priyono, Slamet

2018-04-01

Development of the synthesis of LiB(C2O4)2 compounds continues to evolve along with the need for electrolyte salts to support the research of the manufacture of lithium ion batteries. A study had been conducted on the effect of Li2CO3 substitution on the synthesis of LiB(C2O4)2 or LiBOB compounds. LiBOB was a major candidate to replace LiPF6 as a highly toxic lithium battery electrolyte and harmful to human health. Synthesis of Lithium bis(oxalato) borate used powder metallurgy method. The raw materials used are H2C2O4.2H2O, Li2CO3 or LiOH and H2BO3 from Merck Germany products. The materials are mixed with 2: 1: 1 mol ratio until homogeneous. The synthesis of LiBOB refers to previous research, where the heating process was done gradually. The first stage heating is carried out at 120°C for 4 hours, then the next stage heating is carried out at 240°C for 7 hours. The sample variation in this study was to distinguish the lithium source from Li2CO3 and LiOH. Characterization was done by XRD to know the phase formed, FTIR to confirm that functional group of LiB(C2O4)2 compound, SEM to know the morphological structure, and TG/DTA to know the thermal properties. The results of the analysis shows that LiBOB synthesis using Lithium source from Li2CO3 has succeeded to form LiBOB compound with more LiBOB phase composition is 59.1% and 40.9% LiBOB hydrate phase, SEM morphology shows powder consist of elongated round particle porous and similar to LiBOB commercial and show higher thermal stability.

Structural study of anodic films formed on aluminum in nitric acid electrolyte

Energy Technology Data Exchange (ETDEWEB)

Yakovleva, N.M.; Anicai, L.; Yakovlev, A.N.; Dima, L.; Khanina, E.Ya.; Buda, M.; Chupakhina, E.A

2002-09-02

The paper presents the results of investigations of porous Al anodic films formed in HNO{sub 3} electrolytes carried out by means of electrochemical techniques and X-ray diffraction as well as scanning electron microscopy (SEM). It was assumed that both electrochemical formation of a porous oxide and anodic dissolution of metal take place at Al/oxide interface at the same time. The analysis of short-range order (SRO) parameters for relatively high current density, 1x10{sup 3} A/m{sup 2}, and anodizing time, 10 min, leads to the conclusion that films mainly consist of amorphous alumina with {gamma}'-Al{sub 2}O{sub 3}-like SRO and a small amount ({approx}10%) of amorphous aluminum oxyhydroxide. SEM investigation of the films revealed strong dependence of the surface relief on different applied forming conditions. This marked change in the surface relief is discussed taking into account the relatively complex behavior of Al during anodization in HNO{sub 3} electrolytes, that involves both electrochemical growth and dissolution processes of anodic film associated with an electrochemical dissolution of aluminum substrate.

Structural study of anodic films formed on aluminum in nitric acid electrolyte

International Nuclear Information System (INIS)

Yakovleva, N.M.; Anicai, L.; Yakovlev, A.N.; Dima, L.; Khanina, E.Ya.; Buda, M.; Chupakhina, E.A.

2002-01-01

The paper presents the results of investigations of porous Al anodic films formed in HNO 3 electrolytes carried out by means of electrochemical techniques and X-ray diffraction as well as scanning electron microscopy (SEM). It was assumed that both electrochemical formation of a porous oxide and anodic dissolution of metal take place at Al/oxide interface at the same time. The analysis of short-range order (SRO) parameters for relatively high current density, 1x10 3 A/m 2 , and anodizing time, 10 min, leads to the conclusion that films mainly consist of amorphous alumina with γ'-Al 2 O 3 -like SRO and a small amount (∼10%) of amorphous aluminum oxyhydroxide. SEM investigation of the films revealed strong dependence of the surface relief on different applied forming conditions. This marked change in the surface relief is discussed taking into account the relatively complex behavior of Al during anodization in HNO 3 electrolytes, that involves both electrochemical growth and dissolution processes of anodic film associated with an electrochemical dissolution of aluminum substrate

The electrochemical reduction processes of solid compounds in high temperature molten salts.

Science.gov (United States)

Xiao, Wei; Wang, Dihua

2014-05-21

Solid electrode processes fall in the central focus of electrochemistry due to their broad-based applications in electrochemical energy storage/conversion devices, sensors and electrochemical preparation. The electrolytic production of metals, alloys, semiconductors and oxides via the electrochemical reduction of solid compounds (especially solid oxides) in high temperature molten salts has been well demonstrated to be an effective and environmentally friendly process for refractory metal extraction, functional materials preparation as well as spent fuel reprocessing. The (electro)chemical reduction of solid compounds under cathodic polarizations generally accompanies a variety of changes at the cathode/melt electrochemical interface which result in diverse electrolytic products with different compositions, morphologies and microstructures. This report summarizes various (electro)chemical reactions taking place at the compound cathode/melt interface during the electrochemical reduction of solid compounds in molten salts, which mainly include: (1) the direct electro-deoxidation of solid oxides; (2) the deposition of the active metal together with the electrochemical reduction of solid oxides; (3) the electro-inclusion of cations from molten salts; (4) the dissolution-electrodeposition process, and (5) the electron hopping process and carbon deposition with the utilization of carbon-based anodes. The implications of the forenamed cathodic reactions on the energy efficiency, chemical compositions and microstructures of the electrolytic products are also discussed. We hope that a comprehensive understanding of the cathodic processes during the electrochemical reduction of solid compounds in molten salts could form a basis for developing a clean, energy efficient and affordable production process for advanced/engineering materials.

New glyme-cyclic imide lithium salt complexes as thermally stable electrolytes for lithium batteries

Science.gov (United States)

Tamura, Takashi; Hachida, Takeshi; Yoshida, Kazuki; Tachikawa, Naoki; Dokko, Kaoru; Watanabe, Masayoshi

New glyme-Li salt complexes were prepared by mixing equimolar amounts of a novel cyclic imide lithium salt LiN(C 2F 4S 2O 4) (LiCTFSI) and a glyme (triglyme (G3) or tetraglyme (G4)). The glyme-Li salt complexes, [Li(G3)][CTFSI] and [Li(G4)][CTFSI], are solid and liquid, respectively, at room temperature. The thermal stability of [Li(G4)][CTFSI] is much higher than that of pure G4, and the vapor pressure of [Li(G4)][CTFSI] is negligible at temperatures lower than 100 °C. Although the viscosity of [Li(G4)][CTFSI] is high (132.0 mPa s at 30 °C), because of its high molar concentration (ca. 3 mol dm -3), its ionic conductivity at 30 °C is relatively high, i.e., 0.8 mS cm -1, which is slightly lower than that of a conventional organic electrolyte solution (1 mol dm -3 LiTFSI dissolved in propylene carbonate). The self-diffusion coefficients of a Li + cation, a CTFSI - anion, and a glyme molecule were measured by the pulsed gradient spin-echo NMR method (PGSE-NMR). The ionicity (dissociativity) of [Li(G4)][CTFSI] at 30 °C is ca. 0.5, as estimated from the PGSE-NMR diffusivity measurements and the ionic conductivity measurements. Results of linear sweep voltammetry revealed that [Li(G4)][CTFSI] is electrochemically stable in an electrode potential range of 0-4.5 V vs. Li/Li +. The reversible deposition-stripping behavior of lithium was observed by cyclic voltammetry. The [LiCoO 2|[Li(G4)][CTFSI]|Li metal] cell showed a stable charge-discharge cycling behavior during 50 cycles, indicating that the [Li(G4)][CTFSI] complex is applicable to a 4 V class lithium secondary battery.

Corrosion behaviors and effects of corrosion products of plasma electrolytic oxidation coated AZ31 magnesium alloy under the salt spray corrosion test

Science.gov (United States)

Wang, Yan; Huang, Zhiquan; Yan, Qin; Liu, Chen; Liu, Peng; Zhang, Yi; Guo, Changhong; Jiang, Guirong; Shen, Dejiu

2016-08-01

The effects of corrosion products on corrosion behaviors of AZ31 magnesium alloy with a plasma electrolytic oxidation (PEO) coating were investigated under the salt spray corrosion test (SSCT). The surface morphology, cross-sectional microstructure, chemical and phase compositions of the PEO coating were determined using scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction analysis (XRD), respectively. Further, the corrosion process of the samples under the SSCT was examined in a non-aqueous electrolyte (methanol) using electrochemical impedance spectroscopy (EIS) coupled with equivalent circuit. The results show that the inner layer of the coating was destroyed firstly and the corrosion products have significant effects on the corrosion behaviors of the coating. The results above are discussed and an electrochemical corrosion model is proposed in the paper.

Lithium Organic Borate Salt and Sulfite Functional Electrolytes%有机硼酸锂盐及亚硫酸酯类功能电解质材料

Institute of Scientific and Technical Information of China (English)

陈人杰; 何舟影; 吴锋

2011-01-01

随着锂离子电池对高安全性、高容量、高功率等性能的技术需求,新型功能电解质材料的研究开发成为锂离子电池新材料领域研发工作的重点.本文对面向锂离子电池应用的功能电解质材料锂盐和添加剂的最新研究进展作了较为全面的阐述,其中重点介绍了本研究团队近年来在面向改善锂离子电池安全性能、提高其温度适应性、增强电解质与电极材料相容特性等方面研究开发的系列基于双草酸硼酸锂[LiBOB]及二氟草酸硼酸锂[LiODFB]等有机硼酸锂盐和亚硫酸酯类等添加剂的新型功能电解质材料,其表现出高的热稳定性和良好的电化学性能.而且,其中的有机硼酸锂盐和亚硫酸酯还可以作为SEI成膜材料进行应用,其在石墨电极表面可形成稳定的SEI膜,有利于改善电池的循环寿命、自放电、库仑效率和不可逆容量衰减.最后,本文探讨了当前存在的问题及未来的研究方向,并对其应用前景进行了展望.%With the rapid development of lithium ion batteries with higher energy density, higher power density and high security, the research of new functional electrolytes has attracted considerable attention in novel materials field for lithium ion batteries.In this paper, the recent research advances of key technologies on the application of lithium salts and additive functional electrolytes in lithium ion batteries are reviewed, especially on the results of our research team focusing on new functional electrolytes based on lithium organic borate salt, such as lithium bis(oxalato) borate [LiBOB]and lithium oxalyldifluoroborate [LiODFB], and sulfite additives for the purpose of improving security, temperature adaptability and the compatibility between electrolytes and electrodes of lithium ion batteries.These electrolytes exhibit high thermal stability and good electrochemical properties.Moreover, lithium organic borate salt and sulfite have been

Investigations of the Electrochemical Stability of Aqueous Electrolytes for Lithium Battery Applications

KAUST Repository

Wessells, Colin; Ruffο, Riccardo; Huggins, Robert A.; Cui, Yi

2010-01-01

The electrolytic stability windows of several aqueous electrolytes were investigated by a constant current method. The electrode potential range depended upon the value of the imposed current. The magnitude of this behavior varied with the salt

Interplay Between Structure and Conductivity in 1-Ethyl-3-methylimidazolium tetrafluoroborate/(δ-MgCl2)f Electrolytes for Magnesium Batteries

International Nuclear Information System (INIS)

Bertasi, Federico; Vezzù, Keti; Nawn, Graeme; Pagot, Gioele; Di Noto, Vito

2016-01-01

The synthesis, physicochemical properties and conductivity mechanism of a family of ionic liquid-based electrolytes for use in secondary Mg batteries are reported. The electrolytes are obtained by dissolving controlled amounts of δ-MgCl 2 salt into the ionic liquid (IL) 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF 4 ) which acts as a solvent. δ-MgCl 2 consists of an inorganic ribbon of Mg atoms covalently bonded together through bridging chlorine atoms. Due to this peculiar structural motif, with respect to the electrolytes based on conventional Mg salts, it is possible to achieve electrolytes of higher Mg concentration. Thus, concatenated anionic complexes bridged via halogen atoms are formed, improving the electrochemical performance of these materials. Electrolytes with a general formula EMImBF 4 /(δ-MgCl 2 ) f with f ranging from 0 to 0.117 are obtained. The composition of the obtained materials is determined by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES). The properties of these systems are investigated by means of Thermogravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC), and vibrational spectroscopy in both medium (MIR) and far infrared (FIR). Finally, Broadband Electrical Spectroscopy (BES) is carried out with the aim to elucidate the electrical response of the electrolytes in terms of their polarization and relaxation phenomena and to propose a conductivity mechanism. At 20 °C the highest conductivity (0.007 S/cm) is observed for the electrolyte with c Mg = 0.00454 mol Mg /kg IL .

Gravimetric and volumetric determination of the purity of electrolytically refined silver and the produced silver nitrate

Directory of Open Access Journals (Sweden)

Ačanski Marijana M.

2007-01-01

Full Text Available Silver is, along with gold and the platinum-group metals, one of the so called precious metals. Because of its comparative scarcity, brilliant white color, malleability and resistance to atmospheric oxidation, silver has been used in the manufacture of coins and jewelry for a long time. Silver has the highest known electrical and thermal conductivity of all metals and is used in fabricating printed electrical circuits, and also as a coating for electronic conductors. It is also alloyed with other elements such as nickel or palladium for use in electrical contacts. The most useful silver salt is silver nitrate, a caustic chemical reagent, significant as an antiseptic and as a reagent in analytical chemistry. Pure silver nitrate is an intermediate in the industrial preparation of other silver salts, including the colloidal silver compounds used in medicine and the silver halides incorporated into photographic emulsions. Silver halides become increasingly insoluble in the series: AgCl, AgBr, AgI. All silver salts are sensitive to light and are used in photographic coatings on film and paper. The ZORKA-PHARMA company (Sabac, Serbia specializes in the production of pharmaceutical remedies and lab chemicals. One of its products is chemical silver nitrate (argentum-nitricum (l. Silver nitrate is generally produced by dissolving pure electrolytically refined silver in hot 48% nitric acid. Since the purity of silver nitrate, produced in 2002, was not in compliance with the p.a. level of purity, there was doubt that the electrolytically refined silver was pure. The aim of this research was the gravimetric and volumetric determination of the purity of electrolytically refined silver and silver nitrate, produced industrially and in a laboratory. The purity determination was carried out gravimetrically, by the sedimentation of silver(I ions in the form of insoluble silver salts: AgCl, AgBr and Agi, and volumetrically, according to Mohr and Volhardt. The

Electrolyte creepage barrier for liquid electrolyte fuel cells

Science.gov (United States)

Li, Jian [Alberta, CA; Farooque, Mohammad [Danbury, CT; Yuh, Chao-Yi [New Milford, CT

2008-01-22

A dielectric assembly for electrically insulating a manifold or other component from a liquid electrolyte fuel cell stack wherein the dielectric assembly includes a substantially impermeable dielectric member over which electrolyte is able to flow and a barrier adjacent the dielectric member and having a porosity of less than 50% and greater than 10% so that the barrier is able to measurably absorb and chemically react with the liquid electrolyte flowing on the dielectric member to form solid products which are stable in the liquid electrolyte. In this way, the barrier inhibits flow or creepage of electrolyte from the dielectric member to the manifold or component to be electrically insulated from the fuel cell stack by the dielectric assembly.

Separation and Recovery of Uranium Metal from Spent Light Water Reactor Fuel via Electrolytic Reduction and Electrorefining

International Nuclear Information System (INIS)

Herrmann, S.D.; Li, S.X.

2010-01-01

A series of bench-scale experiments was performed in a hot cell at Idaho National Laboratory to demonstrate the separation and recovery of uranium metal from spent light water reactor (LWR) oxide fuel. The experiments involved crushing spent LWR fuel to particulate and separating it from its cladding. Oxide fuel particulate was then converted to metal in a series of six electrolytic reduction runs that were performed in succession with a single salt loading of molten LiCl - 1 wt% Li2O at 650 C. Analysis of salt samples following the series of electrolytic reduction runs identified the diffusion of select fission products from the spent fuel to the molten salt electrolyte. The extents of metal oxide conversion in the post-test fuel were also quantified, including a nominal 99.7% conversion of uranium oxide to metal. Uranium metal was then separated from the reduced LWR fuel in a series of six electrorefining runs that were performed in succession with a single salt loading of molten LiCl-KCl-UCl3 at 500 C. Analysis of salt samples following the series of electrorefining runs identified additional partitioning of fission products into the molten salt electrolyte. Analyses of the separated uranium metal were performed, and its decontamination factors were determined.

Triethyl orthoformate as a new film-forming electrolytes solvent for lithium-ion batteries with graphite anodes

International Nuclear Information System (INIS)

Wang Lishi; Huang Yudai; Jia Dianzeng

2006-01-01

Triethyl orthoformate (TEOF) as a new solvent used in propylene carbonate (PC)-based electrolytes together with graphitic anodes in lithium-ion batteries has been investigated. It can be observed that TEOF was capable of suppressing the co-intercalation of PC solvated lithium-ions into the graphite layer during the first lithiation process and the irreversible discharge capacity of the first cycle is the smallest when using 1.0 M LiPF 6 in PC and TEOF at solvent ratio of 1:1 as the electrolytes. The CV, FTIR, EIS, SEM results show that the PC-based electrolytes containing the solvent TEOF can generate an effective solid electrolytes interphase (SEI) film during the first cycling process, and the film is probably mainly composed of ROCO 2 Li, ROLi, Li 2 CO 3 , etc. The formation of a stable passivating film on the graphite surface is believed to be the reason for the improved cell performance. All these results show that TEOF possesses a promising performance for use as an effective film-forming electrolytes solvent in lithium-ion batteries with graphitic anodes

Electrolytic reduction runs of 0.6 kg scale-simulated oxide fuel in a Li{sub 2}O-LiCl molten salt using metal anode shrouds

Energy Technology Data Exchange (ETDEWEB)

Choi, Eun-Young, E-mail: eychoi@kaeri.re.kr [Korea Atomic Energy Research Institute, Daedoek-daero 989-111, Yuseong-gu, Daejeon 34057 (Korea, Republic of); Lee, Jeong; Heo, Dong Hyun; Lee, Sang Kwon [Korea Atomic Energy Research Institute, Daedoek-daero 989-111, Yuseong-gu, Daejeon 34057 (Korea, Republic of); Jeon, Min Ku [Korea Atomic Energy Research Institute, Daedoek-daero 989-111, Yuseong-gu, Daejeon 34057 (Korea, Republic of); Department of Quantum Energy Chemical Engineering, University of Science and Technology, Gajeong-ro 217, Yuseong-gu, Daejeon 34113 (Korea, Republic of); Hong, Sun Seok [Korea Atomic Energy Research Institute, Daedoek-daero 989-111, Yuseong-gu, Daejeon 34057 (Korea, Republic of); Kim, Sung-Wook [Korea Atomic Energy Research Institute, Daedoek-daero 989-111, Yuseong-gu, Daejeon 34057 (Korea, Republic of); Department of Quantum Energy Chemical Engineering, University of Science and Technology, Gajeong-ro 217, Yuseong-gu, Daejeon 34113 (Korea, Republic of); Kang, Hyun Woo; Jeon, Sang-Chae; Hur, Jin-Mok [Korea Atomic Energy Research Institute, Daedoek-daero 989-111, Yuseong-gu, Daejeon 34057 (Korea, Republic of)

2017-06-15

Ten electrolytic reduction or oxide reduction (OR) runs of a 0.6 kg scale-simulated oxide fuel in a Li{sub 2}O-LiCl molten salt at 650 °C were conducted using metal anode shrouds. During this procedure, an anode shroud surrounds a platinum anode and discharges hot oxygen gas from the salt to outside of the OR apparatus, thereby preventing corrosion of the apparatus. In this study, a number of anode shrouds made of various metals were tested. Each metallic anode shroud consisted of a lower porous shroud for the salt phase and an upper nonporous shroud for the gas phase. A stainless steel (STS) wire mesh with five-ply layer was a material commonly used for the lower porous shroud for the OR runs. The metals tested for the upper nonporous shroud in the different OR runs are STS, nickel, and platinum- or silver-lined nickel. The lower porous shroud showed no significant damage during two consecutive OR runs, but exhibited signs of damage from three or more runs due to thermal stress. The upper nonporous shrouds made up of either platinum- or silver-lined nickel showed excellent corrosion resistance to hot oxygen gas while STS or nickel without any platinum or silver lining exhibited poor corrosion resistance. - Highlights: •Electrolytic reduction runs of a 0.6 kg scale-simulated oxide fuel in a Li{sub 2}O-LiCl molten salt at 650 °C were conducted using metal anode shrouds. •Each metallic anode shroud consisted of a lower porous shroud for the salt phase and an upper nonporous shroud for the gas phase. •The upper nonporous shrouds made up of noble metal-lined nickel showed excellent corrosion resistance to hot oxygen gas.

Conductivity through Polymer Electrolytes and Its Implications in Lithium-Ion Batteries: Real-World Application of Periodic Trends

Science.gov (United States)

Compton, Owen C.; Egan, Martin; Kanakaraj, Rupa; Higgins, Thomas B.; Nguyen, SonBinh T.

2012-01-01

Periodic conductivity trends are placed in the scope of lithium-ion batteries, where increases in the ionic radii of salt components affect the conductivity of a poly(ethyleneoxide)-based polymer electrolyte. Numerous electrolytes containing varying concentrations and types of metal salts are prepared and evaluated in either one or two laboratory…

Electrochemical oxidation of quaternary ammonium electrolytes : Unexpected side reactions in organic electrochemistry

NARCIS (Netherlands)

Nouri Nigjeh, Eslam; de Vries, Marcel; Bruins, Andries P.; Bischoff, Rainer; Permentier, Hjalmar P.

Quaternary ammonium salts are among the most widely used electrolytes in organic electrochemistry, but there is little known about their unwanted side oxidation reactions. We have, therefore, studied the constant potential oxidation products of quaternary ammonium electrolytes using mass

Role of salt concentration in blend polymer for energy storage conversion devices

Energy Technology Data Exchange (ETDEWEB)

Arya, Anil; Sharma, A. L., E-mail: alsharmaiitkgp@gmail.com [Centre for Physical Sciences, Central university of Punjab, Bathinda-151001. INDIA (India); Sadiq, M. [Department of Physics, I.I.T. (BHU), Varanasi-India (India)

2016-05-06

Solid Polymer Electrolytes (SPE) are materials of considerable interest worldwide, which serves dual purpose of electrolyte and separator between electrode compartments in renewable energy conversion/storage devices such as; high energy density batteries, electrochromic display devices, and supercapacitors. Polymer blend electrolytes are prepared for various concentration of salt (Ö/Li) with the constant ratio (0.5 gm) of each PEO and PAN polymers (blend polymer) using solution casting technique. Solid polymeric ionic conductor as a separator is the ultimate substitute to eliminate the drawback related to liquid and gel polymer ionic conductors. In the present work, solid polymer electrolyte film consisting of PEO, PAN and LiPF{sub 6} are examined for various concentration of lithium salt by keeping PEO/PAN blend ratio as a constant with a view to optimize the dominant salt concentration which could give the maximum conductivity at ambient temperature.

Conductivity of SDC and (Li/Na){sub 2}CO{sub 3} composite electrolytes in reducing and oxidising atmospheres

Energy Technology Data Exchange (ETDEWEB)

Boden, Andreas; Lagergren, Carina; Lindbergh, Goeran [KTH Chemical Science and Engineering, Applied Electrochemistry, SE-100 44 Stockholm (Sweden); Di, Jing; Wang, Cheng Yang [School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China)

2007-10-25

Composite electrolytes made of samarium-doped cerium oxide and a mixture of lithium carbonate and sodium carbonate salts are investigated with respect to their structure, morphology and ionic conductivity. The composite electrolytes are considered promising for use in so called intermediate temperature solid oxide fuel cells (IT-SOFC), operating at 400-600 C. The electrolytes are tested in both gaseous anode (reducing) and cathode (oxidising) environments and at different humidities and carbon dioxide partial pressures. For the structure and morphology measurements, it was concluded that no changes occur to the materials after usage. From measurements of melting energies, it was concluded that the melting point of the carbonate salt phase decreases with decreasing fraction of carbonate salt and that a partial melting occurs before the bulk melting point of the salt is reached. For all the composites, two regions may be observed for the conductivity, one below the carbonate salt melting point and one above the melting point. The conductivity is higher when electrolytes are tested in anode gas than when tested in cathode gas, at least for electrolytes with less than half the volume fraction consisting of carbonate salt. The higher the content of carbonate salt phase, the higher the conductivity of the composite for the temperature region above the carbonate melting point. Below the melting point, though, the conductivity does not follow this trend. Calculations on activation energies for the conductivity show no trend or value that indicates a certain transport mechanism for ion transport, either when changing between the different composites or between different gas environments. (author)

Salt-occluded zeolite waste forms: Crystal structures and transformability

International Nuclear Information System (INIS)

Richardson, J.W. Jr.

1996-01-01

Neutron diffraction studies of salt-occluded zeolite and zeolite/glass composite samples, simulating nuclear waste forms loaded with fission products, have revealed complex structures, with cations assuming the dual roles of charge compensation and occlusion (cluster formation). These clusters roughly fill the 6--8 angstrom diameter pores of the zeolites. Samples are prepared by equilibrating zeolite-A with complex molten Li, K, Cs, Sr, Ba, Y chloride salts, with compositions representative of anticipated waste systems. Samples prepared using zeolite 4A (which contains exclusively sodium cations) as starting material are observed to transform to sodalite, a denser aluminosilicate framework structure, while those prepared using zeolite 5A (sodium and calcium ions) more readily retain the zeolite-A structure. Because the sodalite framework pores are much smaller than those of zeolite-A, clusters are smaller and more rigorously confined, with a correspondingly lower capacity for waste containment. Details of the sodalite structures resulting from transformation of zeolite-A depend upon the precise composition of the original mixture. The enhanced resistance of salt-occluded zeolites prepared from zeolite 5A to sodalite transformation is thought to be related to differences in the complex chloride clusters present in these zeolite mixtures. Data relating processing conditions to resulting zeolite composition and structure can be used in the selection of processing parameters which lead to optimal waste forms

New electrolytes for aluminum production: Ionic liquids

Science.gov (United States)

Zhang, Mingming; Kamavarum, Venkat; Reddy, Ramana G.

2003-11-01

In this article, the reduction, refining/recycling, and electroplating of aluminum from room-temperature molten salts are reviewed. In addition, the characteristics of several non-conventional organic solvents, electrolytes, and molten salts are evaluated, and the applicability of these melts for production of aluminum is discussed with special attention to ionic liquids. Also reviewed are electrochemical processes and conditions for electrodeposition of aluminum using ionic liquids at near room temperatures.

Inclusion of salt form on prescription medication labeling as a source of patient confusion: a pilot study

Directory of Open Access Journals (Sweden)

McDougall DJ

2016-03-01

Full Text Available Background: It has been estimated that 10,000 patient injuries occur in the US annually due to confusion involving drug names. An unexplored source of patient misunderstandings may be medication salt forms. Objective: The objective of this study was to assess patient knowledge and comprehension regarding the salt forms of medications as a potential source of medication errors. Methods: A 12 item questionnaire which assessed patient knowledge of medication names on prescription labels was administered to a convenience sample of patients presenting to a family practice clinic. Descriptive statistics were calculated and multivariate analyses were performed. Results: There were 308 responses. Overall, 41% of patients agreed they find their medication names confusing. Participants correctly answered to salt form questions between 12.1% and 56.9% of the time. Taking more prescription medications and higher education level were positively associated with providing more correct answers to 3 medication salt form knowledge questions, while age was negatively associated. Conclusions: Patient misconceptions about medication salt forms are common. These findings support recommendations to standardize the inclusion or exclusion of salt forms. Increasing patient education is another possible approach to reducing confusion.

Purification of used eutectic (LiCl-KCl) salt electrolyte from pyroprocessing

Science.gov (United States)

Cho, Yung-Zun; Lee, Tae-Kyo; Eun, Hee-Chul; Choi, Jung-Hoon; Kim, In-Tae; Park, Geun-Il

2013-06-01

The separation characteristics of surrogate rare-earth fission products in a eutectic (LiCl-KCl) molten salt were investigated. This system is based on the eutectic salt used for the pyroprocessing treatment of used nuclear fuel (UNF). The investigation was performed using an integrated rare-earth separation apparatus comprising a precipitation reactor, a solid detachment device, and a layer separation device. To separate rare-earth fission products, a phosphate precipitation method using both Li3PO4 and K3PO4 as a precipitant was performed. The use of an equivalent phosphate precipitant composed of 0.408 molar ratio-K3PO4 and 0.592 molar ratio-Li3PO4 can preserve the original eutectic ratio, LiCl-0.592 molar ratio (or 45.2 wt%), as well as provide a high separation efficiency of over 99.5% under conditions of 550 °C and Ar sparging when using La, Nd, Ce, and Pr chlorides. The mixture of La, Nd, Ce, and Pr phosphate had a typical monoclinic (or monazite) structure, which has been proposed as a reliable host matrix for the permanent disposal of a high-level waste form. To maximize the reusability of purified eutectic waste salt after rare-earth separation, the successive rare-earth separation process, which uses both phosphate precipitation and an oxygen sparging method, were introduced and tested with eight rare-earth (Y, La, Ce, Pr, Nd, Sm, Eu and Gd) chlorides. In the successive rare-earth separation process, the phosphate reaction was terminated within 1 h at 550 °C, and a 4-8 h oxygen sparging time were required to obtain over a 99% separation efficiency at 700-750 °C. The mixture of rare-earth precipitates separated by the successive rare-earth separation process was found to be phosphate, oxychloride, and oxide. Through the successive rare-earth separation process, the eutectic ratio of purified salt maintained its original value, and impurity content including the residual precipitant of purified salt can be minimized.

Formation of nanotubes in poly (vinylidene fluoride): Application as solid polymer electrolyte in DSC fabricated using carbon counter electrode

Energy Technology Data Exchange (ETDEWEB)

Muthuraaman, B. [Department of Energy, University of Madras, Guindy campus, Chennai 600025 (India); Maruthamuthu, P., E-mail: pmaruthu@yahoo.com [Department of Energy, University of Madras, Guindy campus, Chennai 600025 (India)

2011-09-01

Highlights: > Incorporation of a {pi}-electron donor compound as dopant in poly(vinylidene fluoride) along with redox couple (I{sup -}/I{sub 3}{sup -}) which forms brush like nanotubes. > Investigations about the use of conducting carbon coated FTO as a durable counter electrode and its effects in DSC. > High charge separation and the channelized flow of electrons in the nanotubes in electrolyte favors stable performance. - Abstract: In the present work, we report the incorporation of 2,2'-Azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) in poly(vinylidene fluoride) (PVDF) along with the redox couple (I{sup -}/I{sub 3}{sup -}). When ABTS, a {pi}-electron donor, is used to dope PVDF, the polymer composite forms brush-like nanotubes and has been successfully used as a solid polymer electrolyte in dye-sensitized solar cells. Under the given conditions, the electrolyte composition forms nanotubes while it is doped with ABTS, a {pi}-electron donor. With this new electrolyte, a dye-sensitized solar cell was fabricated using N3 dye adsorbed over TiO{sub 2} nanoparticles as the photoanode and conducting carbon cement coated FTO as counter electrode.

Gel electrolytes and electrodes

Science.gov (United States)

Fleischmann, Sven; Bunte, Christine; Mikhaylik, Yuriy V.; Viner, Veronika G.

2017-09-05

Gel electrolytes, especially gel electrolytes for electrochemical cells, are generally described. In some embodiments, the gel electrolyte layers comprise components a) to c). Component a) may be at least one layer of at least one polymer comprising polymerized units of: a1) at least one monomer containing an ethylenically unsaturated unit and an amido group and a2) at least one crosslinker. Component b) may be at least one conducting salt and component c) may be at least one solvent. Electrodes may comprise the components a), d) and e), wherein component a) may be at least one layer of at least one polymer as described herein. Component d) may be at least one electroactive layer and component e) may be at least one ceramic layer. Furthermore, electrochemical cells comprising component a) which may be at least one layer of at least one polymer as described herein, are also provided.

Influence of mixed electrolytes and pH on adsorption of bovine serum albumin in hydrophobic interaction chromatography.

Science.gov (United States)

Hackemann, Eva; Hasse, Hans

2017-10-27

Using salt mixtures instead of single salts can be beneficial for hydrophobic interaction chromatography (HIC). The effect of electrolytes on the adsorption of proteins, however, depends on the pH. Little is known on that dependence for mixed electrolytes. Therefore, the effect of the pH on protein adsorption from aqueous solutions containing mixed salts is systematically studied in the present work for a model system: the adsorption of bovine serum albumin (BSA) on the mildly hydrophobic resin Toyopearl PPG-600M. The pH is adjusted to 4.0, 4.7 or 7.0 using 25mM sodium phosphate or sodium citrate buffer. Binary and ternary salt mixtures of sodium chloride, ammonium chloride, sodium sulfate and ammonium sulfate as well as the pure salts are used at overall ionic strengths between 1500 and 4200mM. The temperature is always 25°C. The influence of the mixed electrolytes on the adsorption behavior of BSA changes completely with varying pH. Positive as well as negative cooperative effects of the mixed electrolytes are observed. The results are analyzed using a mathematical model which was recently introduced by our group. In that model the influence of the electrolytes is described by a Taylor series expansion in the individual ion molarities. After suitable parametrization using a subset of the data determined in the present work, the model successfully predicts the influence of mixed electrolytes on the protein adsorption. Furthermore, results for BSA from the present study are compared to literature data for lysozyme, which are available for the same adsorbent, temperature and salts. By calculating the ratio of the loading of the adsorbent for both proteins particularly favorable separation conditions can be selected. Hence, a model-based optimization of solvents for protein separation is possible. Copyright © 2017 Elsevier B.V. All rights reserved.

Investigations of the sorption of pertechnetate on salts of molybdophosphoric acid

International Nuclear Information System (INIS)

Suess, M.; Pfrepper, G.

1983-01-01

Studies were made to investigate the sorption of pertechnetate on neutral and acid salts of molybdophosphoric acid from nitric acid and in the presence of electrolytes and non-electrolytes. Particular, distribution coefficients from 10 to 100 were found. The sorption of pertechnetate can be increased by the addition of K + , NH 4 + , Rb + and Cs + salts, by the addition of non-electrolytes the distribution coefficients decrease. A saturation capacity of about 0.19 mmol Tc/g ammonium phosphomolybdate was determined from the adsorption isotherms. The formation of alkali metal pertechnetate associates in the sorbent phase can be supposed. (author)

Ex-vivo absorption study of lysine R-lipoate salt, a new pharmaceutical form of R-ALA.

Science.gov (United States)

Amenta, Francesco; Buccioni, Michela; Ben, Diego Dal; Lambertucci, Catia; Navia, Aleix Martí; Ngouadjeu Ngnintedem, Michael A; Ricciutelli, Massimo; Spinaci, Andrea; Volpini, Rosaria; Marucci, Gabriella

2018-06-15

Alpha-lipoic acid (ALA) oral supplements were used in many pathologies associated with increased oxidative stress. Although only R-ALA is considered the biologically active form, R,S-ALA is used in therapeutic applications even showing poor water solubility. The aim of this work was to study the absorption and transport mechanism across the intestinal barrier of new R-ALA stable and water soluble form, consisting in the lysine R-ALA salt, in presence and absence of specific inhibitors of Na + /multivitamin (SMVT) and monocarboxylic acids (MCT). The absorption of a new ALA form was investigated at rat everted sacs in comparison with R-ALA, S-ALA, and R,S-ALA. Results showed that duodenum is the best portion of intestine for ALA forms absorption. The absorption percentage of R-ALA, S-ALA, R,S-ALA, and lysine R-ALA salt was 66%, 43%, 55%, and 70%, respectively. The modest effect of the SMVT inhibitor biotin demonstrated that this transporter system is not principally involved in the absorption of lysine R-lipoate salt across the rat intestinal barrier. On the contrary, the MCT inhibitor octanoic acid significantly reduced the transport of this salt, whit an absorption decrease of R-ALA and lysine R-lipoate salt of 28% and 24%, respectively. Since the highest concentration of these inhibitors did not completely inhibit the absorption of lysine R-lipoate salt, other transport mechanisms probably operate for its intracellular delivery. The new form of ALA, lysine R-lipoate salt, was the most absorbed respect to the other ALA forms demonstrating that this compound is more suitable for oral administration. This new salt could represent a promising candidate for ALA oral supplementation. Copyright © 2018 Elsevier B.V. All rights reserved.

Order of wetting transitions in electrolyte solutions.

Science.gov (United States)

Ibagon, Ingrid; Bier, Markus; Dietrich, S

2014-05-07

For wetting films in dilute electrolyte solutions close to charged walls we present analytic expressions for their effective interface potentials. The analysis of these expressions renders the conditions under which corresponding wetting transitions can be first- or second-order. Within mean field theory we consider two models, one with short- and one with long-ranged solvent-solvent and solvent-wall interactions. The analytic results reveal in a transparent way that wetting transitions in electrolyte solutions, which occur far away from their critical point (i.e., the bulk correlation length is less than half of the Debye length) are always first-order if the solvent-solvent and solvent-wall interactions are short-ranged. In contrast, wetting transitions close to the bulk critical point of the solvent (i.e., the bulk correlation length is larger than the Debye length) exhibit the same wetting behavior as the pure, i.e., salt-free, solvent. If the salt-free solvent is governed by long-ranged solvent-solvent as well as long-ranged solvent-wall interactions and exhibits critical wetting, adding salt can cause the occurrence of an ion-induced first-order thin-thick transition which precedes the subsequent continuous wetting as for the salt-free solvent.

Characterization of Novel Castor Oil-Based Polyurethane Polymer Electrolytes

Directory of Open Access Journals (Sweden)

Salmiah Ibrahim

2015-04-01

Full Text Available Castor oil-based polyurethane as a renewable resource polymer has been synthesized for application as a host in polymer electrolyte for electrochemical devices. The polyurethane was added with LiI and NaI in different wt% to form a film of polymer electrolytes. The films were characterized by using attenuated total reflectance-Fourier transform infrared spectroscopy, dynamic mechanical analysis, electrochemical impedance spectroscopy, linear sweep voltammetry and transference number measurement. The highest conductivity of 1.42 × 10−6 S cm−1 was achieved with the addition of 30 wt% LiI and 4.28 × 10−7 S·cm−1 upon addition of 30 wt% NaI at room temperature. The temperature dependence conductivity plot indicated that both systems obeyed Arrhenius law. The activation energy for the PU-LiI and PU-NaI systems were 0.13 and 0.22 eV. Glass transition temperature of the synthesized polyurethane decreased from −15.8 °C to ~ −26 to −28 °C upon salts addition. These characterizations exhibited the castor oil-based polyurethane polymer electrolytes have potential to be used as alternative membrane for electrochemical devices.

Ionic conductivity in polyethylene-b-poly(ethylene oxide)/lithium perchlorate solid polymer electrolytes

International Nuclear Information System (INIS)

Guilherme, L.A.; Borges, R.S.; Moraes, E. Mara S.; Silva, G. Goulart; Pimenta, M.A.; Marletta, A.; Silva, R.A.

2007-01-01

The ionic conductivity and phase arrangement of solid polymeric electrolytes based on the block copolymer polyethylene-b-poly(ethylene oxide) (PE-b-PEO) and LiClO 4 have been investigated. One set of electrolytes was prepared from copolymers with 75% of PEO units and another set was based on a blend of copolymer with 50% PEO units and homopolymers. The differential scanning calorimetry (DSC) results, for electrolytes based on the copolymer with 75% of PEO units, were dominated by the PEO phase. The PEO block crystallinity dropped and the glass transition increased with salt addition due to the coordination of the cation by PEO oxygen. The conductivity for copolymers 75% PEO-based electrolyte with 15 wt% of salt was higher than 10 -5 S/cm at room temperature and reached to 10 -3 S/cm at 100 deg. C on a heating measurement. The blend of PE-b-PEO (50% PEO)/PEO/PE showed a complex thermal behavior with decoupled melting of the blocks and the homopolymers. Upon salt addition the endotherms associated with PEO domains disappeared and the PE crystals remained untouched. The conductivity results were limited at 100 deg. C to values close to 10 -4 S/cm and at room temperature values close to 3 x 10 -6 S/cm were obtained for the 15 wt% salt electrolyte. Raman study showed that the ionic association of the highly concentrated blend electrolytes at room temperature is not significant. Therefore, the lower values of conductivity in the case of the blend with 50% PEO can be assigned to the higher content of PE domains leading to a morphology with lower connectivity for ionic conduction both in the crystalline and melted state of the PE domains

Nitrile functionalized silyl ether with dissolved LiTFSI as new electrolyte solvent for lithium-ion batteries

International Nuclear Information System (INIS)

Pohl, Benjamin; Grünebaum, Mariano; Drews, Mathias; Passerini, Stefano; Winter, Martin; Wiemhöfer, Hans‑Dieter

2015-01-01

Highlights: • A new electrolyte based on a nitrile-silyl ether solvent and LiTFSI as lithium salt was successfully tested. • This electrolyte shows higher ionic conductivities as compared to earlier published silicon based solvents. • Due to the absence of ether groups, the electrochemical stability is extended to 5.4 V vs. Li/Li + . • With LiTFSI, the electrolyte can be cycled up to 4.15 V vs. Li/Li + without causing anodic aluminum dissolution. - Abstract: 3-((Trimethylsilyl) oxy) propionitrile is introduced as non-volatile solvent for lithium-ion battery electrolytes using LiTFSI as lithium salt. The thermal and chemical stability of the electrolytes offer an enhanced safety as compared to conventional volatile carbonate electrolytes. In cell tests, the investigated LiTFSI nitrile silyl ether electrolyte shows compatibility with LiFePO 4 , LiNi 0.33 Mn 0.33 Co 0.33 O 2 and graphite active materials.

Lithium current sources with an electrolyte based on aprotonic solvents

Energy Technology Data Exchange (ETDEWEB)

Shembel, Ye.M.; Ksenzhek, O.S.; Litvinova, V.I.; Martynenko, T.L.; Raykhelson, L.B.; Sokolov, L.A.; Strizhko, A.S.

1984-01-01

Lithium current sources with an electrolyte based on aprotonic solvents are examined. The effect of the composition of the electrolyte solution on the solubility of SO2 and the excess pressure of the gas above the electrolyte solution is established. The temperature characteristics of the electrolyte are studied from the standpoint of salt solubility, the association between the discharge conditions, the macrostructure of the porous inert cathode and the degree of usage of the active cathode substance of the SO2 as the necessary aspects for solving the problems of optimizing a lithium and SO2 system.

Self-Assembled Polymeric Ionic Liquid-Functionalized Cellulose Nano-crystals: Constructing 3D Ion-conducting Channels Within Ionic Liquid-based Composite Polymer Electrolytes.

Science.gov (United States)

Shi, Qing Xuan; Xia, Qing; Xiang, Xiao; Ye, Yun Sheng; Peng, Hai Yan; Xue, Zhi Gang; Xie, Xiao Lin; Mai, Yiu-Wing

2017-09-04

Composite polymeric and ionic liquid (IL) electrolytes are some of the most promising electrolyte systems for safer battery technology. Although much effort has been directed towards enhancing the transport properties of polymer electrolytes (PEs) through nanoscopic modification by incorporating nano-fillers, it is still difficult to construct ideal ion conducting networks. Here, a novel class of three-dimensional self-assembled polymeric ionic liquid (PIL)-functionalized cellulose nano-crystals (CNC) confining ILs in surface-grafted PIL polymer chains, able to form colloidal crystal polymer electrolytes (CCPE), is reported. The high-strength CNC nano-fibers, decorated with PIL polymer chains, can spontaneously form three-dimensional interpenetrating nano-network scaffolds capable of supporting electrolytes with continuously connected ion conducting networks with IL being concentrated in conducting domains. These new CCPE have exceptional ionic conductivities, low activation energies (close to bulk IL electrolyte with dissolved Li salt), high Li + transport numbers, low interface resistances and improved interface compatibilities. Furthermore, the CCPE displays good electrochemical properties and a good battery performance. This approach offers a route to leak-free, non-flammable and high ionic conductivity solid-state PE in energy conversion devices. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cost-driven materials selection criteria for redox flow battery electrolytes

Science.gov (United States)

Dmello, Rylan; Milshtein, Jarrod D.; Brushett, Fikile R.; Smith, Kyle C.

2016-10-01

Redox flow batteries show promise for grid-scale energy storage applications but are presently too expensive for widespread adoption. Electrolyte material costs constitute a sizeable fraction of the redox flow battery price. As such, this work develops a techno-economic model for redox flow batteries that accounts for redox-active material, salt, and solvent contributions to the electrolyte cost. Benchmark values for electrolyte constituent costs guide identification of design constraints. Nonaqueous battery design is sensitive to all electrolyte component costs, cell voltage, and area-specific resistance. Design challenges for nonaqueous batteries include minimizing salt content and dropping redox-active species concentration requirements. Aqueous battery design is sensitive to only redox-active material cost and cell voltage, due to low area-specific resistance and supporting electrolyte costs. Increasing cell voltage and decreasing redox-active material cost present major materials selection challenges for aqueous batteries. This work minimizes cost-constraining variables by mapping the battery design space with the techno-economic model, through which we highlight pathways towards low price and moderate concentration. Furthermore, the techno-economic model calculates quantitative iterations of battery designs to achieve the Department of Energy battery price target of 100 per kWh and highlights cost cutting strategies to drive battery prices down further.

Alternative Electrochemical Salt Waste Forms, Summary of FY/CY2011 Results

International Nuclear Information System (INIS)

Riley, Brian J.; McCloy, John S.; Crum, Jarrod V.; Rodriguez, Carmen P.; Windisch, Charles F.; Lepry, William C.; Matyas, Josef; Westman, Matthew P.; Rieck, Bennett T.; Lang, Jesse B.; Pierce, David A.

2011-01-01

This report summarizes the 2011 fiscal+calendar year efforts for developing waste forms for a spent salt generated in reprocessing nuclear fuel with an electrochemical separations process. The two waste forms are tellurite (TeO2-based) glasses and sol-gel-derived high-halide mineral analogs to stable minerals found in nature.

Alternative Electrochemical Salt Waste Forms, Summary of FY/CY2011 Results

Energy Technology Data Exchange (ETDEWEB)

Riley, Brian J.; McCloy, John S.; Crum, Jarrod V.; Rodriguez, Carmen P.; Windisch, Charles F.; Lepry, William C.; Matyas, Josef; Westman, Matthew P.; Rieck, Bennett T.; Lang, Jesse B.; Pierce, David A.

2011-12-01

This report summarizes the 2011 fiscal+calendar year efforts for developing waste forms for a spent salt generated in reprocessing nuclear fuel with an electrochemical separations process. The two waste forms are tellurite (TeO2-based) glasses and sol-gel-derived high-halide mineral analogs to stable minerals found in nature.

Salt forms of the pharmaceutical amide dihydrocarbamazepine.

Science.gov (United States)

Buist, Amanda R; Kennedy, Alan R

2016-02-01

Carbamazepine (CBZ) is well known as a model active pharmaceutical ingredient used in the study of polymorphism and the generation and comparison of cocrystal forms. The pharmaceutical amide dihydrocarbamazepine (DCBZ) is a less well known material and is largely of interest here as a structural congener of CBZ. Reaction of DCBZ with strong acids results in protonation of the amide functionality at the O atom and gives the salt forms dihydrocarbamazepine hydrochloride {systematic name: [(10,11-dihydro-5H-dibenzo[b,f]azepin-5-yl)(hydroxy)methylidene]azanium chloride, C15H15N2O(+)·Cl(-)}, dihydrocarbamazepine hydrochloride monohydrate {systematic name: [(10,11-dihydro-5H-dibenzo[b,f]azepin-5-yl)(hydroxy)methylidene]azanium chloride monohydrate, C15H15N2O(+)·Cl(-)·H2O} and dihydrocarbamazepine hydrobromide monohydrate {systematic name: [(10,11-dihydro-5H-dibenzo[b,f]azepin-5-yl)(hydroxy)methylidene]azanium bromide monohydrate, C15H15N2O(+)·Br(-)·H2O}. The anhydrous hydrochloride has a structure with two crystallographically independent ion pairs (Z' = 2), wherein both cations adopt syn conformations, whilst the two hydrated species are mutually isostructural and have cations with anti conformations. Compared to neutral dihydrocarbamazepine structures, protonation of the amide group is shown to cause changes to both the molecular (C=O bond lengthening and C-N bond shortening) and the supramolecular structures. The amide-to-amide and dimeric hydrogen-bonding motifs seen for neutral polymorphs and cocrystalline species are replaced here by one-dimensional polymeric constructs with no direct amide-to-amide bonds. The structures are also compared with, and shown to be closely related to, those of the salt forms of the structurally similar pharmaceutical carbamazepine.

X-ray diffraction studies of chitosan acetate-based polymer electrolytes

International Nuclear Information System (INIS)

Osman, Z.; Ibrahim, Z.A.; Abdul Kariem Arof

2002-01-01

Chitosan is the product when partially deacetylated chitin dissolves in dilute acetic acid. This paper presents the x-ray diffraction patterns of chitosan acetate, plasticised chitosan acetate and plasticised-salted chitosan acetate films. The results show that the chitosan acetate based polymer electrolyte films are not completely amorphous but it is partially crystalline. X-ray diffraction study also confirms the occurrence of the complexation between chitosan and the salt and the interaction between salt and plasticizer. The salt-chitosan interaction is clearly justified by infrared spectroscopy. (Author)

Solid oxide fuel cells with bi-layered electrolyte structure

Energy Technology Data Exchange (ETDEWEB)

Zhang, Xinge; Robertson, Mark; Deces-Petit, Cyrille; Xie, Yongsong; Hui, Rob; Qu, Wei; Kesler, Olivera; Maric, Radenka; Ghosh, Dave [Institute for Fuel Cell Innovation, National Research Council Canada, 4250 Wesbrook Mall, Vancouver, B.C. V6T 1W5 (Canada)

2008-01-10

In this work, we have developed solid oxide fuel cells with a bi-layered electrolyte of 2 {mu}m SSZ and 4 {mu}m SDC using tape casting, screen printing, and co-firing processes. The cell reached power densities of 0.54 W cm{sup -2} at 650 C and 0.85 W cm{sup -2} at 700 C, with open circuit voltage (OCV) values larger than 1.02 V. The electrical leaking between anode and cathode through an SDC electrolyte has been blocked in the bi-layered electrolyte structure. However, both the electrolyte resistance (R{sub el}) and electrode polarization resistance (R{sub p,a+c}) increased in comparison to cells with single-layered SDC electrolytes. The formation of a solid solution of (Ce, Zr)O{sub 2-x} during sintering process and the flaws in the bi-layered electrolyte structure seem to be the main causes for the increase in the R{sub el} value (0.32 {omega} cm{sup 2}) at 650 C, which is almost one order of magnitude higher than the calculated value. (author)

Alternative Electrochemical Salt Waste Forms, Summary of FY11-FY12 Results

Energy Technology Data Exchange (ETDEWEB)

Riley, Brian J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Mccloy, John S. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Crum, Jarrod V. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Lepry, William C. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Rodriguez, Carmen P. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Windisch, Charles F. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Matyas, Josef [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Westman, Matthew P. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Rieck, Bennett T. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Lang, Jesse B. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Olszta, Matthew J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Pierce, David A. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

2014-01-17

The Fuel Cycle Research and Development Program, sponsored by the U.S. Department of Energy Office of Nuclear Energy, is currently investigating alternative waste forms for wastes generated from nuclear fuel processing. One such waste results from an electrochemical separations process, called the “Echem” process. The Echem process utilizes a molten KCl-LiCl salt to dissolve the fuel. This process results in a spent salt containing alkali, alkaline earth, lanthanide halides and small quantities of actinide halides, where the primary halide is chloride with a minor iodide fraction. Pacific Northwest National Laboratory (PNNL) is concurrently investigating two candidate waste forms for the Echem spent-salt: high-halide minerals (i.e., sodalite and cancrinite) and tellurite (TeO2)-based glasses. Both of these candidates showed promise in fiscal year (FY) 2009 and FY2010 with a simplified nonradioactive simulant of the Echem waste. Further testing was performed on these waste forms in FY2011 and FY2012 to assess the possibility of their use in a sustainable fuel cycle. This report summarizes the combined results from FY2011 and FY2012 efforts.

Effect of the graphite electrode material on the characteristics of molten salt electrolytically produced carbon nanomaterials

International Nuclear Information System (INIS)

Kamali, Ali Reza; Schwandt, Carsten; Fray, Derek J.

2011-01-01

The electrochemical erosion of a graphite cathode during the electrolysis of molten lithium chloride salt may be used for the preparation of nano-structured carbon materials. It has been found that the structures and morphologies of these carbon nanomaterials are dependent on those of the graphite cathodes employed. A combination of tubular and spherical carbon nanostructures has been produced from a graphite with a microstructure of predominantly planar micro-sized grains and a minor fraction of more irregular nano-sized grains, whilst only spherical carbon nanostructures have been produced from a graphite with a microstructure of primarily nano-sized grains. Based on the experimental results, a best-fit regression equation is proposed that relates the crystalline domain size of the graphite reactants and the carbon products. The carbon nanomaterials prepared possess a fairly uniform mesoporosity with a sharp peak in pore size distribution at around 4 nm. The results are of crucial importance to the production of carbon nanomaterials by way of the molten salt electrolytic method. - Highlights: → Carbon nanomaterials are synthesised by LiCl electrolysis with graphite electrodes. → The degree of crystallinity of graphite reactant and carbon product are related. → A graphite reactant is identified that enables the preparation of carbon nanotubes. → The carbon products possess uniform mesoporosity with narrow pore size distribution.

Thermal Analysis of Surrogate Simulated Molten Salts with Metal Chloride Impurities for Electrorefining Used Nuclear Fuel

Energy Technology Data Exchange (ETDEWEB)

Toni Y. Gutknecht; Guy L. Fredrickson; Vivek Utgikar

2012-04-01

This project is a fundamental study to measure thermal properties (liquidus, solidus, phase transformation, and enthalpy) of molten salt systems of interest to electrorefining operations, which are used in both the fuel cycle research & development mission and the spent fuel treatment mission of the Department of Energy. During electrorefining operations the electrolyte accumulates elements more active than uranium (transuranics, fission products and bond sodium). The accumulation needs to be closely monitored because the thermal properties of the electrolyte will change as the concentration of the impurities increases. During electrorefining (processing techniques used at the Idaho National Laboratory to separate uranium from spent nuclear fuel) it is important for the electrolyte to remain in a homogeneous liquid phase for operational safeguard and criticality reasons. The phase stability of molten salts in an electrorefiner may be adversely affected by the buildup of fission products in the electrolyte. Potential situations that need to be avoided are: (i) build up of fissile elements in the salt approaching the criticality limits specified for the vessel (ii) freezing of the salts due to change in the liquidus temperature and (iii) phase separation (non-homogenous solution) of elements. The stability (and homogeneity) of the phases can potentially be monitored through the thermal characterization of the salts, which can be a function of impurity concentration. This work describes the experimental results of typical salts compositions, consisting of chlorides of strontium, samarium, praseodymium, lanthanum, barium, cerium, cesium, neodymium, sodium and gadolinium (as a surrogate for both uranium and plutonium), used in the processing of used nuclear fuels. Differential scanning calorimetry was used to analyze numerous salt samples providing results on the thermal properties. The property of most interest to pyroprocessing is the liquidus temperature. It was

Investigations of oxygen reduction reactions in non-aqueous electrolytes and the lithium-air battery

Science.gov (United States)

O'Laoire, Cormac Micheal

Unlocking the true energy capabilities of the lithium metal negative electrode in a lithium battery has until now been limited by the low capacity intercalation and conversion reactions at the positive electrodes. This is overcome by removing these electrodes and allowing lithium to react directly with oxygen in the atmosphere forming the Li-air battery. Chapter 2 discusses the intimate role of electrolyte, in particular the role of ion conducting salts on the mechanism and kinetics of oxygen reduction in non-aqueous electrolytes designed for such applications and in determining the reversibility of the electrode reactions. Such fundamental understanding of this high energy density battery is crucial to harnessing its full energy potential. The kinetics and mechanisms of O2 reduction in solutions of hexafluorophosphate salts of the general formula X+ PF6-, where, X = tetra butyl ammonium (TBA), K, Na and Li, in acetonitrile have been studied on glassy carbon electrodes using cyclic voltammetry (CV) and rotating disk electrode (RDE) techniques. Our results show that cation choice strongly influences the reduction mechanism of O2. Electrochemical data supports the view that alkali metal oxides formed via electrochemical and chemical reactions passivate the electrode surface inhibiting the kinetics and reversibility of the processes. The O2 reduction mechanisms in the presence of the different cations have been supplemented by kinetic parameters determined from detailed analyses of the CV and RDE data. The organic solvent present in the Li+-conducting electrolyte has a major role on the reversibility of each of the O2 reduction products as found from the work discussed in the next chapter. A fundamental study of the influence of solvents on the oxygen reduction reaction (ORR) in a variety of non-aqueous electrolytes was conducted in chapter 4. In this work special attention was paid to elucidate the mechanism of the oxygen electrode processes in the rechargeable Li

Characteristics of an integrated cathode assembly for the electrolytic reduction of uranium oxide in a LiCl-Li2O molten salt

International Nuclear Information System (INIS)

Sung Bin Park; Byung Heung Park; Sang Mun Jeong; Jin Mok Hur; Chung Seok Seo; Seong Won Park; Seung-Hoon Choi

2006-01-01

Electrochemical behavior of the reduction of uranium oxide was studied in a LiCl-Li 2 O molten salt system with an integrated cathode assembly. The mechanism for the electrolytic reduction of uranium oxide was studied through cyclic voltammetry. By means of a chronopotentiometry, the effects of the thickness of the uranium oxide, the thickness of the MgO membrane and the material of the conductor of an integrated cathode assembly on the overpotential of the cathode were investigated. From the voltamograms, the reduction potential of the uranium oxide and Li 2 O was obtained and the two mechanisms of the electrolytic reduction were considered with regard to the applied cathode potential. From the chronopotentiograms, the exchange current, the transfer coefficient and the maximum allowable current based on the Tafel behavior were obtained with regard to the thickness of the uranium oxide, and of the MgO membrane and the material of the conductor of an integrated cathode assembly. (author)

R and D activities on the management of waste chloride salts in KAERI

International Nuclear Information System (INIS)

In-Tae, Kim; Hwan-Seo, Park; Jeong-Gook, Kim; Hee-Chul, Yang; Yong-Joon, Cho; Eung-Ho Kim

2007-01-01

Full text of publication follows. Electrochemical treatment of spent oxide fuels has been intensively studied in KAERI to reduce the volume, heat load and radiotoxicity of high-level wastes. It consists of an electrolytic reduction process to convert the oxide fuel into a metallic form and an electro-refining process to separate TRU elements from the electro-reduced metal ingot. Two types of waste salts are expected to generate from the electrochemical pyro-processes, that is, LiCl salt from the reduction process and LiCl+KCl eutectic salt form the refining process. The R and D strategy of the waste salt management in KAERI can be categorized into two parts: 1) enhancement of safety by the stabilisation/solidification of waste salt that is to be finally disposed of and 2) reduction of the waste generation by the regeneration/recycle of the spent salt after removal of radionuclides in it. A sol-gel technique and a zeolite occlusion technique are under development to stabilize the waste salt. The LiCl salt is stabilised by a low-temperature sol-gel process and then the gel product is solidified into a ceramic-like waste form with an addition of glass frit. Another method uses Zeolite-4A to occlude the LiCl salt into its cage and adsorption site to immobilize the radionuclides. The product, salt-occluded zeolite, is fabricated into another type of a ceramic waste form. For the regeneration and recycle of the spent salt, the radionuclides in the salt are removed by a zeolite process for the LiCl salt and by an oxidation/distillation process for the eutectic salt. The target nuclides to be removed in each process are Cs/Sr and rare earth (RE) elements, respectively. In the oxidation/ distillation process, the rare earth chloride nuclides are oxidised by an oxygen sparging method, and the products are precipitated in the form of oxide or oxychloride REs. After separation of the RE elements from the precipitates by distillation, the refined spent salt with a low content

Ion-ion and ion-solvent interactions in lithium imidazolide electrolytes studied by Raman spectroscopy and DFT models.

Science.gov (United States)

Scheers, Johan; Niedzicki, Leszek; Zukowska, Grażyna Z; Johansson, Patrik; Wieczorek, Władysław; Jacobsson, Per

2011-06-21

Molecular level interactions are of crucial importance for the transport properties and overall performance of ion conducting electrolytes. In this work we explore ion-ion and ion-solvent interactions in liquid and solid polymer electrolytes of lithium 4,5-dicyano-(2-trifluoromethyl)imidazolide (LiTDI)-a promising salt for lithium battery applications-using Raman spectroscopy and density functional theory calculations. High concentrations of ion associates are found in LiTDI:acetonitrile electrolytes, the vibrational signatures of which are transferable to PEO-based LiTDI electrolytes. The origins of the spectroscopic changes are interpreted by comparing experimental spectra with simulated Raman spectra of model structures. Simple ion pair models in vacuum identify the imidazole nitrogen atom of the TDI anion to be the most important coordination site for Li(+), however, including implicit or explicit solvent effects lead to qualitative changes in the coordination geometry and improved correlation of experimental and simulated Raman spectra. To model larger aggregates, solvent effects are found to be crucial, and we finally suggest possible triplet and dimer ionic structures in the investigated electrolytes. In addition, the effects of introducing water into the electrolytes-via a hydrate form of LiTDI-are discussed.

Lithium Ion Transport Across and Between Phase Boundaries in Heterogeneous Polymer Electrolytes, Based on PVdF

National Research Council Canada - National Science Library

Greenbaum, Steven

1998-01-01

.... In the first reported attempt to exploit 17O NMR to study lithium battery electrolytes, we have prepared 17O-enriched Li triflate and several electrolytes containing the isotopically enriched salt...

A study on microstructure and corrosion resistance of ZrO2-containing PEO coatings formed on AZ31 Mg alloy in phosphate-based electrolyte

International Nuclear Information System (INIS)

Zhuang, J.J.; Guo, Y.Q.; Xiang, N.; Xiong, Y.; Hu, Q.; Song, R.G.

2015-01-01

Graphical abstract: - Highlights: • PEO coatings were formed in K 2 ZrF 6 -containing electrolyte. • K 2 ZrF 6 is capable to optimize the microstructure of PEO coating. • Corrosion resistance of PEO coatings is effected by K 2 ZrF 6 concentration in the electrolyte. • Potentiodynamic polarization results are well matched with the EIS test results. • Long time immersion test confirmed the electrochemical results. - Abstract: ZrO 2 -containing ceramic coatings formed on the AZ31 Mg alloy were fabricated in an alkaline electrolyte containing sodium phosphate and potassium fluorozirconate (K 2 ZrF 6 ) by plasma electrolytic oxidation (PEO). X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) techniques were used to study the phase structure and composition of the coatings. It is indicated that the coatings formed in the K 2 ZrF 6 -containing electrolyte were composed of MgO, MgF 2 and t-ZrO 2 . Morphological investigation carried out by scanning electron microscopy (SEM) and stereoscopic microscopy, revealed that the uniformity of coatings increased and roughness of coatings decreased after the addition of K 2 ZrF 6 . Electrochemical investigation was achieved by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) test. The results showed that the PEO coating formed in K 2 ZrF 6 -containing electrolyte exhibited an improved corrosion resistance than that of the coating formed in K 2 ZrF 6 -free electrolyte. In addition, the polarization and EIS tests results both showed that the suitable concentration (2.5 g/l) of K 2 ZrF 6 is of significant ability to improve the corrosion resistance of coatings. However, 5 g/l and 10 g/l K 2 ZrF 6 has a negative effect on improving the corrosion resistance of PEO coatings compared with the coating formed in 2.5 g/l K 2 ZrF 6 -containing electrolyte.

Electrical transport study of potato starch-based electrolyte system-II

International Nuclear Information System (INIS)

Tiwari, Tuhina; Kumar, Manindra; Srivastava, Neelam; Srivastava, P.C.

2014-01-01

Highlights: • Cheap and bio-degradable polymer electrolyte. • High conductivity ∼ 9.59 × 10 −3 Scm −1 . • Detailed ion dynamics stud. -- Abstract: Glutaraldehyde (GA) crosslinked potato starch, after mixing with sodium iodide (NaI), resulted in electrolyte film having conductivity (σ) ∼ 10 −3 S/cm and ionic transference number (t ion ) ≥ 0.99. Out of two preparation mediums, namely methanol and acetone, methanol based electrolyte system seems to be better. Super-linear power law (SLPL) phenomenon is observed in MHz frequency range and both lattice site potential and coulomb cage potential due to neighboring mobile charge carriers seems to be responsible for existence of SLPL, and variation of power law exponent ‘n’ with salt concentration. These ion dynamics results are supported by dielectric data also. Estimated number of charge carriers ‘N’ and mobility ‘μ’ are discussed with reference to different variants (medium of preparation, plasticizer, and salt content). Material's conductivity strongly depends on humidity

Energy storage devices having anodes containing Mg and electrolytes utilized therein

Science.gov (United States)

Shao, Yuyan; Liu, Jun

2015-08-18

For a metal anode in a battery, the capacity fade is a significant consideration. In energy storage devices having an anode that includes Mg, the cycling stability can be improved by an electrolyte having a first salt, a second salt, and an organic solvent. Examples of the organic solvent include diglyme, triglyme, tetraglyme, or a combination thereof. The first salt can have a magnesium cation and be substantially soluble in the organic solvent. The second salt can enhance the solubility of the first salt and can have a magnesium cation or a lithium cation. The first salt, the second salt, or both have a BH.sub.4 anion.

Electrochemical properties of quaternary ammonium salts for electrochemical capacitors

Energy Technology Data Exchange (ETDEWEB)

Ue, Makoto; Takeda, Masayuki; Takehara, Masahiro; Mori, Shoichiro [Mitsubishi Chemical Corp., Inashiki, Ibaraki (Japan). Tsukuba Research Center

1997-08-01

The limiting reduction and oxidation potentials and electrolytic conductivities of new quaternary ammonium salts were examined for electrochemical capacitor applications, whose anions have already been tested as lithium salts for lithium battery applications. The anodic stability was in the following order BR{sub 4}{sup {minus}} < ClO{sub 4}{sup {minus}} {le} CF{sub 3}SO{sub 3}{sup {minus}} < (CF{sub 3}SO{sub 2}){sub 2}N{sup {minus}} {le} C{sub 4}F{sub 9}SO{sub 3}{sup {minus}} < BF{sub 4}{sup {minus}} < PF{sub 6}{sup {minus}} {le} AsF{sub 6}{sup {minus}} < SbF{sub 6}{sup {minus}}. The electrolytic conductivities of Me{sub 4{minus}n}Et{sub n}N(CF{sub 3}SO{sub 2}){sub 2}N (n = 0--4) were examined in comparison with Me{sub 4{minus}n}Et{sub n}NBF{sub 4} counterparts. These imide salts showed good solubility, relatively high conductivity, and anodic stability in propylene carbonate. Et{sub 4}N(CF{sub 3}SO{sub 2}){sub 2}N was found to be a good supporting salt for low permittivity organic solvents, and it afforded a highly conductive electrolyte system based on the ethylene carbonate-dimethyl carbonate mixed solvent, which is useful for electrochemical capacitor applications.

Salt briquette: the form of salt monopoly in madura, 1883-1911

Science.gov (United States)

Wisnu; Alrianingrum, S.; Artono; Liana, C.

2018-01-01

This study describes the history of the salt monopoly in Indonesia because it is associated with the issue of salt crisis lately, widely reported in various media. This study tried to find answers to the relationship between monopoly and crisis events through the study of history. Monopoly policy by the government of the colonial period is actually an industrial modernization effort, but it turned out another impact. Although the colonial government wanted to issue a policy that ends strengthens the position of the government in the industry, but ultimately backfire and disasters in the salt industry at the time. This article discusses only the focus of the salt monopoly in Madura as a selection of events, arguing the island as a center of salt in Indonesia. The method used in this study using a review of history. Therefore, their explanations using historical sources. Methodologically through the process of collecting historical sources, criticize these sources, synthesize and interpret the analysis in an array of historical writing. In conclusion, although the salt monopoly policy gives a great advantage to the colonial government, but the overall population of Madura remains in a poor state. It is evident that the Madurese to migrate Madurese to various areas outside the island of Madura, to fix the economy.

Laser-Induced Breakdown Spectroscopy (LIBS) in a Novel Molten Salt Aerosol System.

Science.gov (United States)

Williams, Ammon N; Phongikaroon, Supathorn

2017-04-01

In the pyrochemical separation of used nuclear fuel (UNF), fission product, rare earth, and actinide chlorides accumulate in the molten salt electrolyte over time. Measuring this salt composition in near real-time is advantageous for operational efficiency, material accountability, and nuclear safeguards. Laser-induced breakdown spectroscopy (LIBS) has been proposed and demonstrated as a potential analytical approach for molten LiCl-KCl salts. However, all the studies conducted to date have used a static surface approach which can lead to issues with splashing, low repeatability, and poor sample homogeneity. In this initial study, a novel molten salt aerosol approach has been developed and explored to measure the composition of the salt via LIBS. The functionality of the system has been demonstrated as well as a basic optimization of the laser energy and nebulizer gas pressure used. Initial results have shown that this molten salt aerosol-LIBS system has a great potential as an analytical technique for measuring the molten salt electrolyte used in this UNF reprocessing technology.

Defining a metal-based waste form for IFR pyroprocessing wastes

International Nuclear Information System (INIS)

McDeavitt, S.M.; Park, J.Y.; Ackerman, J.P.

1994-01-01

Pyrochemical electrorefining to recover actinides from metal nuclear fuel is a key element of the Integral Fast Reactor (IFR) fuel cycle. The process separates the radioactive fission products from the long-lived actinides in a molten LiCl-KCl salt, and it generates a lower waste volume with significantly less long-term toxicity as compared to spent nuclear fuel. The process waste forms include a mineral-based waste form that will contain fission products removed from an electrolyte salt and a metal-based waste form that will contain metallic fission products and the fuel cladding and process materials. Two concepts for the metal-based waste form are being investigated: (1) encapsulating the metal constituents in a Cu-Al alloy and (2) alloying the metal constituents into a uniform stainless steel-based waste form. Results are given from our recent studies of these two concepts

Modeling Insight into Battery Electrolyte Electrochemical Stability and Interfacial Structure.

Science.gov (United States)

Borodin, Oleg; Ren, Xiaoming; Vatamanu, Jenel; von Wald Cresce, Arthur; Knap, Jaroslaw; Xu, Kang

2017-12-19

Electroactive interfaces distinguish electrochemistry from chemistry and enable electrochemical energy devices like batteries, fuel cells, and electric double layer capacitors. In batteries, electrolytes should be either thermodynamically stable at the electrode interfaces or kinetically stable by forming an electronically insulating but ionically conducting interphase. In addition to a traditional optimization of electrolytes by adding cosolvents and sacrificial additives to preferentially reduce or oxidize at the electrode surfaces, knowledge of the local electrolyte composition and structure within the double layer as a function of voltage constitutes the basis of manipulating an interphase and expanding the operating windows of electrochemical devices. In this work, we focus on how the molecular-scale insight into the solvent and ion partitioning in the electrolyte double layer as a function of applied potential could predict changes in electrolyte stability and its initial oxidation and reduction reactions. In molecular dynamics (MD) simulations, highly concentrated lithium aqueous and nonaqueous electrolytes were found to exclude the solvent molecules from directly interacting with the positive electrode surface, which provides an additional mechanism for extending the electrolyte oxidation stability in addition to the well-established simple elimination of "free" solvent at high salt concentrations. We demonstrate that depending on their chemical structures, the anions could be designed to preferentially adsorb or desorb from the positive electrode with increasing electrode potential. This provides additional leverage to dictate the order of anion oxidation and to effectively select a sacrificial anion for decomposition. The opposite electrosorption behaviors of bis(trifluoromethane)sulfonimide (TFSI) and trifluoromethanesulfonate (OTF) as predicted by MD simulation in highly concentrated aqueous electrolytes were confirmed by surface enhanced infrared

Effect of sulfolane on the performance of lithium bis(oxalato)borate-based electrolytes for advanced lithium ion batteries

International Nuclear Information System (INIS)

Li Shiyou; Zhao Yangyu; Shi Xinming; Li Bucheng; Xu Xiaoli; Zhao Wei; Cui Xiaoling

2012-01-01

Highlights: ► High purity of LiBOB is obtained by the compressing dry granulation method. ► LiBOB-SL/DEC electrolyte is an excellent candidate electrolyte for lithium ion batteries. ► It shows high oxidation potentials (>5.3 V) and satisfactory conductivities. ► In Li/MCMB cells, this novel electrolyte exhibits excellent film-forming characteristics and low impedances of the interface films. ► In LiFePO 4 /Li cells, this novel electrolyte exhibits stable cycle performance and high discharge voltage plateau (>3.35 V). - Abstract: Lithium bis(oxalato)borate (LiBOB) is a promising salt for lithium ion batteries. However, before applying in lithium ion batteries, it is necessary to prepare high purity LiBOB with a simple method, and find more appropriate solvent systems to exert the perfect electrochemical performance of LiBOB. In this paper, LiBOB is synthesized by the compressing dry granulation method, with the yield of 97%. Moreover, the electrochemical performances of LiBOB-sulfolane (SL)/diethyl carbonate (DEC) electrolyte are investigated. It shows high oxidation potentials (>5.3 V) and satisfactory conductivities, also the temperature dependence of the conductivity is well in accord with the Vogel–Tamman–Fulcher (VTF) behavior. When used in Li/MCMB (mesophase carbon microbeads) cells, this novel electrolyte exhibits not only excellent film-forming characteristics, but also low impedances of the interface films. When used in LiFePO 4 /Li cells, compared to the cell with the electrolyte system of LiBOB-EC/DEC electrolyte, LiBOB-SL/DEC electrolyte exhibit several advantages, such as more stable cycle performance, and higher discharge voltage plateau (>3.35 V).

Universal low-temperature MWCNT-COOH-based counter electrode and a new thiolate/disulfide electrolyte system for dye-sensitized solar cells.

Science.gov (United States)

Hilmi, Abdulla; Shoker, Tharallah A; Ghaddar, Tarek H

2014-06-11

A new thiolate/disulfide organic-based electrolyte system composed of the tetrabutylammonium salt of 2-methyl-5-trifluoromethyl-2H-[1,2,4]triazole-3-thiol (S(-)) and its oxidized form 3,3'-dithiobis(2-methyl-5-trifluoromethyl-2H-[1,2,4]triazole) (DS) has been formulated and used in dye-sensitized solar cells (DSSCs). The electrocatalytic activity of different counter electrodes (CEs) has been evaluated by means of measuring J-V curves, cyclic voltammetry, Tafel plots, and electrochemical impedance spectroscopy. A stable and low-temperature CE based on acid-functionalized multiwalled carbon nanotubes (MWCNT-COOH) was investigated with our S(-)/DS, I(-)/I3(-), T(-)/T2, and Co(II/III)-based electrolyte systems. The proposed CE showed superb electrocatalytic activity toward the regeneration of the different electrolytes. In addition, good stability of solar cell devices based on the reported electrolyte and CE was shown.

Solid polymer electrolyte from phosphorylated chitosan

Energy Technology Data Exchange (ETDEWEB)

Fauzi, Iqbal, E-mail: arcana@chem.itb.ac.id; Arcana, I Made, E-mail: arcana@chem.itb.ac.id [Inorganic and Physical Chemistry Research Groups, Faculty of Mathematics and Natural Sciences, Institut Teknologi Bandung, Jl. Ganesha 10, Bandung 40132 (Indonesia)

2014-03-24

Recently, the need of secondary battery application continues to increase. The secondary battery which using a liquid electrolyte was indicated had some weakness. A solid polymer electrolyte is an alternative electrolytes membrane which developed in order to replace the liquid electrolyte type. In the present study, the effect of phosphorylation on to polymer electrolyte membrane which synthesized from chitosan and lithium perchlorate salts was investigated. The effect of the component’s composition respectively on the properties of polymer electrolyte, was carried out by analyzed of it’s characterization such as functional groups, ion conductivity, and thermal properties. The mechanical properties i.e tensile resistance and the morphology structure of membrane surface were determined. The phosphorylation processing of polymer electrolyte membrane of chitosan and lithium perchlorate was conducted by immersing with phosphoric acid for 2 hours, and then irradiated on a microwave for 60 seconds. The degree of deacetylation of chitosan derived from shrimp shells was obtained around 75.4%. Relative molecular mass of chitosan was obtained by viscometry method is 796,792 g/mol. The ionic conductivity of chitosan membrane was increase from 6.33 × 10{sup −6} S/cm up to 6.01 × 10{sup −4} S/cm after adding by 15 % solution of lithium perchlorate. After phosphorylation, the ionic conductivity of phosphorylated lithium chitosan membrane was observed 1.37 × 10{sup −3} S/cm, while the tensile resistance of 40.2 MPa with a better thermal resistance. On the strength of electrolyte membrane properties, this polymer electrolyte membrane was suggested had one potential used for polymer electrolyte in field of lithium battery applications.

Manganese oxide electrochemical capacitor with potassium poly(acrylate) hydrogel electrolyte

Science.gov (United States)

Lee, Kuang-Tsin; Wu, Nae-Lih

An aqueous gel electrolyte has for the first time been successfully applied to the MnO 2· nH 2O-based pseudocapacitive electrochemical capacitors (ECs). The gel electrolyte is made of potassium poly(acrylate) (PAAK) polymer and aqueous solution of KCl. With the selected composition, PAAK:KCl:H 2O = 9.0%:6.7%:84.3% by weight, the gel shows no fluidity, possessing an ionic conductivity in the order of 10 -1 S cm -1. The gel electrolyte has been found to give substantially higher specific capacitances than those in the liquid electrolyte with the same salt (KCl) composition (1 M) and high power capability (>10 kW/kg).

Manganese oxide electrochemical capacitor with potassium poly(acrylate) hydrogel electrolyte

Energy Technology Data Exchange (ETDEWEB)

Lee, Kuang-Tsin; Wu, Nae-Lih [Department of Chemical Engineering, National Taiwan University, Taipei 106 (China)

2008-04-15

An aqueous gel electrolyte has for the first time been successfully applied to the MnO{sub 2}.nH{sub 2}O-based pseudocapacitive electrochemical capacitors (ECs). The gel electrolyte is made of potassium poly(acrylate) (PAAK) polymer and aqueous solution of KCl. With the selected composition, PAAK:KCl:H{sub 2}O = 9.0%:6.7%:84.3% by weight, the gel shows no fluidity, possessing an ionic conductivity in the order of 10{sup -1} S cm{sup -1}. The gel electrolyte has been found to give substantially higher specific capacitances than those in the liquid electrolyte with the same salt (KCl) composition (1 M) and high power capability (>10 kW/kg). (author)

Enhanced Cycling Stability of Rechargeable Li-O2 Batteries Using High Concentration Electrolytes

Energy Technology Data Exchange (ETDEWEB)

Liu, Bin; Xu, Wu; Yan, Pengfei; Sun, Xiuliang; Bowden, Mark E.; Read, Jeffrey; Qian, Jiangfeng; Mei, Donghai; Wang, Chong M.; Zhang, Jiguang

2016-01-26

The electrolyte stability against reactive reduced-oxygen species is crucial for the development of rechargeable Li-O2 batteries. In this work, we systematically investigated the effect of lithium salt concentration in 1,2-dimethoxyethane (DME)-based electrolytes on the cycling stability of Li-O2 batteries. Cells with high concentration electrolyte illustrate largely enhanced cycling stability under both the full discharge/charge (2.0-4.5 V vs. Li/Li+) and the capacity limited (at 1,000 mAh g-1) conditions. These cells also exhibit much less reaction-residual on the charged air electrode surface, and much less corrosion to the Li metal anode. The density functional theory calculations are conducted on the molecular orbital energies of the electrolyte components and the Gibbs activation barriers for superoxide radical anion to attack DME solvent and Li+-(DME)n solvates. In a highly concentrated electrolyte, all DME molecules have been coordinated with salt and the C-H bond scission of a DME molecule becomes more difficult. Therefore, the decomposition of highly concentrated electrolyte in a Li-O2 battery can be mitigated and both air-cathodes and Li-metal anodes exhibits much better reversibility. As a results, the cyclability of Li-O2 can be largely improved.

A study on microstructure and corrosion resistance of ZrO{sub 2}-containing PEO coatings formed on AZ31 Mg alloy in phosphate-based electrolyte

Energy Technology Data Exchange (ETDEWEB)

Zhuang, J.J.; Guo, Y.Q.; Xiang, N. [Jiangsu Key Laboratory of Materials Surface Science and Technology, Changzhou University, Changzhou 213164 (China); Jiangsu Collaborative Innovation Center of Photovoltaic Science and Engineering, Changzhou University, Changzhou 213164, Jiangsu (China); Xiong, Y.; Hu, Q. [Jiangsu Key Laboratory of Materials Surface Science and Technology, Changzhou University, Changzhou 213164 (China); College of Mechanical Engineering, Zhejiang University of Technology, Hangzhou 310032 (China); Song, R.G., E-mail: songrg@hotmail.com [Jiangsu Key Laboratory of Materials Surface Science and Technology, Changzhou University, Changzhou 213164 (China); Jiangsu Collaborative Innovation Center of Photovoltaic Science and Engineering, Changzhou University, Changzhou 213164, Jiangsu (China)

2015-12-01

Graphical abstract: - Highlights: • PEO coatings were formed in K{sub 2}ZrF{sub 6}-containing electrolyte. • K{sub 2}ZrF{sub 6} is capable to optimize the microstructure of PEO coating. • Corrosion resistance of PEO coatings is effected by K{sub 2}ZrF{sub 6} concentration in the electrolyte. • Potentiodynamic polarization results are well matched with the EIS test results. • Long time immersion test confirmed the electrochemical results. - Abstract: ZrO{sub 2}-containing ceramic coatings formed on the AZ31 Mg alloy were fabricated in an alkaline electrolyte containing sodium phosphate and potassium fluorozirconate (K{sub 2}ZrF{sub 6}) by plasma electrolytic oxidation (PEO). X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) techniques were used to study the phase structure and composition of the coatings. It is indicated that the coatings formed in the K{sub 2}ZrF{sub 6}-containing electrolyte were composed of MgO, MgF{sub 2} and t-ZrO{sub 2}. Morphological investigation carried out by scanning electron microscopy (SEM) and stereoscopic microscopy, revealed that the uniformity of coatings increased and roughness of coatings decreased after the addition of K{sub 2}ZrF{sub 6}. Electrochemical investigation was achieved by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) test. The results showed that the PEO coating formed in K{sub 2}ZrF{sub 6}-containing electrolyte exhibited an improved corrosion resistance than that of the coating formed in K{sub 2}ZrF{sub 6}-free electrolyte. In addition, the polarization and EIS tests results both showed that the suitable concentration (2.5 g/l) of K{sub 2}ZrF{sub 6} is of significant ability to improve the corrosion resistance of coatings. However, 5 g/l and 10 g/l K{sub 2}ZrF{sub 6} has a negative effect on improving the corrosion resistance of PEO coatings compared with the coating formed in 2.5 g/l K{sub 2}ZrF{sub 6}-containing electrolyte.

Effect of alumina sol addition to micro-arc oxidation electrolyte on the properties of MAO coatings formed on magnesium alloy AZ91D

International Nuclear Information System (INIS)

Laleh, M.; Rouhaghdam, A. Sabour; Shahrabi, T.; Shanghi, A.

2010-01-01

Oxide coatings were formed on AZ91D magnesium alloy using micro-arc oxidation process in alkaline electrolyte without and with addition of alumina sol. The microstructures and compositions of the MAO coatings were analyzed by scanning electron microscope (SEM) and X-ray diffraction (XRD). Corrosion behaviors of the coatings were evaluated with electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization tests in 3.5%NaCl solution. Porosities of the coatings were measured by potentiodynamic polarization tests. It was found that the coating produced in the electrolyte with alumina sol has more compact and uniform morphology than that produced in the electrolyte without alumina sol. The results of corrosion tests showed that the coating formed in electrolyte with alumina sol enhances the corrosion resistance of the substrate significantly. XRD patterns showed that the coating produced in the electrolyte with alumina sol has more MgAl 2 O 4 phase than MgO.

The use of anions with sulfate function in electrolyte for lithium battery. Study of transport mechanism; Utilisation d'anions a fonction sulfate dans des electrolytes pour batterie au lithium. Etude des mecanismes de transport

Energy Technology Data Exchange (ETDEWEB)

Chauvin, Ch.

2005-05-15

Lithium salts based on oligo-ether sulfate were synthesized and characterised. They incorporate oxy-ethylene units which enable the lithium cation salvation and, potentially, their use as ionic liquids. Their properties as lithium salts dissolved in liquid or polymer electrolytes were evaluated. Their electrochemical and thermal stabilities are sufficient for lithium battery application. Due to their weak dissociation in POE, their conductivities are fairly low. On the other hand, they have high cationic transference numbers. In mixture with usual salts as LiTFSI, they provide a good compromise between conductivities/transference number/cost. The second part of this study deals with the synthesis and characterisation of an ionomer with sulfate function and polyether backbone. The electrochemical, physical and chemical properties of this material show that it could be used as polymer electrolyte. Its potential as cross-linked gelled polymer electrolyte is outstanding. Structural analyses on an ionomeric monocrystal have been corroborated with quantum chemistry calculations. (author)

Physiological Evaluation of Alkali-Salt Tolerance of Thirty Switchgrass (Panicum virgatum Lines.

Directory of Open Access Journals (Sweden)

Guofu Hu

Full Text Available Soil salt-alkalization is a major limiting factor for crop production in many regions. Switchgrass (Panicum virgatum L. is a warm-season C4 perennial rhizomatous bunchgrass and a target lignocellulosic biofuel species. The objective of this study was to evaluate relative alkali-salt tolerance among 30 switchgrass lines. Tillers of each switchgrass line were transplanted into pots filled with fine sand. Two months after transplanting, plants at E5 developmental stage were grown in either half strength Hoagland's nutrient solution with 0 mM Na+ (control or half strength Hoagland's nutrient solution with 150 mM Na+ and pH of 9.5 (alkali-salt stress treatment for 20 d. Alkali-salt stress damaged cell membranes [higher electrolyte leakage (EL], reduced leaf relative water content (RWC, net photosynthetic rate (Pn, stomatal conductance (gs, and transpiration rate (Tr. An alkali-salt stress tolerance trait index (ASTTI for each parameter was calculated based on the ratio of the value under alkali-salt stress and the value under non-stress conditions for each parameter of each line. Relative alkali-salt tolerance was determined based on principal components analysis and cluster analysis of the physiological parameters and their ASTTI values. Significant differences in alkali-salt stress tolerance were found among the 30 lines. Lowland lines TEM-SEC, Alamo, TEM-SLC and Kanlow were classified as alkali-salt tolerant. In contrast, three lowland lines (AM-314/MS-155, BN-13645-64 and two upland lines (Caddo and Blackwell-1 were classified as alkali-salt sensitive. The results suggest wide variations exist in alkali-salt stress tolerance among the 30 switchgrass lines. The approach of using a combination of principal components and cluster analysis of the physiological parameters and related ASTTI is feasible for evaluating alkali-salt tolerance in switchgrass.

Physiological Evaluation of Alkali-Salt Tolerance of Thirty Switchgrass (Panicum virgatum) Lines.

Science.gov (United States)

Hu, Guofu; Liu, Yiming; Zhang, Xunzhong; Yao, Fengjiao; Huang, Yan; Ervin, Erik H; Zhao, Bingyu

2015-01-01

Soil salt-alkalization is a major limiting factor for crop production in many regions. Switchgrass (Panicum virgatum L.) is a warm-season C4 perennial rhizomatous bunchgrass and a target lignocellulosic biofuel species. The objective of this study was to evaluate relative alkali-salt tolerance among 30 switchgrass lines. Tillers of each switchgrass line were transplanted into pots filled with fine sand. Two months after transplanting, plants at E5 developmental stage were grown in either half strength Hoagland's nutrient solution with 0 mM Na+ (control) or half strength Hoagland's nutrient solution with 150 mM Na+ and pH of 9.5 (alkali-salt stress treatment) for 20 d. Alkali-salt stress damaged cell membranes [higher electrolyte leakage (EL)], reduced leaf relative water content (RWC), net photosynthetic rate (Pn), stomatal conductance (gs), and transpiration rate (Tr). An alkali-salt stress tolerance trait index (ASTTI) for each parameter was calculated based on the ratio of the value under alkali-salt stress and the value under non-stress conditions for each parameter of each line. Relative alkali-salt tolerance was determined based on principal components analysis and cluster analysis of the physiological parameters and their ASTTI values. Significant differences in alkali-salt stress tolerance were found among the 30 lines. Lowland lines TEM-SEC, Alamo, TEM-SLC and Kanlow were classified as alkali-salt tolerant. In contrast, three lowland lines (AM-314/MS-155, BN-13645-64) and two upland lines (Caddo and Blackwell-1) were classified as alkali-salt sensitive. The results suggest wide variations exist in alkali-salt stress tolerance among the 30 switchgrass lines. The approach of using a combination of principal components and cluster analysis of the physiological parameters and related ASTTI is feasible for evaluating alkali-salt tolerance in switchgrass.

Association constants of telluronium salts

International Nuclear Information System (INIS)

Kovach, N.A.; Rivkin, B.B.; Sadekov, T.D.; Shvajka, O.P.

1996-01-01

Association constants in acetonitrile of triphenyl telluronium salts, which are dilute electrolytes, are determined through the conductometry method. Satisfactory correlation dependence of constants of interion association and threshold molar electroconductivity on the Litvinenko-Popov constants for depositing groups is identified. 6 refs

Galvanic high energy cells with molten electrolytes

Energy Technology Data Exchange (ETDEWEB)

Borger, W.; Kappus, W.; Kunze, D.; Laig-Hoerstebrock, H.; Panesar, H.; Sterr, G.

1981-01-01

To develop a galvanic cell with molten salt electrolyte for electric vehicle propulsion and load leveling as well as to fabricate ten prototype cells with a capacity of at least 150 Ah (5 hour rate) and an energy density of 80 Wh/kg was the objective of this project.

Phthaloylchitosan-Based Gel Polymer Electrolytes for Efficient Dye-Sensitized Solar Cells

Directory of Open Access Journals (Sweden)

S. N. F. Yusuf

2014-01-01

Full Text Available Phthaloylchitosan-based gel polymer electrolytes were prepared with tetrapropylammonium iodide, Pr4NI, as the salt and optimized for conductivity. The electrolyte with the composition of 15.7 wt.% phthaloylchitosan, 31.7 wt.% ethylene carbonate (EC, 3.17 wt.% propylene carbonate (PC, 19.0 wt.% of Pr4NI, and 1.9 wt.% iodine exhibits the highest room temperature ionic conductivity of 5.27 × 10−3 S cm−1. The dye-sensitized solar cell (DSSC fabricated with this electrolyte exhibits an efficiency of 3.5% with JSC of 7.38 mA cm−2, VOC of 0.72 V, and fill factor of 0.66. When various amounts of lithium iodide (LiI were added to the optimized gel electrolyte, the overall conductivity is observed to decrease. However, the efficiency of the DSSC increases to a maximum value of 3.71% when salt ratio of Pr4NI : LiI is 2 : 1. This cell has JSC, VOC and fill factor of 7.25 mA cm−2, 0.77 V and 0.67, respectively.

Corrosion Behavior of Superalloys in Hot Lithium Molten Salt

International Nuclear Information System (INIS)

Cho, Soo-Haeng; Hur, Jin-Mok; Seo, Chung-Seok; Park, Seoung-Won

2006-01-01

The Li-reduction process involves the chemical reduction of spent fuel oxides by liquid lithium metal in a molten LiCl salt bath at 650 .deg. C followed by a separate electrochemical reduction of lithium oxide (Li 2 O), which builds up in the salt bath. This process requires a high purity inert gas atmosphere inside remote hot cell nuclear facility to prevent unwanted Li oxidation and fires during the handling of chemically active Li metal. In light of the limitations of the Li-reduction process, a direct electrolytic reduction technology is being developed by KAERI to enhance process safety and economic viability. The electrolytic reduction of spent oxide fuel involves the liberation of oxygen in a molten LiCl electrolyte, which results in a chemically aggressive environment that is too corrosive for typical structural materials. Even so, the electrochemical process vessel must be resilient at ∼ 650 .deg. C in the presence of oxygen to enable high processing rates and an extended service life. But, the mechanism and the rate of the corrosion of metals in LiCl-Li 2 O molten salt under oxidation condition are not clear. In the present work, the corrosion behavior and corrosion mechanism of superalloys have been studied in the molten salt of LiCl-Li 2 O under oxidation condition

Tests of prototype salt stripper system for IFR fuel cycle

International Nuclear Information System (INIS)

Carls, E.L.; Blaskovitz, R.J.; Johnson, T.R.; Ogata, T.

1993-01-01

One of the waste treatment steps for the on-site reprocessing of spent fuel from the Integral Fast Reactor fuel cycles is stripping of the electrolyte salt used in the electrorefining process. This involves the chemical reduction of the actinides and rare earth chlorides forming metals which then dissolve in a cadmium pool. To develop the equipment for this step, a prototype salt stripper system has been installed in an engineering scale argon-filled glovebox. Pumping trails were successful in transferring 90 kg of LiCl-KCl salt containing uranium and rare earth metal chlorides at 500 degree C from an electrorefiner to the stripper vessel at a pumping rate of about 5 L/min. The freeze seal solder connectors which were used to join sections of the pump and transfer line performed well. Stripping tests have commenced employing an inverted cup charging device to introduce a Cd-15 wt % Li alloy reductant to the stripper vessel

Salt Lakes of the African Rift System: A Valuable Research ...

African Journals Online (AJOL)

Salt Lakes of the African Rift System: A Valuable Research Opportunity for Insight into Nature's Concenrtated Multi-Electrolyte Science. JYN Philip, DMS Mosha. Abstract. The Tanzanian rift system salt lakes present significant cultural, ecological, recreational and economical values. Beyond the wealth of minerals, resources ...

Properties of solid electrolyte interphase formed by prop-1-ene-1,3-sultone on graphite anode of Li-ion batteries

International Nuclear Information System (INIS)

Li, Bin; Xu, Mengqing; Li, Benzhen; Liu, Yanlin; Yang, Liang; Li, Weishan; Hu, Shejun

2013-01-01

Highlights: • SEI formed by PES on NG was characterized with charge/discharge test, SEM, FTIR, and XPS. • NG in PC-based electrolyte can be well protected using PES. • Sulfur-containing species is the main component of the SEI formed by PES. • Preferable reduction of PES results in the formation of protective SEI on NG. -- Abstract: The physical and chemical properties of the solid electrolyte interphase (SEI) formed by prop-1-ene-1,3-sultone (PES) on graphite anode in propylene carbonate (PC) based electrolyte for lithium ion battery were investigated by charge–discharge test, scanning electron spectroscopy with energy dispersive X-ray spectroscopy (SEM–EDS), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). It is found that the charge–discharge performance of the cell LiCoO 2 /natural graphite (NG) using PC-based electrolyte containing 3 wt% PES is superior to that containing 6 wt% propane sultone (PS), an SEI formation additive that has the similar molecular structure to PES but is reduced not as easily as PES. The results from SEM–EDS, FTIR and XPS show that the structure of graphite has been protected and some S-containing species are proven to be components of the SEI, suggesting that the preferable reduction of PES plays an important role in the formation of a protective SEI on NG

Electrolyte Suitable for Use in a Lithium Ion Cell or Battery

Science.gov (United States)

McDonald, Robert C. (Inventor)

2014-01-01

Electrolyte suitable for use in a lithium ion cell or battery. According to one embodiment, the electrolyte includes a fluorinated lithium ion salt and a solvent system that solvates lithium ions and that yields a high dielectric constant, a low viscosity and a high flashpoint. In one embodiment, the solvent system includes a mixture of an aprotic lithium ion solvating solvent and an aprotic fluorinated solvent.

Electrical transport study of potato starch-based electrolyte system-II

Energy Technology Data Exchange (ETDEWEB)

Tiwari, Tuhina; Kumar, Manindra [Department of Physics (Mahila Mahavidyalay), Banaras Hindu University, Varanasi (India); Srivastava, Neelam, E-mail: neelamsrivastava_bhu@yahoo.co.in [Department of Physics (Mahila Mahavidyalay), Banaras Hindu University, Varanasi (India); Srivastava, P.C. [Department of Physics, Banaras Hindu University, Varanasi (India)

2014-03-15

Highlights: • Cheap and bio-degradable polymer electrolyte. • High conductivity ∼ 9.59 × 10{sup −3} Scm{sup −1}. • Detailed ion dynamics stud. -- Abstract: Glutaraldehyde (GA) crosslinked potato starch, after mixing with sodium iodide (NaI), resulted in electrolyte film having conductivity (σ) ∼ 10{sup −3} S/cm and ionic transference number (t{sub ion}) ≥ 0.99. Out of two preparation mediums, namely methanol and acetone, methanol based electrolyte system seems to be better. Super-linear power law (SLPL) phenomenon is observed in MHz frequency range and both lattice site potential and coulomb cage potential due to neighboring mobile charge carriers seems to be responsible for existence of SLPL, and variation of power law exponent ‘n’ with salt concentration. These ion dynamics results are supported by dielectric data also. Estimated number of charge carriers ‘N’ and mobility ‘μ’ are discussed with reference to different variants (medium of preparation, plasticizer, and salt content). Material's conductivity strongly depends on humidity.

Ionic liquid electrolytes for dye-sensitized solar cells.

Science.gov (United States)

Gorlov, Mikhail; Kloo, Lars

2008-05-28

The potential of room-temperature molten salts (ionic liquids) as solvents for electrolytes for dye-sensitized solar cells has been investigated during the last decade. The non-volatility, good solvent properties and high electrochemical stability of ionic liquids make them attractive solvents in contrast to volatile organic solvents. Despite this, the relatively high viscosity of ionic liquids leads to mass-transport limitations. Here we review recent developments in the application of different ionic liquids as solvents or components of liquid and quasi-solid electrolytes for dye-sensitized solar cells.

Ionic conduction in polyether-based lithium arylfluorosulfonimide ionic melt electrolytes

International Nuclear Information System (INIS)

Herath, Mahesha B.; Creager, Stephen E.; Rajagopal, Rama V.; Geiculescu, Olt E.; DesMarteau, Darryl D.

2009-01-01

We report synthesis, characterization and ion transport in polyether-based ionic melt electrolytes consisting of Li salts of low-basicity anions covalently attached to polyether oligomers. Purity of the materials was investigated by HPLC analysis and electrospray ionization mass spectrometry. The highest ionic conductivity of 7.1 x 10 -6 S/cm at 30 deg. C was obtained for the sample consisting of a lithium salt of an arylfluorosulfonimide anion attached to a polyether oligomer with an ethyleneoxide (EO) to lithium ratio of 12. The conductivity order of various ionic melts having different polyether chain lengths suggests that at higher EO:Li ratios the conductivity of the electrolytes at room temperature is determined in part by the amount of crystallization of the polyether portion of the ionic melt.

Electrolytes for high voltage electrochemical double layer capacitors: A perspective article

Science.gov (United States)

Balducci, A.

2016-09-01

The development of innovative electrolyte components is nowadays considered one of the most important aspects for the realization of high energy electrochemical double capacitors (EDLCs). Consequently, in the last years many investigations have been dedicated towards new solvents, new salts and ionic liquids able to replace the current electrolytes. This perspective article aims to supply a critical analysis about the results obtained so far on the development of new electrolytes for high energy EDLCs and to outline the advantages as well as the limits related to the use of these innovative components. Furthermore, this article aims to give indications about the strategies could be used in the future for a further development of advanced electrolytes.

Lithium-Ion Electrolytes with Improved Safety Tolerance to High Voltage Systems

Science.gov (United States)

Smart, Marshall C. (Inventor); Bugga, Ratnakumar V. (Inventor); Prakash, Surya G. (Inventor); Krause, Frederick C. (Inventor)

2015-01-01

The invention discloses various embodiments of electrolytes for use in lithium-ion batteries, the electrolytes having improved safety and the ability to operate with high capacity anodes and high voltage cathodes. In one embodiment there is provided an electrolyte for use in a lithium-ion battery comprising an anode and a high voltage cathode. The electrolyte has a mixture of a cyclic carbonate of ethylene carbonate (EC) or mono-fluoroethylene carbonate (FEC) co-solvent, ethyl methyl carbonate (EMC), a flame retardant additive, a lithium salt, and an electrolyte additive that improves compatibility and performance of the lithium-ion battery with a high voltage cathode. The lithium-ion battery is charged to a voltage in a range of from about 2.0 V (Volts) to about 5.0 V (Volts).

Structural study of salt forms of amides; paracetamol, benzamide and piperine

Science.gov (United States)

Kennedy, Alan R.; King, Nathan L. C.; Oswald, Iain D. H.; Rollo, David G.; Spiteri, Rebecca; Walls, Aiden

2018-02-01

Single crystal x-ray diffraction has been used to investigate the structures of six complexes containing O-atom protonated cations derived from the pharmaceutically relevant amides benzamide (BEN), paracetamol (PAR) and piperine (PIP). The structures of the salt forms [PAR(H)][SO3C6H4Cl], [BEN(H)][O3SC6H4Cl] and [BEN(H)][Br]·H2O are reported along with those of the hemi-halide salt forms [PAR(H)][I3]. PAR, [PIP(H)][I3]·PIP and [PIP(H)][I3]0·5[I]0.5. PIP. The structure of the cocrystal BEN. HOOCCH2Cl is also presented for comparison. The geometry of the amide group is found to systematically change upon protonation, with the Cdbnd O distance increasing and the Csbnd N distance decreasing. The hemi-halide species all feature strongly hydrogen bonded amide(H)/amide pairs. The amide group Cdbnd O and Csbnd N distances for both elements of each such pair are intermediate between those found for simple neutral amide and protonated amide forms. It was found that crystallising paracetamol from aqueous solutions containing Ba2+ ions gave orthorhombic paracetamol.

Investigations of the Electrochemical Stability of Aqueous Electrolytes for Lithium Battery Applications

KAUST Repository

Wessells, Colin

2010-01-01

The electrolytic stability windows of several aqueous electrolytes were investigated by a constant current method. The electrode potential range depended upon the value of the imposed current. The magnitude of this behavior varied with the salt solution, its concentration, and pH of the electrolyte. At a leakage current density of 50 μA/cm2, a 5 M solution of LiNO3 had an electrolytic window of 2.3 V, spanning from -0.55 to 1.75 V with respect to the standard hydrogen electrode. These results demonstrate the feasibility of operating lithium batteries at voltages appreciably above the theoretical decomposition voltage of water. © 2010 The Electrochemical Society.

Ionic-Liquid-Tethered Nanoparticles: Hybrid Electrolytes

KAUST Repository

Moganty, Surya S.

2010-10-22

A new class of solventless electrolytes was created by tethering ionic liquids to hard inorganic ZrO2 nanostructures (see picture; NIM=nanoscale ionic material). These hybrid fluids exhibit exceptional redox stability windows, excellent thermal stability, good lithium transference numbers, long-term interfacial stability in the presence of a lithium anode and, when doped with lithium salt, reasonable ionic conductivities.

Thermal history and polymer electrolyte structure: implications for solid-state battery design

Energy Technology Data Exchange (ETDEWEB)

Neat, R.; Glasse, M.; Linford, R.

1986-01-01

Studies on PEO/LiCF/sub 3/SO/sub 3/ polymeric electrolytes using polarising microscopy, SEM/EDX, DSC and complex plane analysis show that thin electrolyte films prepared by slow evaporation from CH/sub 3/CN solution are spherulitic in nature. More than one type of spherulite is present across the composition range and each spherulite type contains both amorphous and crystalline regions. The structural behaviour on heating and cooling is discussed with particular reference to electrolyte films of overall composition PEO/sub 20/:LiCF/sub 3/SO/sub 3/. For these high ratio triflate films, in contrast to similar PEO/LiClO/sub 4/ films, high melting salt-rich regions are unexpectedly present in conjunction with low melting, low salt spherulites. No evidence is found for the presence of pure PEO spherulites, but the low melting spherulites may have a crystalline skeleton of pure PEO. Evidence is presented for the dependence of conductivity on thermal history.

Thermodynamics of aqueous electrolytes at various temperatures, pressures, and compositions. [Virial coefficients

Energy Technology Data Exchange (ETDEWEB)

Pitzer, K.S.

1979-09-01

It is shown that the properties of fully ionized aqueous electrolyte systems can be represented by relatively simple equations over wide ranges of composition. There are only a few systems for which data are available over the full range to fused salt. A simple equation commonly used for nonelectrolytes fits the measured vapor pressure of water reasonably well and further refinements are clearly possible. Over the somewhat more limited composition range up to saturation of typical salts such as NaCl, the equations representing thermodynamic properties with a Debye-Hueckel term plus second and third virial coefficients are very successful and these coefficients are known for nearly 300 electrolytes at room temperature. These same equations effectively predict the properties of mixed electrolytes. A stringent test is offered by the calculation of all of the solubility relationships of the system Na-K-Mg-Ca-Cl-So{sub 4}-H{sub 2}0 and the calculated results of Harvie and Weare show excellent agreement with

Method of electrolytically decontaminating of radioactive metal wastes

International Nuclear Information System (INIS)

Oonuma, Tsutomu; Tanaka, Akio; Yamadera, Toshio.

1985-01-01

Purpose: To significantly reduce the volume of secondary wastes by separating from electrolytes metal ions containing radioactive metal ions dissolved therein in the form of elemental metals of a reduced volume with ease, as well as regenerating the electrolytes for re-use. Method: Contaminated portions at the surface of the radioactive metal wastes are dissolved in electrolytes and, when the metal ion concentration in the electrolytes reaches a predetermined level, the electrolytes are introduced to an acid recovery step and an electrodeposition step. The recovered acid is re-used as the electrolytes, while dissolved metal ions containing radioactive metal ions are deposited as elemental metals in the electrodeposition step. The electrolytes usable herein include those acids easily forming stable complex compounds with the metals or those not forming hydroxides of the contaminated metals. Combination of sodium sulfate and sulfuric acid, sodium chloride and hydrochloride or the like is preferred. (Kamimura, M.)

Molten salt: Corrosion problems and electrometallurgy in nuclear applications

International Nuclear Information System (INIS)

Santarini, G.

1981-01-01

A bibliographic survey is given of corrosion problems and electrometallurgical problems of molten salt in nuclear reactor applications. Due to the high potential to be achieved, their high ionic conductivity and the rapidity of reactions in a molten salt atmosphere, molten salts are interesting solvents for various electrometallurgical processes. Another important field of application is in the separation or electrolytical refining of various metals (Be, U, Pu, Th, Hf, Zr). However, these very characteristics of molten salts may also cause serious corrosion problems. Results obtained for the molten-salt reactor and the different causes of corrosion are reviewed an possible countermeasures analyzed. (orig.)

FTIR Spectroscopic and DC Ionic conductivity Studies of PVDF-HFP: LiBF4: EC Plasticized Polymer Electrolyte Membrane

Science.gov (United States)

Sangeetha, M.; Mallikarjun, A.; Jaipal Reddy, M.; Siva Kumar, J.

2017-08-01

In the present paper; the FTIR and Temperature dependent DC Ionic conductivity studies of polymer (80 Wt% PVDF-HFP) with inorganic lithium tetra fluoroborate salt (20 Wt% LiBF4) as ionic charge carrier and plasticized with various weight ratios of Ethylene carbonate plasticizer (10 Wt% to 70 Wt% EC) as gel polymer electrolytes. Solution casting method is used for the preparation of plasticized polymer-salt electrolyte films. FTIR analysis shows the good complexation between PVDF-HFP: LiBF4 and the presence of functional groups in the plasticized polymer-salt electrolyte membrane. Also the analysis and results show that the highest DC ionic conductivity of 1.66 × 10-3 SCm -1 was found at 373 K for a particular concentration of 80 Wt% PVDF-HFP: 20 Wt% LiBF4: 40 Wt% EC porous gel type polymer-salt plasticized porous membrane. Increase of temperature results expansion and segmental motion of polymer chain that generates free volume in turn promotes hopping of the lithium ions satisfying Vogel-Tammann-Fulcher equation.

Polarization behavior of lithium electrode in polymetric solid electrolytes

Energy Technology Data Exchange (ETDEWEB)

Matsuda, Yoshiharu (Dept. of Applied Chemistry and Chemical Engineering, Faculty of Engineering, Yamaguchi Univ., Ube (Japan)); Morita, Masayuki (Dept. of Applied Chemistry and Chemical Engineering, Faculty of Engineering, Yamaguchi Univ., Ube (Japan)); Tsutsumi, Hiromori (Dept. of Applied Chemistry and Chemical Engineering, Faculty of Engineering, Yamaguchi Univ., Ube (Japan))

1993-04-15

Complexes of novel polymer matrices and lithium salts have been prepared as polymeric solid electrolytes for lithium batteries. Poly(ethylene oxide)-grafted poly(methylmethacrylate) (PEO-PMMA) and poly(methylsiloxane) (PMS) were used as the matrices. The conductance behavior of the complexes and the basic polarization characteristics of the lithium electrode in the polymeric electrolytes were studied. As high conductivities as 10[sup -3] S cm[sup -1] were obtained at room temperature for the PMMA-based electrolytes containing some liquid plasticizer. Limiting current densities of 3 to 5 mA cm[sup -2] were observed for the anodic and cathodic polarization of the lithium electrode. The transport number of Li[sup +] was approximately unity in 'single-ion type' PMS-based electrolyte, in which the polarization curve of the lithium electrode showed no current hysteresis. (orig.)

Nuclear magnetic resonance studies in solid polymeric electrolyte. Estudos por ressonancia magnetica nuclear em eletrolitos polimericos solidos

Energy Technology Data Exchange (ETDEWEB)

Donoso, J P; Mattoso, L H.C.; Cavalcante, M G [Sao Paulo Univ., Sao Carlos, SP (Brazil). Inst. de Fisica e Quimica; Gorecki, W; Berthier, C; Armand, M [Universite J. Fourier, Grenoble (France)

1990-01-01

Solid complexes formed between Poly (ethylene oxide) and various alkali metal salts, are generally referred to as polymer electrolytes conductivity and NMR properties were investigated in POE - Li Cl sub(7)O sub(4) and POE - Li BF sub(4) complexes. Our sup(1)H, Li and sup(19)F relaxation study suggest that cation motion is controlled by segmental motions of the polymer chain while the anion have additional mobility associated with BG sub(4) rotation. (author).

Lithium conducting ionic liquids based on lithium borate salts

Energy Technology Data Exchange (ETDEWEB)

Zygadlo-Monikowska, E.; Florjanczyk, Z.; Sluzewska, K.; Ostrowska, J.; Langwald, N.; Tomaszewska, A. [Warsaw University of Technology, Faculty of Chemistry, ul. Noakowskiego 3, 00-664 Warsaw (Poland)

2010-09-15

The simple reaction of trialkoxyborates with butyllithium resulted in the obtaining of new lithium borate salts: Li{l_brace}[CH{sub 3}(OCH{sub 2}CH{sub 2}){sub n}O]{sub 3}BC{sub 4}H{sub 9}{r_brace}, containing oxyethylene substituents (EO) of n=1, 2, 3 and 7. Salts of n {>=} 2 show properties of room temperature ionic liquid (RTIL) of low glass transition temperature, T{sub g} of the order from -70 to -80 C. The ionic conductivity of the salts depends on the number of EO units, the highest conductivity is shown by the salt with n = 3; in bulk its ambient temperature conductivity is 2 x 10{sup -5} S cm{sup -1} and in solution in cyclic propylene sulfite or EC/PC mixture, conductivity increases by an order of magnitude. Solid polymer electrolytes with borate salts over a wide concentration range, from 10 to 90 mol.% were obtained and characterized. Three types of polymeric matrices: poly(ethylene oxide) (PEO), poly(trimethylene carbonate) (PTMC) and two copolymers of acrylonitrile and butyl acrylate p(AN-BuA) were used in them as polymer matrices. It has been found that for systems of low salt concentration (10 mol.%) the best conducting properties were shown by solid polymer electrolytes with PEO, whereas for systems of high salt concentration, of the polymer-in-salt type, good results were achieved for PTMC as polymer matrix. (author)

Theoretical studies on the stability of the salts formed by DTDO with ...

Indian Academy of Sciences (India)

ment, nitrate and dinitramide have been widely used as counter ... as, ammonium nitrate6,7 and ammonium dinitramide,8,9 for which the ... thermal stability of the salt (2) formed from DTDO and ... charge decomposition analysis (ECDA):21.

Corrosion evaluation of zirconium doped oxide coatings on aluminum formed by plasma electrolytic oxidation.

Science.gov (United States)

Bajat, Jelena; Mišković-Stanković, Vesna; Vasilić, Rastko; Stojadinović, Stevan

2014-01-01

The plasma electrolytic oxidation (PEO) of aluminum in sodium tungstate (Na(2)WO(4) · (2)H(2)O) and Na(2)WO(4) · (2)H(2)O doped with Zr was analyzed in order to obtain oxide coatings with improved corrosion resistance. The influence of current density in PEO process and anodization time was investigated, as well as the influence of Zr, with the aim to find out how they affect the chemical content, morphology, surface roughness, and corrosion stability of oxide coatings. It was shown that the presence of Zr increases the corrosion stability of oxide coatings for all investigated PEO times. Evolution of EIS spectra during the exposure to 3% NaCl, as a strong corrosive agent, indicated the highest corrosion stability for PEO coating formed on aluminum at 70 mA/cm(2) for 2 min in a zirconium containing electrolyte.

Strongly nonlinear dynamics of electrolytes in large ac voltages

DEFF Research Database (Denmark)

Olesen, Laurits Højgaard; Bazant, Martin Z.; Bruus, Henrik

2010-01-01

to suppress the strongly nonlinear regime in the limit of concentrated electrolytes, ionic liquids, and molten salts. Beyond the model problem, our reduced equations for thin double layers, based on uniformly valid matched asymptotic expansions, provide a useful mathematical framework to describe additional...

Investigation of Ion-Solvent Interactions in Nonaqueous Electrolytes Using in Situ Liquid SIMS

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yanyan; Su, Mao; Yu, Xiaofei; Zhou, Yufan; Wang, Jungang; Cao, Ruiguo; Xu, Wu; Wang, Chongmin; Baer, Donald R.; Borodin, Oleg; Xu, Kang; Wang, Yanting; Wang, Xue-Lin; Xu, Zhijie; Wang, Fuyi; Zhu, Zihua

2018-02-06

Ion-solvent interactions in non-aqueous electrolytes are of fundamental interest and practical importance, yet debates regarding ion preferential solvation and coordination numbers persist. In this work, in situ liquid SIMS was used to examine ion-solvent interactions in three representative electrolytes, i.e., lithium hexafluorophosphate (LiPF6) at 1.0 M in ethylene carbonate (EC)-dimethyl carbonate (DMC), and lithium bis(fluorosulfonyl)imide (LiFSI) at both low (1.0 M) and high (4.0 M) concentrations in 1,2-dimethoxyethane (DME). In the positive ion mode, solid molecular evidence strongly supports the preferential solvation of Li+ by EC. Besides, from the negative spectra, we also found that PF6- forms association with EC, which has been neglected by previous studies due to the relatively weak interaction. While in both LiFSI in DME electrolytes, no evidence shows that FSI- is associated with DME. Furthermore, strong salt ion cluster signals were observed in the 1.0 M LiPF6 in EC-DMC electrolyte, suggesting that a significant amount of Li+ ions stay in vicinity of anions. In sharp comparison, weak ion cluster signals were detected in dilute LiFSI in DME electrolyte, suggesting most ions are well separated, in agreement with our molecular dynamics (MD) simulation results. These findings indicate that with virtues of little bias on detecting positive and negative ions and the capability of directly analyzing concentrated electrolytes, in situ liquid SIMS is a powerful tool that can provide key evidence for improved understanding on the ion-solvent interactions in non-aqueous electrolytes. Therefore, we anticipate wide applications of in situ liquid SIMS on investigations of various ion-solvent interactions in the near future.

Enhanced conductivity of sodium versus lithium salts measured by impedance spectroscopy. Sodium cobaltacarboranes as electrolytes of choice.

Science.gov (United States)

Fuentes, Isabel; Andrio, Andreu; Teixidor, Francesc; Viñas, Clara; Compañ, Vicente

2017-06-14

The development of new types of ion conducting materials is one of the most important challenges in the field of energy. Lithium salt polymer electrolytes have been the most convenient, and thus the most widely used in the design of the new generation of batteries. However, in this work, we have observed that Na + ions provide a higher conductivity, or at least a comparable conductivity to that of Li + ions in the same basic material. This provides an excellent possibility to use Na + ions in the design of a new generation of batteries, instead of lithium, to enhance conductivity and ensure wide supply. Our results indicate that the dc-conductivity is larger when the anion is [Co(C 2 B 9 H 11 ) 2 ] - , [COSANE] - , compared to tetraphenylborate, [TPB] - . Our data also prove that the dc-conductivity behavior of Li + and Na + salts is opposite with the two anions. At 40 °C, the conductivity values change from 1.05 × 10 -2 S cm -1 (Li[COSANE]) and 1.75 × 10 -2 S cm -1 (Na[COSANE]) to 2.8 × 10 -3 S cm -1 (Li[TPB]) and 1.5 × 10 -3 S cm -1 (Na[TPB]). These findings indicate that metallacarboranes can be useful components of mixed matrix membranes (MMMs), providing excellent conductivity when the medium contains sufficient amounts of ionic components and a certain degree of humidity.

Benchmarking of electrolyte mass transport in next generation lithium batteries

Directory of Open Access Journals (Sweden)

Jonas Lindberg

2017-12-01

Full Text Available Beyond conductivity and viscosity, little is often known about the mass transport properties of next generation lithium battery electrolytes, thus, making performance estimation uncertain when concentration gradients are present, as conductivity only describes performance in the absence of these gradients. This study experimentally measured the diffusion resistivity, originating from voltage loss due to a concentration gradient, together with the ohmic resistivity, obtained from ionic conductivity measurements, hence, evaluating electrolytes both with and without the presence of concentration gradients. Under galvanostatic conditions, the concentration gradients, of all electrolytes examined, developed quickly and the diffusion resistivity rapidly dominated the ohmic resistivity. The electrolytes investigated consisted of lithium salt in: room temperature ionic liquids (RTIL, RTIL mixed organic carbonates, dimethyl sulfoxide (DMSO, and a conventional Li-ion battery electrolyte. At steady state the RTIL electrolytes displayed a diffusion resistivity ~ 20 times greater than the ohmic resistivity. The DMSO-based electrolyte showed mass transport properties similar to the conventional Li-ion battery electrolyte. In conclusion, the results presented in this study show that the diffusion polarization must be considered in applications where high energy and power density are desired.

On the use of voltammetric methods to determine electrochemical stability limits for lithium battery electrolytes

Science.gov (United States)

Georén, Peter; Lindbergh, Göran

In previous studies a novel amphiphilic co-polymer was developed for use in lithium-ion batteries. In order to evaluate the electrochemical stability of that electrolyte and compare it with others, a voltammetric method was applied on a set of electrolytes with different salts, solvents and polymers. However, initially the voltammetric methodology was studied. Platinum was found to be the most suited electrode material, experiencing no significant interfering reactions and a proper diffusion-controlled kinetic behaviour when sweep rate was varied. Furthermore, the influence on the voltammograms of adding water traces to the electrolytes was studied. It could be established that the oxidation peak around 3.8 V versus Li was related to water reactions. It was concluded that quantitative voltage values of the stability limits were difficult to assess using voltammetry. On the other hand, the method seemed well suited for comparison of electrolytes and to investigate the influences of electrolyte components on the stability. The voltammetric results varied little between the different electrolytes evaluated and the anodic and cathodic limits, as defined here, were in the range of 1 and 4.5 V vs. Li, respectively. Although the novel polymer did not affect the stability limit significantly it seemed to promote the breakdown reaction rate in all electrolytes tested. Furthermore, the use of LiTFSI salt reduced the stability window.

Enhanced lithium battery with polyethylene oxide-based electrolyte containing silane-Al2 O3 ceramic filler.

Science.gov (United States)

Zewde, Berhanu W; Admassie, Shimelis; Zimmermann, Jutta; Isfort, Christian Schulze; Scrosati, Bruno; Hassoun, Jusef

2013-08-01

A solid polymer electrolyte prepared by using a solvent-free, scalable technique is reported. The membrane is formed by low-energy ball milling followed by hot-pressing of dry powdered polyethylene oxide polymer, LiCF3 SO3 salt, and silane-treated Al2 O3 (Al2 O3 -ST) ceramic filler. The effects of the ceramic fillers on the properties of the ionically conducting solid electrolyte membrane are characterized by using electrochemical impedance spectroscopy, XRD, differential scanning calorimeter, SEM, and galvanostatic cycling in lithium cells with a LiFePO4 cathode. We demonstrate that the membrane containing Al2 O3 -ST ceramic filler performs well in terms of ionic conductivity, thermal properties, and lithium transference number. Furthermore, we show that the lithium cells, which use the new electrolyte together with the LiFePO4 electrode, operate within 65 and 90 °C with high efficiency and long cycle life. Hence, the Al2 O3 -ST ceramic can be efficiently used as a ceramic filler to enhance the performance of solid polymer electrolytes in lithium batteries. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect upon biocompatibility and biocorrosion properties of plasma electrolytic oxidation in trisodium phosphate electrolytes.

Science.gov (United States)

Kim, Yu-Kyoung; Park, Il-Song; Lee, Kwang-Bok; Bae, Tae-Sung; Jang, Yong-Seok; Oh, Young-Min; Lee, Min-Ho

2016-03-01

Surface modification to improve the corrosion resistance and biocompatibility of the Mg-Al-Zn-Ca alloy was conducted via plasma electrolytic oxidation (PEO) in an electrolyte that included phosphate. Calcium phosphate can be easily induced on the surface of a PEO coating that includes phosphate in a physiological environment because Ca(2+) ions in body fluids can be combined with PO4 (3-). Cytotoxicity of the PEO coating formed in electrolytes with various amounts of Na3PO4 was identified. In particular, the effects that PEO films have upon oxidative stress and differentiation of osteoblast activity were studied. As the concentration of Na3PO4 in the electrolyte increased, the oxide layer was found to become thicker, which increased corrosion resistance. However, the PEO coating formed in electrolytes with over 0.2 M of added Na3PO4 exhibited more microcracks and larger pores than those formed in smaller Na3PO4 concentrations owing to a large spark discharge. A nonuniform oxide film that included more phosphate caused more cytotoxicity and oxidative stress, and overabundant phosphate content in the oxide layer interrupted the differentiation of osteoblasts. The corrosion resistance of the magnesium alloy and the thickness of the oxide layer were increased by the addition of Na3PO4 in the electrolyte for PEO treatment. However, excessive phosphate content in the oxide layer led to oxidative stress, which resulted in reduced cell viability and activity.

Effect of additive on electrochemical corrosion properties of plasma electrolytic oxidation coatings formed on CP Ti under different processing frequency

Energy Technology Data Exchange (ETDEWEB)

Babaei, Mahdi, E-mail: mahdi.babaei@ut.ac.ir; Dehghanian, Changiz; Vanaki, Mojtaba

2015-12-01

Highlights: • PEO coatings formed on Cp Ti from phosphate electrolyte with zirconate additive. • The SEM results provide information of microdischarge behavior. • The effect of additive on structure and long-term corrosion behavior was investigated. • The additive influence on coating performance varies with processing frequency. - Abstract: The plasma electrolytic oxidation (PEO) coating containing zirconium oxide was fabricated on CP Ti at different processing frequencies viz., 100 Hz and 1000 Hz in a (Na{sub 2}ZrO{sub 3}, Na{sub 2}SiO{sub 3})-additive containing NaH{sub 2}PO{sub 4}-based solution, and long-term electrochemical corrosion behavior of the coatings was studied using electrochemical impedance spectroscopy (EIS) in 3.5 wt.% NaCl solution. Electrochemical degradation behavior of two-layered coatings formed at different frequencies was turned out to be governed by concentration of electrolyte additive. With increasing additive concentration, the coating obtained at frequency of 1000 Hz exhibited enhanced corrosion resistance. However, corrosion resistance of the coating prepared at 100 Hz was found to decrease with increased additive, which was attributed to intensified microdischarges damaging the protective effect of inner layer. Nevertheless, the electrolyte additive was found to mitigate the long-term degradation of the coatings to a significant extent.

The effects of functional ionic liquid on properties of solid polymer electrolyte

International Nuclear Information System (INIS)

An Yongxin; Cheng Xinqun; Zuo Pengjian; Liao Lixia; Yin Geping

2011-01-01

Highlights: → The functional ionic liquid(IL)-polymer electrolytes were successfully prepared. → The ionic conductivity of PEO electrolytes was raised to above 10-4 S.cm-1 at room temperature by functional IL. → The cells using functional IL-PEO electrolyte show higher reversible capacity and long cycle life. - Abstract: Polyethylene oxide (PEO) based solid state electrolytes have been thought as promising electrolytes to replace the organic liquid electrolyte for lithium ion batteries. But the lower ionic conductivities at room temperature restrict their application. In this paper, functional ionic liquid and polymer mixed electrolytes are prepared from N-methyoxymethyl-N-methylpiperidinium bis(trifluoromethanesulfonyl)imide (PP1.1O1TFSI) and polyethylene oxide. The PP1.1O1TFSI, a kind of room-temperature molten salt, was added to the conventional P(EO) 20 LiTFSI polymer electrolyte and resulted in a significant improvement of the ionic conductivity at room temperature. LiFePO 4 /Li and Li 4 Ti 5 O 12 /Li cells using this kind of electrolyte show high reversible capacity and stable cycle performance.

"Solvent-in-salt" systems for design of new materials in chemistry, biology and energy research.

Science.gov (United States)

Azov, Vladimir A; Egorova, Ksenia S; Seitkalieva, Marina M; Kashin, Alexey S; Ananikov, Valentine P

2018-02-21

Inorganic and organic "solvent-in-salt" (SIS) systems have been known for decades but have attracted significant attention only recently. Molten salt hydrates/solvates have been successfully employed as non-flammable, benign electrolytes in rechargeable lithium-ion batteries leading to a revolution in battery development and design. SIS with organic components (for example, ionic liquids containing small amounts of water) demonstrate remarkable thermal stability and tunability, and present a class of admittedly safer electrolytes, in comparison with traditional organic solvents. Water molecules tend to form nano- and microstructures (droplets and channel networks) in ionic media impacting their heterogeneity. Such microscale domains can be employed as microreactors for chemical and enzymatic synthesis. In this review, we address known SIS systems and discuss their composition, structure, properties and dynamics. Special attention is paid to the current and potential applications of inorganic and organic SIS systems in energy research, chemistry and biochemistry. A separate section of this review is dedicated to experimental methods of SIS investigation, which is crucial for the development of this field.

Saltstone: cement-based waste form for disposal of Savannah River Plant low-level radioactive salt waste

International Nuclear Information System (INIS)

Langton, C.A.

1984-01-01

Defense waste processing at the Savannah River Plant will include decontamination and disposal of approximately 400 million liters of waste containing NaNO 3 , NaOH, Na 2 SO 4 , and NaNO 2 . After decontamination, the salt solution is classified as low-level waste. A cement-based waste form, saltstone, has been designed for disposal of Savannah River Plant low-level radioactive salt waste. Bulk properties of this material have been tailored with respect to salt leach rate, permeability, and compressive strength. Microstructure and mineralogy of leached and unleached specimens were characterized by SEM and x-ray diffraction analyses. The disposal system for the DWPF salt waste includes reconstitution of the crystallized salt as a solution containing 32 wt % solids. This solution will be decontaminated to remove 137 Cs and 90 Sr and then stabilized in a cement-based waste form. Laboratory and field tests indicate that this stabilization process greatly reduces the mobility of all of the waste constitutents in the surface and near-surface environment. Engineered trenches for subsurface burial of the saltstone have been designed to ensure compatibility between the waste form and the environment. The total disposal sytem, saltstone-trench-surrounding soil, has been designed to contain radionuclides, Cr, and Hg by both physical encapsulation and chemical fixation mechanisms. Physical encapsulation of the salts is the mechanism employed for controlling N and OH releases. In this way, final disposal of the SRP low-level waste can be achieved and the quality of the groundwater at the perimeter of the disposal site meets EPA drinking water standards

Preparation and characterization of plasticized palm-based polyurethane solid polymer electrolyte

Energy Technology Data Exchange (ETDEWEB)

Daud, Farah Nadia; Ahmad, Azizan; Badri, Khairiah Haji [School of Chemical Science and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor Darul Ehsan (Malaysia)

2013-11-27

Palm-based polyurethane solid polymer electrolyte was prepared via prepolymerization method between palm kernel oil based polyols (PKO-p) and 2,4’-diphenylmethane diisocyanate (2,4’-MDI) in acetone at room temperature with the vary amount of lithium trifuoromethanesulfonate (LiCF{sub 3}SO{sub 3}) salt and polyethylene glycol (PEG). The film was analyzed using attenuated total reflection infrared (ATR-IR) spectroscopy, electrochemical impedance spectroscopy (EIS) and X-ray diffractometry (XRD). EIS result indicated ionic conductivity obtained with 30 wt% LiCF3SO3 increased to 6.55 × 10{sup −6} S cm{sup −1} when 10 wt.% of plasticizer was added into the system. FTIR analysis showed the interaction between lithium ions and amine (-N-H) at 3600–3100 cm{sup −1}, carbonyl (-C=O) at 1750–1650 cm{sup −1} and ether (-C-O-C-) at 1150–1000 cm{sup −1} of the polyurethane forming polymer-salt complexes. The XRD result confirmed that LiCF{sub 3}SO{sub 3} salt completely dissociated within the polyurethane film with the absence of crystalline peaks of LiCF{sub 3}SO{sub 3}.

Preparation and characterization of plasticized palm-based polyurethane solid polymer electrolyte

International Nuclear Information System (INIS)

Daud, Farah Nadia; Ahmad, Azizan; Badri, Khairiah Haji

2013-01-01

Palm-based polyurethane solid polymer electrolyte was prepared via prepolymerization method between palm kernel oil based polyols (PKO-p) and 2,4’-diphenylmethane diisocyanate (2,4’-MDI) in acetone at room temperature with the vary amount of lithium trifuoromethanesulfonate (LiCF 3 SO 3 ) salt and polyethylene glycol (PEG). The film was analyzed using attenuated total reflection infrared (ATR-IR) spectroscopy, electrochemical impedance spectroscopy (EIS) and X-ray diffractometry (XRD). EIS result indicated ionic conductivity obtained with 30 wt% LiCF3SO3 increased to 6.55 × 10 −6 S cm −1 when 10 wt.% of plasticizer was added into the system. FTIR analysis showed the interaction between lithium ions and amine (-N-H) at 3600–3100 cm −1 , carbonyl (-C=O) at 1750–1650 cm −1 and ether (-C-O-C-) at 1150–1000 cm −1 of the polyurethane forming polymer-salt complexes. The XRD result confirmed that LiCF 3 SO 3 salt completely dissociated within the polyurethane film with the absence of crystalline peaks of LiCF 3 SO 3

Crosslinked Polymer Ionic Liquid/Ionic Liquid Blends Prepared by Photopolymerization as Solid-State Electrolytes in Supercapacitors.

Science.gov (United States)

Wang, Po-Hsin; Wang, Tzong-Liu; Lin, Wen-Churng; Lin, Hung-Yin; Lee, Mei-Hwa; Yang, Chien-Hsin

2018-04-07

A photopolymerization method is used to prepare a mixture of polymer ionic liquid (PIL) and ionic liquid (IL). This mixture is used as a solid-state electrolyte in carbon nanoparticle (CNP)-based symmetric supercapacitors. The solid electrolyte is a binary mixture of a PIL and its corresponding IL. The PIL matrix is a cross-linked polyelectrolyte with an imidazole salt cation coupled with two anions of Br - in PIL-M-(Br) and TFSI - in PIL-M-(TFSI), respectively. The corresponding ionic liquids have imidazolium salt cation coupled with two anions of Br - and TFSI - , respectively. This study investigates the electrochemical characteristics of PILs and their corresponding IL mixtures used as a solid electrolyte in supercapacitors. Results show that a specific capacitance, maximum power density and energy density of 87 and 58 F·g - ¹, 40 and 48 kW·kg - ¹, and 107 and 59.9 Wh·kg - ¹ were achieved in supercapacitors based on (PIL-M-(Br)) and (PIL-M-(TFSI)) solid electrolytes, respectively.

Enhancing ionic conductivity in composite polymer electrolytes with well-aligned ceramic nanowires

Science.gov (United States)

Liu, Wei; Lee, Seok Woo; Lin, Dingchang; Shi, Feifei; Wang, Shuang; Sendek, Austin D.; Cui, Yi

2017-04-01

In contrast to conventional organic liquid electrolytes that have leakage, flammability and chemical stability issues, solid electrolytes are widely considered as a promising candidate for the development of next-generation safe lithium-ion batteries. In solid polymer electrolytes that contain polymers and lithium salts, inorganic nanoparticles are often used as fillers to improve electrochemical performance, structure stability, and mechanical strength. However, such composite polymer electrolytes generally have low ionic conductivity. Here we report that a composite polymer electrolyte with well-aligned inorganic Li+-conductive nanowires exhibits an ionic conductivity of 6.05 × 10-5 S cm-1 at 30 ∘C, which is one order of magnitude higher than previous polymer electrolytes with randomly aligned nanowires. The large conductivity enhancement is ascribed to a fast ion-conducting pathway without crossing junctions on the surfaces of the aligned nanowires. Moreover, the long-term structural stability of the polymer electrolyte is also improved by the use of nanowires.

Screening nitrogen-rich bases and oxygen-rich acids by theoretical calculations for forming highly stable salts.

Science.gov (United States)

Zhang, Xueli; Gong, Xuedong

2014-08-04

Nitrogen-rich heterocyclic bases and oxygen-rich acids react to produce energetic salts with potential application in the field of composite explosives and propellants. In this study, 12 salts formed by the reaction of the bases 4-amino-1,2,4-trizole (A), 1-amino-1,2,4-trizole (B), and 5-aminotetrazole (C), upon reaction with the acids HNO3 (I), HN(NO2 )2 (II), HClO4 (III), and HC(NO2 )3 (IV), are studied using DFT calculations at the B97-D/6-311++G** level of theory. For the reactions with the same base, those of HClO4 are the most exothermic and spontaneous, and the most negative Δr Gm in the formation reaction also corresponds to the highest decomposition temperature of the resulting salt. The ability of anions and cations to form hydrogen bonds decreases in the order NO3 (-) >N(NO2 )2 (-) >ClO4 (-) >C(NO2 )3 (-) , and C(+) >B(+) >A(+) . In particular, those different cation abilities are mainly due to their different conformations and charge distributions. For the salts with the same anion, the larger total hydrogen-bond energy (EH,tot ) leads to a higher melting point. The order of cations and anions on charge transfer (q), second-order perturbation energy (E2 ), and binding energy (Eb ) are the same to that of EH,tot , so larger q leads to larger E2 , Eb , and EH,tot . All salts have similar frontier orbitals distributions, and their HOMO and LUMO are derived from the anion and the cation, respectively. The molecular orbital shapes are kept as the ions form a salt. To produce energetic salts, 5-aminotetrazole and HClO4 are the preferred base and acid, respectively. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of Ca(PF6)2, formed via nitrosonium oxidation of calcium.

Science.gov (United States)

Keyzer, Evan N; Matthews, Peter D; Liu, Zigeng; Bond, Andrew D; Grey, Clare P; Wright, Dominic S

2017-04-20

The development of rechargeable Ca-ion batteries as an alternative to Li systems has been limited by the availability of suitable electrolyte salts. We present the synthesis of complexes of Ca(PF 6 ) 2 (a key potential Ca battery electrolyte salt) via the treatment of Ca metal with NOPF 6 , and explore their conversion to species containing PO 2 F 2 - under the reaction conditions.

Identifying compatibility of lithium salts with LiFePO4 cathode using a symmetric cell

Science.gov (United States)

Tong, Bo; Wang, Jiawei; Liu, Zhenjie; Ma, Lipo; Zhou, Zhibin; Peng, Zhangquan

2018-04-01

The electrochemical performance of lithium-ion batteries is dominated by the interphase electrochemistry between the electrolyte and electrode materials. A multitude of efforts have been dedicated to the solid electrolyte interphase (SEI) formed on the anode. However, the interphase on the cathode, namely the cathode electrolyte interphase (CEI), is left aside, partially due to the fact that it is hard to single out the CEI considering the complicated anode-cathode inter-talk. Herein, a partially delithiated lithium iron phosphate (Li0.25FePO4) electrode is used as the anode. Owing to a high voltage plateau (≈3.45 V vs. Li/Li+), negligible reduction reactions of electrolyte occur on the L0.25FePO4 anode. Therefore, the CEI can be investigated exclusively. Using a LiFePO4|Li0.25FePO4 symmetric cell configuration, we scrutinize the compatibility of the electrolytes containing a wide spectrum of lithium salts, Li[(FSO2)(Cm F2m+1SO2)N] (m = 0, 1, 2, 4), with the LiFePO4, in both cycling and calendar tests. It is found that the Li[(FSO2)(n-C4F9SO2)N] (LiFNFSI)-based electrolyte exhibits the highest compatibility with LiFePO4.

Potentiometric Sensor for Real-Time Monitoring of Multivalent Ion Concentrations in Molten Salt

International Nuclear Information System (INIS)

Zink, Peter A.; Jue, Jan-Fong; Serrano, Brenda E.; Fredrickson, Guy L.; Cowan, Ben F.; Herrmann, Steven D.; Li, Shelly X.

2010-01-01

Electrorefining of spent metallic nuclear fuel in high temperature molten salt systems is a core technology in pyroprocessing, which in turn plays a critical role in the development of advanced fuel cycle technologies. In electrorefining, spent nuclear fuel is treated electrochemically in order to effect separations between uranium, noble metals, and active metals, which include the transuranics. The accumulation of active metals in a lithium chloride-potassium chloride (LiCl-KCl) eutectic molten salt electrolyte occurs at the expense of the UCl3-oxidant concentration in the electrolyte, which must be periodically replenished. Our interests lie with the accumulation of active metals in the molten salt electrolyte. The real-time monitoring of actinide concentrations in the molten salt electrolyte is highly desirable for controlling electrochemical operations and assuring materials control and accountancy. However, real-time monitoring is not possible with current methods for sampling and chemical analysis. A new solid-state electrochemical sensor is being developed for real-time monitoring of actinide ion concentrations in a molten salt electrorefiner. The ultimate function of the sensor is to monitor plutonium concentrations during electrorefining operations, but in this work gadolinium was employed as a surrogate material for plutonium. In a parametric study, polycrystalline sodium beta double-prime alumina (Na-β(double p rime)-alumina) discs and tubes were subject to vapor-phase exchange with gadolinium ions (Gd3+) using a gadolinium chloride salt (GdCl3) as a precursor to produce gadolinium beta double-prime alumina (Gd-β(double p rime)-alumina) samples. Electrochemical impedance spectroscopy and microstructural analysis were performed on the ion-exchanged discs to determine the relationship between ion exchange and Gd3+ ion conductivity. The ion-exchanged tubes were configured as potentiometric sensors in order to monitor real-time Gd3+ ion concentrations in

Electrochemical behavior of ionically crosslinked polyampholytic gel electrolytes

International Nuclear Information System (INIS)

Chen Wanyu; Tang Haitao; Ou Ziwei; Wang Hong; Yang Yajiang

2007-01-01

An ionic complex of anionic and cationic monomers was obtained by protonation of (N,N-diethylamino)ethylmethacrylate (DEA) with acrylic acid (AAc). Free radical copolymerization of the ionic complex and acrylamide (AAm), yielded the ionically crosslinked polyampholytic gel electrolytes [poly(AAc-DEA-AAm), designated as PADA] using two types of organic solvents containing a lithium salt. The PADA gel electrolyte exhibited good thermal stability shown by the DSC thermogram. The impedance analysis at temperatures ranging from -30 to 75 deg. C indicated that the ionic conductivities of the PADA gel electrolytes were rather close to those of liquid electrolytes. The temperature dependence of the ionic conductivities was found to be in accord with the Arrhenius equation. Moreover, the ionic conductivities of PADA gel electrolytes increased with an increase of the molar ratios of cationic/anionic monomers. The ionic conductivities of PADA gels prepared in solvent mixtures of propylene carbonate, ethyl methyl ether and dioxolane (3:1:1, v/v) were higher than those of PADA gels prepared in propylene carbonate only. Significantly, the ionic conductivities of two kinds of PADA gel electrolytes were in the range of 10 -3 and 10 -4 S cm -1 even at -30 deg. C. The electrochemical windows of PADA gel electrolytes measured by cyclic voltammetry were in the range from -1 V to 4.5 V

Amorphous salts formed from rapid dehydration of multicomponent chloride and ferric sulfate brines: Implications for Mars

Science.gov (United States)

Sklute, Elizabeth C.; Rogers, A. Deanne; Gregerson, Jason C.; Jensen, Heidi B.; Reeder, Richard J.; Dyar, M. Darby

2018-03-01

Salts with high hydration states have the potential to maintain high levels of relative humidity (RH) in the near subsurface of Mars, even at moderate temperatures. These conditions could promote deliquescence of lower hydrates of ferric sulfate, chlorides, and other salts. Previous work on deliquesced ferric sulfates has shown that when these materials undergo rapid dehydration, such as that which would occur upon exposure to present day Martian surface conditions, an amorphous phase forms. However, the fate of deliquesced halides or mixed ferric sulfate-bearing brines are presently unknown. Here we present results of rapid dehydration experiments on Ca-, Na-, Mg- and Fe-chloride brines and multicomponent (Fe2(SO4)3 ± Ca, Na, Mg, Fe, Cl, HCO3) brines at ∼21 °C, and characterize the dehydration products using visible/near-infrared (VNIR) reflectance spectroscopy, mid-infrared attenuated total reflectance spectroscopy, and X-ray diffraction (XRD) analysis. We find that rapid dehydration of many multicomponent brines can form amorphous solids or solids with an amorphous component, and that the presence of other elements affects the persistence of the amorphous phase under RH fluctuations. Of the pure chloride brines, only Fe-chloride formed an amorphous solid. XRD patterns of the multicomponent amorphous salts show changes in position, shape, and magnitude of the characteristic diffuse scattering observed in all amorphous materials that could be used to help constrain the composition of the amorphous salt. Amorphous salts deliquesce at lower RH values compared to their crystalline counterparts, opening up the possibility of their role in potential deliquescence-related geologic phenomena such as recurring slope lineae (RSLs) or soil induration. This work suggests that a wide range of aqueous mixed salt solutions can lead to the formation of amorphous salts and are possible for Mars; detailed studies of the formation mechanisms, stability and transformation

Amorphous salts formed from rapid dehydration of multicomponent chloride and ferric sulfate brines: Implications for Mars

Science.gov (United States)

Sklute, Elizabeth C.; Rogers, A. Deanne; Gregerson, Jason C.; Jensen, Heidi B.; Reeder, Richard J.; Dyar, M. Darby

2018-01-01

Salts with high hydration states have the potential to maintain high levels of relative humidity (RH) in the near subsurface of Mars, even at moderate temperatures. These conditions could promote deliquescence of lower hydrates of ferric sulfate, chlorides, and other salts. Previous work on deliquesced ferric sulfates has shown that when these materials undergo rapid dehydration, such as that which would occur upon exposure to present day Martian surface conditions, an amorphous phase forms. However, the fate of deliquesced halides or mixed ferric sulfate-bearing brines are presently unknown. Here we present results of rapid dehydration experiments on Ca–, Na–, Mg– and Fe–chloride brines and multi-component (Fe2 (SO4)3 ± Ca, Na, Mg, Fe, Cl, HCO3) brines at ∼21°C, and characterize the dehydration products using visible/near-infrared (VNIR) reflectance spectroscopy, mid-infrared attenuated total reflectance spectroscopy, and X-ray diffraction (XRD) analysis. We find that rapid dehydration of many multicomponent brines can form amorphous solids or solids with an amorphous component, and that the presence of other elements affects the persistence of the amorphous phase under RH fluctuations. Of the pure chloride brines, only Fe–chloride formed an amorphous solid. XRD patterns of the multicomponent amorphous salts show changes in position, shape, and magnitude of the characteristic diffuse scattering observed in all amorphous materials that could be used to help constrain the composition of the amorphous salt. Amorphous salts deliquesce at lower RH values compared to their crystalline counterparts, opening up the possibility of their role in potential deliquescence-related geologic phenomena such as recurring slope lineae (RSLs) or soil induration. This work suggests that a wide range of aqueous mixed salt solutions can lead to the formation of amorphous salts and are possible for Mars; detailed studies of the formation mechanisms, stability and

Amorphous salts formed from rapid dehydration of multicomponent chloride and ferric sulfate brines: Implications for Mars.

Science.gov (United States)

Sklute, Elizabeth C; Rogers, A Deanne; Gregerson, Jason C; Jensen, Heidi B; Reeder, Richard J; Dyar, M Darby

2018-03-01

Salts with high hydration states have the potential to maintain high levels of relative humidity (RH) in the near subsurface of Mars, even at moderate temperatures. These conditions could promote deliquescence of lower hydrates of ferric sulfate, chlorides, and other salts. Previous work on deliquesced ferric sulfates has shown that when these materials undergo rapid dehydration, such as that which would occur upon exposure to present day Martian surface conditions, an amorphous phase forms. However, the fate of deliquesced halides or mixed ferric sulfate-bearing brines are presently unknown. Here we present results of rapid dehydration experiments on Ca-, Na-, Mg- and Fe-chloride brines and multi-component (Fe 2 (SO 4 ) 3 ± Ca, Na, Mg, Fe, Cl, HCO 3 ) brines at ∼21°C, and characterize the dehydration products using visible/near-infrared (VNIR) reflectance spectroscopy, mid-infrared attenuated total reflectance spectroscopy, and X-ray diffraction (XRD) analysis. We find that rapid dehydration of many multicomponent brines can form amorphous solids or solids with an amorphous component, and that the presence of other elements affects the persistence of the amorphous phase under RH fluctuations. Of the pure chloride brines, only Fe-chloride formed an amorphous solid. XRD patterns of the multicomponent amorphous salts show changes in position, shape, and magnitude of the characteristic diffuse scattering observed in all amorphous materials that could be used to help constrain the composition of the amorphous salt. Amorphous salts deliquesce at lower RH values compared to their crystalline counterparts, opening up the possibility of their role in potential deliquescence-related geologic phenomena such as recurring slope lineae (RSLs) or soil induration. This work suggests that a wide range of aqueous mixed salt solutions can lead to the formation of amorphous salts and are possible for Mars; detailed studies of the formation mechanisms, stability and transformation

Molten salt electrorefining method

International Nuclear Information System (INIS)

Tanaka, Hiroshi; Nakamura, Hitoshi; Shoji, Yuichi; Matsumaru, Ken-ichi.

1994-01-01

A molten cadmium phase (lower side) and a molten salt phase (upper side) are filled in an electrolytic bath. A basket incorporating spent nuclear fuels is inserted/disposed in the molten cadmium phase. A rotatable solid cathode is inserted/disposed in the molten salt phase. The spent fuels, for example, natural uranium, incorporated in the basket is dissolved in the molten cadmium phase. In this case, the uranium concentration in the molten salt phase is determined as from 0.5 to 20wt%. Then, electrolysis is conducted while setting a stirring power for stirring at least the molten salt phase of from 2.5 x 10 2 to 1 x 10 4 based on a reynolds number. Crystalline nuclei of uranium are precipitated uniformly on the surface of the solid cathode, and they grow into fine dendrites. With such procedures, since short-circuit between the cathode precipitates and the molten cadmium phase (anode) is scarcely caused, to improve the recovering rate of uranium. (I.N.)

Lithium salt with a super-delocalized perfluorinated sulfonimide anion as conducting salt for lithium-ion cells: Physicochemical and electrochemical properties

Science.gov (United States)

Zhang, Heng; Han, Hongbo; Cheng, Xiaorong; Zheng, Liping; Cheng, Pengfei; Feng, Wenfang; Nie, Jin; Armand, Michel; Huang, Xuejie; Zhou, Zhibin

2015-11-01

Lithium salt with a super-delocalized imide anion, namely (trifluoromethane(S-trifluoromethanesulfonylimino)sulfonyl) (trifluoromethanesulfonyl)imide ([CF3SO(=NSO2CF3)2]-), [sTFSI]-), has been prepared and studied as conducting salt for Li-ion cells. The fundamental physicochemical and electrochemical properties of neat Li[sTFSI] and its carbonate-based liquid electrolyte have been characterized with various chemical and electrochemical tools. Li[sTFSI] shows a low melting point at 118 °C, and is thermally stable up to 300 °C without decomposition on the spectra of differential scanning calorimetry-thermogravimetry-mass spectrometry (DSC-TG-MS). The electrolyte of 1.0 M (mol dm-3) Li[sTFSI] in ethylene carbonate (EC)/ethyl-methyl-carbonate (EMC) (3:7, v/v) containing 0.3% water does not show any hydrolytic decomposition on the spectra of 1H and 19F NMR, after storage at 85 °C for 10 days. The conductivities of 1.0 M Li[sTFSI]-EC/EMC (3:7, v/v) are slightly lower than those of Li[(CF3SO2)2N] (LiTFSI), but higher than those of Li[(C2F5SO2)2N] (LiBETI). The electrochemical behavior of Al foil in the Li[sTFSI]-based electrolyte has been investigated by using cyclic voltammetry and chronoamperometry, and scanning electron microscope (SEM). It is illustrated that Al metal does not corrode in the high potential region (3-5 V vs. Li/Li+) in the Li[sTFSI]-based electrolyte. On Pt electrode, the Li[sTFSI]-based electrolyte is highly resistant to oxidation (ca. 5 V vs. Li/Li+), and is also resistant to reduction to allow Li deposition and stripping. The applicability of Li[sTFSI] as conducting salt for Li-ion cells has been tested using graphite/LiCoO2 cells. It shows that the cell with Li[sTFSI] displays better cycling performance than that with LiPF6.

Protic Salt Polymer Membranes: High-Temperature Water-Free Proton-Conducting Membranes

Energy Technology Data Exchange (ETDEWEB)

Gervasio, Dominic Francis [Univ. of Arizona, Tucson, AZ (United States)

2010-09-30

This research on proton-containing (protic) salts directly addresses proton conduction at high and low temperatures. This research is unique, because no water is used for proton ionization nor conduction, so the properties of water do not limit proton fuel cells. A protic salt is all that is needed to give rise to ionized proton and to support proton mobility. A protic salt forms when proton transfers from an acid to a base. Protic salts were found to have proton conductivities that are as high as or higher than the best aqueous electrolytes at ambient pressures and comparable temperatures without or with water present. Proton conductivity of the protic salts occurs providing two conditions exist: i) the energy difference is about 0.8 eV between the protic-salt state versus the state in which the acid and base are separated and 2) the chemical constituents rotate freely. The physical state of these proton-conducting salts can be liquid, plastic crystal as well as solid organic and inorganic polymer membranes and their mixtures. Many acids and bases can be used to make a protic salt which allows tailoring of proton conductivity, as well as other properties that affect their use as electrolytes in fuel cells, such as, stability, adsorption on catalysts, environmental impact, etc. During this project, highly proton conducting (~ 0.1S/cm) protic salts were made that are stable under fuel-cell operating conditions and that gave highly efficient fuel cells. The high efficiency is attributed to an improved oxygen electroreduction process on Pt which was found to be virtually reversible in a number of liquid protic salts with low water activity (< 1% water). Solid flexible non-porous composite membranes, made from inorganic polymer (e.g., 10%indium 90%tin pyrophosphate, ITP) and organic polymer (e.g., polyvinyl pyridinium phosphate, PVPP), were found that give conductivity and fuel cell performances similar to phosphoric acid electrolyte with no need for hydration at

Fluctuation-enhanced electric conductivity in electrolyte solutions.

Science.gov (United States)

Péraud, Jean-Philippe; Nonaka, Andrew J; Bell, John B; Donev, Aleksandar; Garcia, Alejandro L

2017-10-10

We analyze the effects of an externally applied electric field on thermal fluctuations for a binary electrolyte fluid. We show that the fluctuating Poisson-Nernst-Planck (PNP) equations for charged multispecies diffusion coupled with the fluctuating fluid momentum equation result in enhanced charge transport via a mechanism distinct from the well-known enhancement of mass transport that accompanies giant fluctuations. Although the mass and charge transport occurs by advection by thermal velocity fluctuations, it can macroscopically be represented as electrodiffusion with renormalized electric conductivity and a nonzero cation-anion diffusion coefficient. Specifically, we predict a nonzero cation-anion Maxwell-Stefan coefficient proportional to the square root of the salt concentration, a prediction that agrees quantitatively with experimental measurements. The renormalized or effective macroscopic equations are different from the starting PNP equations, which contain no cross-diffusion terms, even for rather dilute binary electrolytes. At the same time, for infinitely dilute solutions the renormalized electric conductivity and renormalized diffusion coefficients are consistent and the classical PNP equations with renormalized coefficients are recovered, demonstrating the self-consistency of the fluctuating hydrodynamics equations. Our calculations show that the fluctuating hydrodynamics approach recovers the electrophoretic and relaxation corrections obtained by Debye-Huckel-Onsager theory, while elucidating the physical origins of these corrections and generalizing straightforwardly to more complex multispecies electrolytes. Finally, we show that strong applied electric fields result in anisotropically enhanced "giant" velocity fluctuations and reduced fluctuations of salt concentration.

Study of the carbon material / electrolyte interface; Etude de l`interface materiau carbone / electrolyte

Energy Technology Data Exchange (ETDEWEB)

Genies, S.; Yazami, R. [Ecole Nationale Superieure d`Electrochimie et d`Electrometallurgie, 38 - Saint-Martin-d`Heres (France); Frison, J.C. [CNET, Centre de Recherches de Lannion, 22 (France); Ledran, J. [CNET, 92 - Issy-les-Moulineaux (France)

1996-12-31

The aim of this work is the comparative study of the properties of the natural graphite/liquid organic electrolyte interface by impedance spectroscopy with respect to different lithium salts (LiX with X = ClO{sub 4}{sup -}, BF{sub 4}{sup -}, CF{sub 3}SO{sub 3}{sup -}, N(CF{sub 3}SO{sub 2}){sub 2}{sup -}, PF{sub 6}{sup -}). The evolution of the interface properties during the first electrochemical reduction suggests different mechanisms of formation of passivation films. A more stable, thin and homogenous film seems to develop when the LiN(CF{sub 3}SO{sub 2}){sub 2} or LiPF{sub 6} lithium salts are used. The chemical diffusion coefficient of lithium in graphite has been determined by impedance spectroscopy. (J.S.) 16 refs.

Study of the carbon material / electrolyte interface; Etude de l`interface materiau carbone / electrolyte

Energy Technology Data Exchange (ETDEWEB)

Genies, S; Yazami, R [Ecole Nationale Superieure d` Electrochimie et d` Electrometallurgie, 38 - Saint-Martin-d` Heres (France); Frison, J C [CNET, Centre de Recherches de Lannion, 22 (France); Ledran, J [CNET, 92 - Issy-les-Moulineaux (France)

1997-12-31

The aim of this work is the comparative study of the properties of the natural graphite/liquid organic electrolyte interface by impedance spectroscopy with respect to different lithium salts (LiX with X = ClO{sub 4}{sup -}, BF{sub 4}{sup -}, CF{sub 3}SO{sub 3}{sup -}, N(CF{sub 3}SO{sub 2}){sub 2}{sup -}, PF{sub 6}{sup -}). The evolution of the interface properties during the first electrochemical reduction suggests different mechanisms of formation of passivation films. A more stable, thin and homogenous film seems to develop when the LiN(CF{sub 3}SO{sub 2}){sub 2} or LiPF{sub 6} lithium salts are used. The chemical diffusion coefficient of lithium in graphite has been determined by impedance spectroscopy. (J.S.) 16 refs.

Hot corrosion behavior of Ni-based superalloys in lithium molten salt

International Nuclear Information System (INIS)

Cho, Soo Haeng; Lim, Jong Ho; Chung, Joon Ho; Hur, Jin Mok; Seo, Chung Seok; Park, Seoung Won

2004-01-01

The Li-reduction process involves the chemical reduction of spent fuel oxides by liquid lithium metal in a molten LiCl salt bath at 650 .deg. C followed by a separate electrochemical reduction of lithium oxide (Li 2 O), which builds up in the salt bath. This process requires a high purity inert gas atmosphere inside remote hot cell nuclear facility to prevent unwanted Li oxidation and fires during the handling of chemically active Li metal. In light of the limitations of the Li-reduction process, a direct electrolytic reduction technology is being developed by KAERI to enhance process safety and economic viability. The electrolytic reduction of spent oxide fuel involves the liberation of oxygen in a molten LiCl electrolyte, which results in a chemically aggressive environment that is too corrosive for typical structural materials. Even so, the electrochemical process vessel must be resilient at 650 .deg. C in the presence of oxygen to enable high processing rates and an extended service life. But, the mechanism and the rate of the corrosion of metals in LiCl-Li 2 O molten salt under oxidation condition are not clear. In the present work, the corrosion behavior and corrosion mechanism of Ni-based superalloys have been studied in the molten salt of LiCl-Li 2 O under oxidation condition

Influence of the external conditions on salt retention and pressure-induced electrical potential measured across a composite membrane

DEFF Research Database (Denmark)

Benavente, Juana; Jonsson, Gunnar Eigil

1999-01-01

Transport on single electrolyte solutions (NaCl and MgCl2) due to pressure gradients across a commercial reverse osmosis membrane was studied by measuring volume flux (J(v)), salt rejection (S) and pressure induced electrical potential (Delta E) in a crossflow cell. The influence on these paramet......Transport on single electrolyte solutions (NaCl and MgCl2) due to pressure gradients across a commercial reverse osmosis membrane was studied by measuring volume flux (J(v)), salt rejection (S) and pressure induced electrical potential (Delta E) in a crossflow cell. The influence......, r = 1, 0.5 and 0.1), respectively. Results show that J(v), S and Delta E values slightly increase when the velocity of the feed solution increases, but the mixed electrolytes strongly affect both salt rejection and pressure-induced electrical potential. A change in the sign of both parameters...... with respect to the value determined with single electrolytes at the same concentration was obtained, which is attributed to a strong coupling among the fluxes of individual ions and their distribution in the membrane when transport of mixed salt is studied. (C) 1999 Elsevier Science B.V. All rights reserved....

Gel polymer electrolytes for batteries

Science.gov (United States)

Balsara, Nitash Pervez; Eitouni, Hany Basam; Gur, Ilan; Singh, Mohit; Hudson, William

2014-11-18

Nanostructured gel polymer electrolytes that have both high ionic conductivity and high mechanical strength are disclosed. The electrolytes have at least two domains--one domain contains an ionically-conductive gel polymer and the other domain contains a rigid polymer that provides structure for the electrolyte. The domains are formed by block copolymers. The first block provides a polymer matrix that may or may not be conductive on by itself, but that can soak up a liquid electrolyte, thereby making a gel. An exemplary nanostructured gel polymer electrolyte has an ionic conductivity of at least 1.times.10.sup.-4 S cm.sup.-1 at 25.degree. C.

Anode-supported single-chamber SOFCs based on gadolinia doped ceria electrolytes

Directory of Open Access Journals (Sweden)

Morales, M.

2008-12-01

Full Text Available The utilization of anode supported electrolytes is a useful strategy to increase the electrical properties of the solid oxide fuel cells, because it is possible to decrease considerably the thickness of the electrolytes. We have prepared successfully singlechamber fuel cells of gadolinia doped ceria electrolytes Ce_1-xGd_xO_2-y (CGO supported on an anode formed by a cermet of Ni-CGO. Mixtures of precursor powders of NiO and gadolinium doped ceria with different particle sizes and compositions were analyzed to obtain optimal bulk porous anodes to be used as anode supported fuel cells. Doped ceria electrolytes were prepared by sol-gel related techniques. Then, ceria based electrolytes were deposited by dip coating at different thickness (15-30 µm using an ink prepared with nanometric powders of electrolytes dispersed in a commercial liquid polymer. Cathodes of La_1-xSr_xCoO_3-s (LSCO were also prepared by sol-gel related techniques and were deposited by dip coating on the electrolyte thick films. Finally, electrical properties were determined in a single-chamber reactor where propane as fuel was mixed with synthetic air above the higher explosive limit. Stable density currents were obtained in these experimental conditions, but flow rates of the carrier gas and propane partial pressure were determinants for the optimization of the electrical properties of the fuel cells.

La utilización de electrolitos soportados en el ánodo es una estrategia muy útil para mejorar las propiedades eléctricas de las pilas de combustible de óxido sólido, debido a que permiten disminuir considerablemente el espesor de los electrolitos. Para este trabajo, se han preparado exitosamente pilas de combustible de óxido sólido con electrolitos de ceria dopada con Gd, Ce1_-xGd_xO_2-y (CGO soportados sobre un ánodo formado por un cermet de Ni/CGO. Dichas pilas se han

FT-IR studies on interactions among components in hexanoyl chitosan-based polymer electrolytes

Science.gov (United States)

Winie, Tan; Arof, A. K.

2006-03-01

Fourier transform infrared (FT-IR) spectroscopic studies have been undertaken to investigate the interactions among components in a system of hexanoyl chitosan-lithium trifluoromethanesulfonate (LiCF 3SO 3)-diethyl carbonate (DEC)/ethylene carbonate (EC). LiCF 3SO 3 interacts with the hexanoyl chitosan to form a hexanoyl chitosan-salt complex that results in the shifting of the N(COR) 2, C dbnd O sbnd NHR and OCOR bands to lower wavenumbers. Interactions between EC and DEC with LiCF 3SO 3 has been noted and discussed. Evidence of interaction between EC and DEC has been obtained experimentally. Studies on polymer-plasticizer spectra suggested that there is no interaction between the polymer host and plasticizers. Competition between plasticizer and polymer on associating with Li + ions was observed from the spectral data for gel polymer electrolytes. The obtained spectroscopic data has been correlated with the conductivity performance of hexanoyl chitosan-based polymer electrolytes.

Inhibition of anodic corrosion of aluminium cathode current collector on recharging in lithium imide electrolytes

Energy Technology Data Exchange (ETDEWEB)

Wang, Xianming; Yasukawa, Eiki; Mori, Shoichiro [Tsukuba Research Center, Mitsubishi Chemical Corp., Ibaraki (Japan)

2000-07-01

Pitting corrosion of aluminum as cathode current collector for lithium rechargeable batteries was found to take place at potential positive of 3.5 V in 1 mol dm {sup -3} LiN(SO{sub 2}CF{sub 3}){sub 2} /EC + DME (1:1) electrolyte. The corrosion mechanism of aluminum in the presence of LiN(SO{sub 2}CF{sub 3}){sub 2} was proposed, and three methods were deduced to inhibit the aluminum corrosion based on this mechanism. As a result, an additive of lithium salts based on perfluorinated inorganic anions, especially LiPF{sub 6}, was found to inhibit the aluminum corrosion to a certain extent by forming a protective film on aluminum surface. The oxidation stability of aluminum in LiN(SO{sub 2}CF{sub 3}){sub 2} -containing electrolytes depended strongly on the solvent structure. The ether solvents such as tetrahydrofuran (THF) and dimethoxyethane (DME) were effective in preventing aluminum corrosion due to their low dielectric constants. Furthermore, LiN(SO{sub 2}C{sub 2}F{sub 5}){sub 2} salt with a larger anion than that of LiN(SO{sub 2}CF{sub 3}){sub 2} was evaluated and good oxidation stability of aluminum was obtained regardless of the kind of solvents. (Author)

New Polymer Electrolyte Cell Systems

Science.gov (United States)

Smyrl, William H.; Owens, Boone B.; Mann, Kent; Pappenfus, T.; Henderson, W.

2004-01-01

PAPERS PUBLISHED: 1. Pappenfus, Ted M.; Henderson, Wesley A.; Owens, Boone B.; Mann, Kent R.; Smyrl, William H. Complexes of Lithium Imide Salts with Tetraglyme and Their Polyelectrolyte Composite Materials. Journal of the Electrochemical Society (2004), 15 1 (2), A209-A2 15. 2. Pappenfus, Ted M.; Henderson, Wesley A.; Owens, Boone B.; Mann, Kent R.; Smyrl, William H. Ionic-liquidlpolymer electrolyte composite materials for electrochemical device applications. Polymeric Materials Science and Engineering (2003), 88 302. 3. Pappenfus, Ted R.; Henderson, Wesley A.; Owens, Boone B.; Mann, Kent R.; and Smyrl, William H. Ionic Conductivity of a poly(vinylpyridinium)/Silver Iodide Solid Polymer Electrolyte System. Solid State Ionics (in press 2004). 4. Pappenfus Ted M.; Mann, Kent R; Smyrl, William H. Polyelectrolyte Composite Materials with LiPFs and Tetraglyme. Electrochemical and Solid State Letters, (2004), 7(8), A254.

Advanced High-Voltage Aqueous Lithium-Ion Battery Enabled by "Water-in-Bisalt" Electrolyte.

Science.gov (United States)

Suo, Liumin; Borodin, Oleg; Sun, Wei; Fan, Xiulin; Yang, Chongyin; Wang, Fei; Gao, Tao; Ma, Zhaohui; Schroeder, Marshall; von Cresce, Arthur; Russell, Selena M; Armand, Michel; Angell, Austen; Xu, Kang; Wang, Chunsheng

2016-06-13

A new super-concentrated aqueous electrolyte is proposed by introducing a second lithium salt. The resultant ultra-high concentration of 28 m led to more effective formation of a protective interphase on the anode along with further suppression of water activities at both anode and cathode surfaces. The improved electrochemical stability allows the use of TiO2 as the anode material, and a 2.5 V aqueous Li-ion cell based on LiMn2 O4 and carbon-coated TiO2 delivered the unprecedented energy density of 100 Wh kg(-1) for rechargeable aqueous Li-ion cells, along with excellent cycling stability and high coulombic efficiency. It has been demonstrated that the introduction of a second salts into the "water-in-salt" electrolyte further pushed the energy densities of aqueous Li-ion cells closer to those of the state-of-the-art Li-ion batteries. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrolytic reduction runs of 0.6 kg scale-simulated oxide fuel in a Li2O-LiCl molten salt using metal anode shrouds

Science.gov (United States)

Choi, Eun-Young; Lee, Jeong; Heo, Dong Hyun; Lee, Sang Kwon; Jeon, Min Ku; Hong, Sun Seok; Kim, Sung-Wook; Kang, Hyun Woo; Jeon, Sang-Chae; Hur, Jin-Mok

2017-06-01

Ten electrolytic reduction or oxide reduction (OR) runs of a 0.6 kg scale-simulated oxide fuel in a Li2O-LiCl molten salt at 650 °C were conducted using metal anode shrouds. During this procedure, an anode shroud surrounds a platinum anode and discharges hot oxygen gas from the salt to outside of the OR apparatus, thereby preventing corrosion of the apparatus. In this study, a number of anode shrouds made of various metals were tested. Each metallic anode shroud consisted of a lower porous shroud for the salt phase and an upper nonporous shroud for the gas phase. A stainless steel (STS) wire mesh with five-ply layer was a material commonly used for the lower porous shroud for the OR runs. The metals tested for the upper nonporous shroud in the different OR runs are STS, nickel, and platinum- or silver-lined nickel. The lower porous shroud showed no significant damage during two consecutive OR runs, but exhibited signs of damage from three or more runs due to thermal stress. The upper nonporous shrouds made up of either platinum- or silver-lined nickel showed excellent corrosion resistance to hot oxygen gas while STS or nickel without any platinum or silver lining exhibited poor corrosion resistance.

Plasma electrolytic oxide coatings on silumin for oxidation CO

Science.gov (United States)

Borisov, V. A.; Sigaeva, S. S.; Anoshkina, E. A.; Ivanov, A. L.; Litvinov, P. V.; Vedruchenko, V. R.; Temerev, V. L.; Arbuzov, A. B.; Kuznetsov, A. A.; Mukhin, V. A.; Suprunov, G. I.; Chumychko, I. A.; Shlyapin, D. A.; Tsyrul'nikov, P. G.

2017-08-01

Some catalysts of CO oxidation on silumin alloy AK12M2, used for the manufacture of pistons for Russian cars were investigated. The catalysts were prepared by the method of plasma electrolytic oxidation of silumin in electrolytes of various compositions with further activation by the salts Ce, Cu, Co, Ni, Mn and Al. The catalytic tests were carried out in a flow reactor in a mixture of 1% CO and 99% air, with the temperature range of 25-500 °C. The most active catalysts in CO oxidation are those activated with Ce and Cu salts on silumin, treated for 3 hours in an electrolyte containing 4 g/l KOH, 40 g/l Na2B4O7 (conversion of CO is 93.7% at a contact time of 0.25 s). However, the catalysts obtained from silumin treated in the electrolyte containing 3 g/l KOH, 30 g/l Na2SiO3 are more suitable for practical usage. Because when the treatment time of those catalysts is 10 - 20 minutes it is possible to achieve comparable CO conversion. The morphology and composition of the catalysts were studied by the methods of a scanning electron microscope with energy-dispersive surface analysis and X-ray phase analysis. The surface of the non-activated sample consists of γ-Al2O3 and SiO2 particles, due to which the active components get attached to the support. CeO2 and CuO are present on the surface of the sample with the active component.

Study on the mass transfer of oxygen in an electrolytic reduction process of ACP

International Nuclear Information System (INIS)

Park, Byung Heung; Park, Sung Bin; Seo, Chung Seok; Park, Seong Won

2005-01-01

The Advanced Spent Fuel Conditioning Process (ACP) is a molten-salt-based back-end fuel cycle technology developed at KAERI. The target fuel type for the process is the oxide fuel unloaded from PWRs which are the main prototype reactor commercially operating in Korea. The volume and the radiotoxicity of the spent fuel decrease to quarters of the initial volume and radiotoxicity after being reduced to metal forms and removing some elements into a molten salt. The reduction of the two properties improves the convenience in managing the spent fuels and makes it possible for disposal sites to be made the best use of. Metallization of the spent oxide fuels is accomplished in an electrolytic reduction cell where a molten LiCl is adopted as an electric medium and Li 2 O is added to increase the activity of the oxygen ion in the system. A porous magnesia filter, a SUS solid conductor, and the metal oxides to be reduced constitute a cathode and anodes are made of platinum. The only cation in the liquid phase is lithium at the first stage and the ion diffuses through the pores of the magnesia filter and then receives electrons to become a metal. The reduced lithium metal snatches oxygen from the metal oxides in the filter and transforms into lithium oxide which diffuses back to the molten salt phase leaving the reduced metal at the inside of the filter. The lithium oxide is dissociated to lithium and oxygen ions once it dissolves in the molten salt if the concentration is within the solubility limit. Hence the actual diffusing element is oxygen in an ionic state rather than the lithium oxide since there is no concentration gradient for the lithium ion to move on - the lithium ion is the main cation in the system though some alkali and alkaline-earth metals dissolve in the molten salt phase to be cations. The analysis of the mass transfer of oxygen in the electrolytic reduction process is, thus, of importance for the metallization process to be completely interpreted

Influence of the lithium salt nature over the surface film formation on a graphite electrode in Li-ion batteries: An XPS study

International Nuclear Information System (INIS)

Leroy, S.; Martinez, H.; Dedryvere, R.; Lemordant, D.; Gonbeau, D.

2007-01-01

The formation of a passivation film (solid electrolyte interphase, SEI) at the surface of the negative electrode of full LiCoO 2 /graphite lithium-ion cells using different salts (LiBF 4 , LiPF 6 , LiTFSI, LiBETI) in carbonate solvents as electrolyte was investigated by X-ray photoelectron spectroscopy (XPS). The analyzes were carried out at different potential stages of the first cycle, showing the potential-dependent character of the surface film species formation and the specificity of each salt. At 3.8 V, for all salts, we have mainly identified carbonated species. Beyond this potential, the specific behavior of LiPF 6 was identified with a high LiF deposit, whereas for other salts, the formation process of the SEI appears controlled by the solvent decomposition of the electrolyte

A new form of MgTa2O6 obtained by the molten salt method

Indian Academy of Sciences (India)

Unknown

Abstract. Using molten salt route (with NaCl/KCl as the salt) we have been able to synthesize a new form of magnesium tantalate at 850°C. Powder X-ray diffraction data could be indexed on an orthorhombic unit cell with lattice parameters, 'a' = 15⋅36(1) Å, 'b' = 13⋅38(1) Å and 'c' = 12⋅10(1) Å. High resolution.

X-ray Raman spectroscopy of lithium-ion battery electrolyte solutions in a flow cell.

Science.gov (United States)

Ketenoglu, Didem; Spiekermann, Georg; Harder, Manuel; Oz, Erdinc; Koz, Cevriye; Yagci, Mehmet C; Yilmaz, Eda; Yin, Zhong; Sahle, Christoph J; Detlefs, Blanka; Yavaş, Hasan

2018-03-01

The effects of varying LiPF 6 salt concentration and the presence of lithium bis(oxalate)borate additive on the electronic structure of commonly used lithium-ion battery electrolyte solvents (ethylene carbonate-dimethyl carbonate and propylene carbonate) have been investigated. X-ray Raman scattering spectroscopy (a non-resonant inelastic X-ray scattering method) was utilized together with a closed-circle flow cell. Carbon and oxygen K-edges provide characteristic information on the electronic structure of the electrolyte solutions, which are sensitive to local chemistry. Higher Li + ion concentration in the solvent manifests itself as a blue-shift of both the π* feature in the carbon edge and the carbonyl π* feature in the oxygen edge. While these oxygen K-edge results agree with previous soft X-ray absorption studies on LiBF 4 salt concentration in propylene carbonate, carbon K-edge spectra reveal a shift in energy, which can be explained with differing ionic conductivities of the electrolyte solutions.

Effect of lithium and sodium salt on the performance of Nb2O5/rGO nanocomposite based supercapacitor

Science.gov (United States)

Ahmed, Sultan; Rafat, M.

2018-03-01

The present work reports the synthesis of Nb2O5/rGO composite using hydrothermal method and thermal annealing process. The prepared composite was found to have suitable characteristics necessary to be used as electrode material in supercapacitors. These characteristics were ascertained employing the techniques of scanning electron microscopy (SEM), x-ray diffraction (XRD), Raman spectroscopy and N2 adsorption-desorption isotherm. Further, the electrochemical performance of the prepared composite was compared in two different organic electrolytes, of lithium and sodium salt using the techniques of electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and charge-discharge measurements. The organic electrolyte solutions were prepared by dispersing 1 M LiClO4/NaClO4 in a mixture of ethylene carbonate/propylene carbonate (1:1 by volume). The observed results indicate that the composite of Nb2O5/rGO offers higher value of specific capacitance in sodium salt electrolyte and higher cyclic stability in lithium salt electrolyte. This is probably due to ion properties of electrolyte. Specific capacitance is observed according to efficient ion/charge diffusion/exchange and relaxation time (Li+ Li+). Thus, the present study reveals the significant effect of electrolyte ions on electrochemical performance of Nb2O5/rGO composite.

The mechanics of pressed-pellet separators in molten salt batteries

Energy Technology Data Exchange (ETDEWEB)

Long, Kevin Nicholas [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Roberts, Christine Cardinal [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Roberts, Scott Alan [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Grillet, Anne [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

2014-06-01

We present a phenomenological constitutive model that describes the macroscopic behavior of pressed-pellet materials used in molten salt batteries. Such materials include separators, cathodes, and anodes. The purpose of this model is to describe the inelastic deformation associated with the melting of a key constituent, the electrolyte. At room temperature, all constituents of these materials are solid and do not transport cations so that the battery is inert. As the battery is heated, the electrolyte, a constituent typically present in the separator and cathode, melts and conducts charge by flowing through the solid skeletons of the anode, cathode, and separator. The electrochemical circuit is closed in this hot state of the battery. The focus of this report is on the thermal-mechanical behavior of the separator, which typically exhibits the most deformation of the three pellets during the process of activating a molten salt battery. Separator materials are composed of a compressed mixture of a powdered electrolyte, an inert binder phase, and void space. When the electrolyte melts, macroscopically one observes both a change in volume and shape of the separator that depends on the applied boundary conditions during the melt transition. Although porous flow plays a critical role in the battery mechanics and electrochemistry, the focus of this report is on separator behavior under flow-free conditions in which the total mass of electrolyte is static within the pellet. Specific poromechanics effects such as capillary pressure, pressure-saturation, and electrolyte transport between layers are not considered. Instead, a phenomenological model is presented to describe all such behaviors including the melting transition of the electrolyte, loss of void space, and isochoric plasticity associated with the binder phase rearrangement. The model is appropriate for use finite element analysis under finite deformation and finite temperature change conditions. The model

Development of electrolytic process in molten salt media for light rare-earth metals production. The metallic cerium electrodeposition; Desenvolvimento de processo de eletrolise em meio de sais fundidos para a producao de metais de terras-raras leves. A obtencao do cerio metalico

Energy Technology Data Exchange (ETDEWEB)

Restivo, T A.G.

1994-12-31

The development of molten salt process and the respective equipment aiming rare-earth metals recovery was described. In the present case, the liquid cerium metal electrodeposition in a molten electrolytes of cerium chloride and an equimolar mixture of sodium and potassium chlorides in temperatures near 800{sup C} was studied. Due the high chemical reactivity of the rare-earth metals in the liquid state and their molten halides, an electrolytic cell was constructed with controlled atmosphere, graphite crucibles and anodes and a tungsten cathode. The electrolytic process variables and characteristics were evaluated upon the current efficiency and metallic product purity. Based on this evaluations, were suggested some alterations on the electrolytic reactor design and upon the process parameters. (author). 90 refs, 37 figs, 20 tabs.

Glasslike behavior in aqueous electrolyte solutions.

Science.gov (United States)

Turton, David A; Hunger, Johannes; Hefter, Glenn; Buchner, Richard; Wynne, Klaas

2008-04-28

When salts are added to water, generally the viscosity increases, suggesting that the ions increase the strength of the water's hydrogen-bond network. However, infrared pump-probe measurements on electrolyte solutions have found that ions have no influence on the rotational dynamics of water molecules, implying no enhancement or breakdown of the hydrogen-bond network. Here, we report optical Kerr effect and dielectric relaxation spectroscopic measurements, which have enabled us to separate the effects of rotational and transitional motions of the water molecules. These data show that electrolyte solutions behave like a supercooled liquid approaching a glass transition in which rotational and translational molecular motions are decoupled. It is now possible to understand previously conflicting viscosity data, nuclear magnetic resonance relaxation, and ultrafast infrared spectroscopy in a single unified picture.

Crosslinked Polymer Ionic Liquid/Ionic Liquid Blends Prepared by Photopolymerization as Solid-State Electrolytes in Supercapacitors

Science.gov (United States)

Wang, Po-Hsin; Wang, Tzong-Liu; Lin, Wen-Churng; Lin, Hung-Yin; Lee, Mei-Hwa; Yang, Chien-Hsin

2018-01-01

A photopolymerization method is used to prepare a mixture of polymer ionic liquid (PIL) and ionic liquid (IL). This mixture is used as a solid-state electrolyte in carbon nanoparticle (CNP)-based symmetric supercapacitors. The solid electrolyte is a binary mixture of a PIL and its corresponding IL. The PIL matrix is a cross-linked polyelectrolyte with an imidazole salt cation coupled with two anions of Br− in PIL-M-(Br) and TFSI− in PIL-M-(TFSI), respectively. The corresponding ionic liquids have imidazolium salt cation coupled with two anions of Br− and TFSI−, respectively. This study investigates the electrochemical characteristics of PILs and their corresponding IL mixtures used as a solid electrolyte in supercapacitors. Results show that a specific capacitance, maximum power density and energy density of 87 and 58 F·g−1, 40 and 48 kW·kg−1, and 107 and 59.9 Wh·kg−1 were achieved in supercapacitors based on (PIL-M-(Br)) and (PIL-M-(TFSI)) solid electrolytes, respectively. PMID:29642456

Crosslinked Polymer Ionic Liquid/Ionic Liquid Blends Prepared by Photopolymerization as Solid-State Electrolytes in Supercapacitors

Directory of Open Access Journals (Sweden)

Po-Hsin Wang

2018-04-01

Full Text Available A photopolymerization method is used to prepare a mixture of polymer ionic liquid (PIL and ionic liquid (IL. This mixture is used as a solid-state electrolyte in carbon nanoparticle (CNP-based symmetric supercapacitors. The solid electrolyte is a binary mixture of a PIL and its corresponding IL. The PIL matrix is a cross-linked polyelectrolyte with an imidazole salt cation coupled with two anions of Br− in PIL-M-(Br and TFSI− in PIL-M-(TFSI, respectively. The corresponding ionic liquids have imidazolium salt cation coupled with two anions of Br− and TFSI−, respectively. This study investigates the electrochemical characteristics of PILs and their corresponding IL mixtures used as a solid electrolyte in supercapacitors. Results show that a specific capacitance, maximum power density and energy density of 87 and 58 F·g−1, 40 and 48 kW·kg−1, and 107 and 59.9 Wh·kg−1 were achieved in supercapacitors based on (PIL-M-(Br and (PIL-M-(TFSI solid electrolytes, respectively.

Tribological and Corrosion Properties of Coatings Produced by Plasma Electrolytic Oxidation on the ZA27 Alloy

Science.gov (United States)

Li, Guangyin; Mao, Yifan; Li, Zhijian; Wang, Linlin; DaCosta, Herbert

2018-05-01

In this paper, a continuous and dense coating was deposited on samples of the ZA27 alloy through the plasma electrolytic oxidation (PEO) process to improve its wear and corrosion performance. A nontoxic and environmentally friendly inorganic salt, Na2SiO3, is chosen as electrolytes with different concentrations. The effect of the concentration of Na2SiO3 aqueous solutions on the coating performances was investigated. The coatings with 3Al2O3·2SiO2 (mullite), Zn2SiO4 and Al2O3 (either crystal phase or with some amorphous SiO2 phases) were formed by the PEO processes. It was found that the coating thickness increased with the increase in electrolyte concentration. However, the wear and corrosion resistance performance of the coatings did not improve as the coating's thickness increased. This was due to the fact that the coating produced with electrolytes of 10 g/L has a porous structure with large pore size. Among all the samples, coating produced by 15 g/L Na2SiO3 has the best wear and corrosion resistance, which is attributed to its continuous and dense structure with thickness of about 47 μm.

Tribological and Corrosion Properties of Coatings Produced by Plasma Electrolytic Oxidation on the ZA27 Alloy

Science.gov (United States)

Li, Guangyin; Mao, Yifan; Li, Zhijian; Wang, Linlin; DaCosta, Herbert

2018-04-01

In this paper, a continuous and dense coating was deposited on samples of the ZA27 alloy through the plasma electrolytic oxidation (PEO) process to improve its wear and corrosion performance. A nontoxic and environmentally friendly inorganic salt, Na2SiO3, is chosen as electrolytes with different concentrations. The effect of the concentration of Na2SiO3 aqueous solutions on the coating performances was investigated. The coatings with 3Al2O3·2SiO2 (mullite), Zn2SiO4 and Al2O3 (either crystal phase or with some amorphous SiO2 phases) were formed by the PEO processes. It was found that the coating thickness increased with the increase in electrolyte concentration. However, the wear and corrosion resistance performance of the coatings did not improve as the coating's thickness increased. This was due to the fact that the coating produced with electrolytes of 10 g/L has a porous structure with large pore size. Among all the samples, coating produced by 15 g/L Na2SiO3 has the best wear and corrosion resistance, which is attributed to its continuous and dense structure with thickness of about 47 μm.

Photodetection in p–n junctions formed by electrolyte-gated transistors of two-dimensional crystals

KAUST Repository

Kozawa, Daichi

2016-11-16

Transition metal dichalcogenide monolayers have attracted much attention due to their strong light absorption and excellent electronic properties. These advantages make this type of two-dimensional crystal a promising one for optoelectronic device applications. In the case of photoelectric conversion devices such as photodetectors and photovoltaic cells, p–n junctions are one of the most important devices. Here, we demonstrate photodetection with WSe2 monolayer films. We prepare the electrolyte-gated ambipolar transistors and electrostatic p–n junctions are formed by the electrolyte-gating technique at 270 K. These p-n junctions are cooled down to fix the ion motion (and p-n junctions) and we observed the reasonable photocurrent spectra without the external bias, indicating the formation of p-n junctions. Very interestingly, two-terminal devices exhibit higher photoresponsivity than that of three-terminal ones, suggesting the formation of highly balanced anion and cation layers. The maximum photoresponsivity reaches 5 mA/W in resonance with the first excitonic peak. Our technique provides important evidence for optoelectronics in atomically thin crystals.

Photodetection in p–n junctions formed by electrolyte-gated transistors of two-dimensional crystals

KAUST Repository

Kozawa, Daichi; Pu, Jiang; Shimizu, Ryo; Kimura, Shota; Chiu, Ming-Hui; Matsuki, Keiichiro; Wada, Yoshifumi; Sakanoue, Tomo; Iwasa, Yoshihiro; Li, Lain-Jong; Takenobu, Taishi

2016-01-01

Transition metal dichalcogenide monolayers have attracted much attention due to their strong light absorption and excellent electronic properties. These advantages make this type of two-dimensional crystal a promising one for optoelectronic device applications. In the case of photoelectric conversion devices such as photodetectors and photovoltaic cells, p–n junctions are one of the most important devices. Here, we demonstrate photodetection with WSe2 monolayer films. We prepare the electrolyte-gated ambipolar transistors and electrostatic p–n junctions are formed by the electrolyte-gating technique at 270 K. These p-n junctions are cooled down to fix the ion motion (and p-n junctions) and we observed the reasonable photocurrent spectra without the external bias, indicating the formation of p-n junctions. Very interestingly, two-terminal devices exhibit higher photoresponsivity than that of three-terminal ones, suggesting the formation of highly balanced anion and cation layers. The maximum photoresponsivity reaches 5 mA/W in resonance with the first excitonic peak. Our technique provides important evidence for optoelectronics in atomically thin crystals.

Infrared studies of PVC-based electrolytes incorporated with lithium triflate and 1-butyl-3-methyl imidazolium trifluoromethanesulfonate as ionic liquid

Science.gov (United States)

Zulkepeli, Nik A. S. Nik; Winie, Tan; Subban, R. H. Y.

2017-09-01

In this work, 1-butyl-3-methylimidazolium trifluoromethanesulfonate (BMIMCF3SO3) is employed as ionic liquid in PVC-based polymer electrolyte system with lithium triflate (LiCF3SO3) as doping salt. The samples in film form were prepared by quantitatively varying the concentration of BMIMCF3SO3 to a fixed ratio of PVC-LiCF3SO3 using solution cast technique. The highest room temperature ionic conductivity of 1.120 × 10-7 Scm-1 was exhibited by PVC-LiCF3SO3-BMIMCF3SO3 containing 3 wt. % BMIMCF3SO3. FTIR spectra of the polymer electrolytes were examined to study the complexation of the PVC-based polymer electrolytes. Intensity of free ions, ion pairs, and ion aggregates were obtained from FTIR deconvolution in an attempt to correlate with ionic conductivity results. The intensity of free ions was found to be high for sample with 3 wt. % BMIMCF3SO3.

New co-crystal and salt form of sulfathiazole with carboxylic acid and ...

Indian Academy of Sciences (India)

e-mail: cmallareddy@gmail.com. MS received 14 May 2014; revised 8 July 2014; accepted 8 July 2014. Abstract. One co-crystal and one salt of an antibacterial drug sulfathiazole with 4-aminobenzamide and 2,4- dinitrobenzoic acid have been synthesized. These new forms are characterized by single crystal X-ray diffrac-.

Chemical stability of conductive ceramic anodes in LiCl–Li{sub 2}O molten salt for electrolytic reduction in pyroprocessing

Energy Technology Data Exchange (ETDEWEB)

Kim, Sung Wook; Kang, Hyun Woo; Jeon, Min Ku; Lee, Sang Kwon; Choi, Eun Young; Park, Woo Shin; Hong, Sun Seok; Oh, Seung Chul; Hur, Jin Mok [Nuclear Fuel Cycle Process Development Group, Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

2016-08-15

Conductive ceramics are being developed to replace current Pt anodes in the electrolytic reduction of spent oxide fuels in pyroprocessing. While several conductive ceramics have shown promising electrochemical properties in small-scale experiments, their long-term stabilities have not yet been investigated. In this study, the chemical stability of conductive La{sub 0.33}Sr{sub 0.67}MnO{sub 3} in LiCl–Li{sub 2}O molten salt at 650°C was investigated to examine its feasibility as an anode material. Dissolution of Sr at the anode surface led to structural collapse, thereby indicating that the lifetime of the La{sub 0.33}Sr{sub 0.67}MnO{sub 3} anode is limited. The dissolution rate of Sr is likely to be influenced by the local environment around Sr in the perovskite framework.

An investigation of 2,5-di-tertbutyl-1,4-bis(methoxyethoxy)benzene in ether-based electrolytes

Energy Technology Data Exchange (ETDEWEB)

Su, Liang; Ferrandon, Magali; Barton, John L.; de la Rosa, Noel Upia; Vaughey, John T.; Brushett, Fikile R.

2017-08-01

The identification and development of conductive electrolytes with high concentrations of redox active species is key to realizing energy-dense nonaqueous flow batteries. Herein, we explore the use of ether solvents (1,3-dioxolane (DOL), 1,2-dimethoxyethane (DME), diethylene glycol dimethyl ether (DEGDME), and tetraethylene glycol dimethyl ether (TEGDME)) as the basis for redox electrolytes containing a lithium ion supporting salt (LiBF4 or LiTFSI) and 2,5-di-tert-butyl-1,4-bis(2-methoxyethoxy)benzene (DBBB) as an active material. An automated high-throughput platform is employed to screen various electrolyte compositions by measuring solution conductivity and solute solubility as a function of solvent and salt type, component concentration, and temperature. Subsequently, the electrochemical and transport properties of select redox electrolytes are characterized by cyclic voltammetry using glassy carbon disk electrodes and by linear sweep voltammetry using carbon fiber ultramicroelectrodes. In general, improvements in electrolyte conductivity and solute solubility are observed with ether-based formulations as compared to previously reported propylene carbonate (PC)-based formulations. In particular, the addition of DOL to a DME-based electrolyte increases the conductivity and decreases the temperature for solubilization at high LiTFSI and DBBB concentrations. The redox behavior of DBBB remains consistent across the range of concentrations tested while the diffusion coefficient scales with changes in solution viscosity.

Electrolytic reduction of Lithium chloride from mixtures with Alkali and Alkali earth metal salts

Energy Technology Data Exchange (ETDEWEB)

Park, B. H.; Lim, J. S.; Lee, C. S. [Korea Univ., Seoul (Korea, Republic of)

1997-12-31

Electrolytic reduction of lithium chloride in lithium/lithium chloride system was experimentally studied. The electrolytic cell was made of alumina in which graphite anode and stainless steel cathode were used. Cell and electrodes were placed in a glove box. Current was measured against the linearly varying applied potential. Preliminary results were presented. (author). 9 refs., 4 figs.

Magnesium sulfate salts and historic building materials: experimental simulation of limestone flaking by relative humidity cycling and crystallization of salts

Directory of Open Access Journals (Sweden)

Pinchin, S.

2008-06-01

Full Text Available Magnesium sulfate salts often result from the combination of incompatible construction materials, such as stone or mortar with high magnesium content and sulfates from adjacent mortars or polluted air. When combined with a source of moisture, these materials react to form soluble salts, often leading to significant damage by flaking of the stone, as the magnesium sulfate responds to fluctuating environmental conditions. Several laboratory experiments were performed to reproduce surface flaking on different types of limestone from Spain and the UK to evaluate the effects of humidity cycling on the damage of stone by salt crystallization. The two salt solutions used for the experiments were a single salt of magnesium sulfate and a mixture of magnesium sulfate, calcium sulfate and sodium chloride, a typical salt mixture found in damaged stone at the site of Howden Minster (UK. A climate chamber with precise and programmable temperature and humidity control was used to test the hypothesis that salt damage in the stone can be readily caused by humidity fluctuations. Damage was monitored using Linear Variable Differential Transformer (LVDT, which measure transducers displacement by dimensional change on the order of microns. In addition, Ion Chromatography, Environmental Scanning Electron Microscopy with energy dispersive X-ray spectroscopy (ESEM-EDX and X-ray Diffraction analyses (XRD were also carried out to analyze salt behavior. Damage by flaking took place in two types of magnesian limestone cubes impregnated with the salt mixture, from Cadeby quarry and York Minster, apparently by deliquescent salts of low equilibrium relative humidity (RHeq, while the rest of the samples developed a salt crust over the surface, but no damage was observed in the stone. It is important to verify hypotheses developed from field observations with laboratory experiments. By combining both field and laboratory data, a clearer understanding the different mechanisms of

Hydration patterns and salting effects in sodium chloride solution.

Science.gov (United States)

Li, Weifeng; Mu, Yuguang

2011-10-07

The salting effects of 2M sodium chloride electrolyte are studied based on a series of model solutes with properties ranging from hydrophobic to hydrophilic. Generally, hydrophobic solutes will be salted out and hydrophilic solutes will be salted in by NaCl solution. The solvation free energy changes are highly correlated with Kirkwood-Buff integrals. The underlying mechanism resorts to the preferential binding of ions and water to solutes. Our results demonstrate that the salting effect not only depends on the salt's position in Hofmeister series, but also on the solutes' specifics. Taking the hydration free energies of solutes and ions as independent variables, a schematic diagram of salting effects is suggested. The resolved multifaceted salting effects rely on the sensitive balance of the tripartite interaction among solutes, ions, and water. © 2011 American Institute of Physics

Organic solvents, electrolytes, and lithium ion cells with good low temperature performance

Science.gov (United States)

Smart, Marshall C. (Inventor); Bugga, Ratnakumar V. (Inventor); Surampudi, Subbarao (Inventor); Huang, Chen-Kuo (Inventor)

2002-01-01

Multi-component organic solvent systems, electrolytes and electrochemical cells characterized by good low temperature performance are provided. In one embodiment, an improved organic solvent system contains a ternary mixture of ethylene carbonate, dimethyl carbonate and diethyl carbonate. In other embodiments, quaternary systems include a fourth component, i.e, an aliphatic ester, an asymmetric alkyl carbonate or a compound of the formula LiOX, where X is R, COOR, or COR, where R is alkyl or fluoroalkyl. Electrolytes based on such organic solvent systems are also provided and contain therein a lithium salt of high ionic mobility, such as LiPF.sub.6. Reversible electrochemical cells, particularly lithium ion cells, are constructed with the improved electrolytes, and preferably include a carbonaceous anode, an insertion type cathode, and an electrolyte interspersed therebetween.

Impedance and dielectric characterizations of ionic partitioning in interfaces that membranous, biomimetic and gold surfaces form with electrolytes

International Nuclear Information System (INIS)

Chilcott, Terry C.; Guo, Chuan

2013-01-01

Silicon dioxide, organic monolayers covalently attached to silicon and gold are used as biosensor substrates and anchoring platforms for hybrid, tethered and supported lipid membranes used in membrane-protein studies. Electrical impedance spectroscopy (EIS) studies of gold in contact with potassium chloride electrolytes of concentrations ranging from 1 mM to 300 mM, characterized the gold–electrolyte interface as principally a Stern layer 20–30 Å thick and conductivity many orders of magnitude less than that of the bulk electrolyte. EIS studies of SiO 2 –electrolyte system that were similar to studies of a tetradecane–electrolyte system are presented herein that reveal an interface comprised of at least two interfacial layers and extending some 10 5 Å into the electrolyte. The average conductivity and thickness values for the layer in contact with the SiO 2 surface (∼10 −6 S m −1 and ∼28 Å, respectively) were of the order of magnitude expected for the Gouy–Chapman layer but the dependency of the thickness on concentration did not reflect the expected dependency of the Debye length over the full range of concentrations. The average values for the next layer (∼10 −3 S m −1 and ∼10 5 Å) exhibited a dependency on concentration similar to that expected for the bulk electrolyte. The theoretical derivations of ionic partitioning arising from the Born (dielectric) energy distributions in both the SiO 2 and gold interfaces were generally consistent with the respective EIS studies and revealed that partitioning in the SiO 2 interface mimicked that in bio-membranous interfaces. The dielectric characterizations suggest that; ionic partitioning in biomimetic interfaces play a role in long-ranging sequestration of organic molecules, the extensiveness of these interfaces contributes to differences in the lipid densities of bilayers formed on biomimetic substrates, and chloride ions have a greater affinity than the smaller potassium ions for gold

Sorption and pertechnetate by salts of molybdophosphoric acid

International Nuclear Information System (INIS)

Suess, M.; Pfrepper, G.

1983-01-01

The sorption of pertechnetate on salts of molybdophosphoric acid from nitric acid and in the presence of electrolytes was investigated. Distribution coefficients from 10 to 100 ml/g were found. The sorption of pertechnetate can be increased by the addition of K + , NH 4 + , Rb + and Cs + salts. A saturation capacity of proportional 0,19 mmol/g ammonium phosphomolybdate was found from the adsorption isotherms. The formation of alkali metal pertechnetate associates in the sorbent phase is supposed. (orig.)

Thermal Characterization of Molten Salt Systems

Energy Technology Data Exchange (ETDEWEB)

Toni Y. Gutknecht; Guy L. Fredrickson

2011-09-01

The phase stability of molten salts in an electrorefiner (ER) may be adversely affected by the buildup of sodium, fission products, and transuranics in the electrolyte. Potential situations that need to be avoided are the following: (1) salt freezing due to an unexpected change in the liquidus temperature, (2) phase separation or non-homogeneity of the molten salt due to the precipitation of solids or formation of immiscible liquids, and (3) any mechanism that can result in the separation and concentration of fissile elements from the molten salt. Any of these situations would result in an off-normal condition outside the established safety basis for electrorefiner (ER) operations. The stability (and homogeneity) of the phases can potentially be monitored through the thermal characterization of the salts, which can be a function of impurity concentration. This report describes the experimental results of typical salts compositions, which consist of chlorides of potassium, lithium, strontium, samarium, praseodymium, lanthanum, barium, cerium, cesium, neodymium, sodium and gadolinium chlorides as a surrogate for both uranium and plutonium, used for the processing of used nuclear fuels.

Utilization of carbon dioxide for polymer electrolytes [I]: Effect of supercritical treatment conditions on ionic conduction in amorphous polyether/salt mixtures

International Nuclear Information System (INIS)

Oe, Yoshiyuki; Tominaga, Yoichi

2011-01-01

Highlights: ► Supercritical CO 2 treatment on amorphous polyether/salt mixtures improves ionic conductivity in the dry state. ► Suitable CO 2 condition for high conductivity exists in near the critical temperature and pressure. ► Conductivity decreases only 20% after 30 days. ► Dissociation of free ClO 4 − and interactions between ether chains and Li + increase in treated electrolytes. - Abstract: Supercritical carbon dioxide (scCO 2 ) as a treatment medium has a possibility to realize excellent room temperature conductivity more than 10 −4 S/cm for polymer electrolytes in the dry state. In this study, a typical high ion-conductive polyether-based electrolyte which consists of poly-[ethylene oxide-co-2-(2-methoxyethoxy)ethyl glycidyl ether] (P(EO/EM)) and lithium perchlorate (LiClO 4 ) was used as a model sample for the scCO 2 treatment. We found the suitable scCO 2 treatment conditions (pressure, temperature and time) for high conductivity. The conductivity of sample treated at 7.5 MPa and 40 °C for 40 min was more than 100-times higher than that of original without the treatment, and the value decreased only 20% after 30 days. DSC measurement revealed that the decrease in glass transition temperature (T g ) is caused by the scCO 2 -treatment. The change of ionic association in the scCO 2 -treated samples was confirmed using FT-IR measurement. The scCO 2 treatment gave rise to increase in peak fraction of free ClO 4 − anions (620–625 cm −1 ) and peak shift of ν(C–O–C) mode to lower frequency region (1060–1070 cm −1 ) depending on ether–Li + interactions.

Supra-molecular Association and Polymorphic Behaviour In Systems Containing Bile Acid Salts

Directory of Open Access Journals (Sweden)

Camillo La Mesa

2007-08-01

Full Text Available A wide number of supra-molecular association modes are observed in mixtures containing water and bile salts, BS, (with, eventually, other components. Molecular or micellar solutions transform into hydrated solids, fibres, lyotropic liquid crystals and/or gels by raising the concentration, the temperature, adding electrolytes, surfactants, lipids and proteins. Amorphous or ordered phases may be formed accordingly. The forces responsible for this very rich polymorphism presumably arise from the unusual combination of electrostatic, hydrophobic and hydrogen-bond contributions to the system stability, with subsequent control of the supra-molecular organisation modes. The stabilising effect due to hydrogen bonds does not occur in almost all surfactants or lipids and is peculiar to bile acids and salts. Some supra-molecular organisation modes, supposed to be related to malfunctions and dis-metabolic diseases in vivo, are briefly reported and discussed.

Battery recycling: recovery of manganese in the form of electrolytic manganese dioxide

International Nuclear Information System (INIS)

Roriz, Elizabeth Rodrigues Rangel; Von Krüge, Paulo; Espinosa, Denise Crocce Romano; Tenorio, Jorge Alberto Soares

2010-01-01

This work seeks to verify the possibility of using depleted batteries as a source of manganese applying the electrolytic process, considering the growing demand for products containing manganese in their composition. It was used an electrolyte solution containing the metal ions: Ca (270mg / L), Ni (3000 mg / L), Co (630 mg / L), Mn (115.300 mg / L) , Ti (400 mg / L) and Pb (20 mg / L) in concentrated sulfuric acid. The production of electrolytic manganese dioxide (EMD) was performed through galvanization using a stabilized source that monitored the potential of the working electrode. It was used an electrode of lead and two counter electrodes of graphite at a temperature of 98 deg C (± 2 deg C) and current density of 1.69A.dm"-"2. The material obtained was analyzed through the process of X-ray fluorescence spectrometry and X-ray diffraction. The results indicated that it is possible to obtain electrolytic manganese dioxide with a purity of about 94% and that the main allotropic variety obtained under the conditions of the experiment was the ε-MnO_2. (author)

Pyrrolidinium FSI and TFSI-Based Polymerized Ionic Liquids as Electrolytes for High-Temperature Lithium-Ion Batteries

Directory of Open Access Journals (Sweden)

Manfred Kerner

2018-02-01

Full Text Available Promising electrochemical and dynamical properties, as well as high thermal stability, have been the driving forces behind application of ionic liquids (ILs and polymerized ionic liquids (PILs as electrolytes for high-temperature lithium-ion batteries (HT-LIBs. Here, several ternary lithium-salt/IL/PIL electrolytes (PILel have been investigated for synergies of having both FSI and TFSI anions present, primarily in terms of physico-chemical properties, for unique application in HT-LIBs operating at 80 °C. All of the electrolytes tested have low Tg and are thermally stable ≥100 °C, and with TFSI as the exclusive anion the electrolytes (set A have higher thermal stabilities ≥125 °C. Ionic conductivities are in the range of 1 mS/cm at 100 °C and slightly higher for set A PILel, which, however, have lower oxidation stabilities than set B PILel with both FSI and TFSI anions present: 3.4–3.7 V vs. 4.2 V. The evolution of the interfacial resistance increases for all PILel during the first 40 h, but are much lower for set B PILel and generally decrease with increasing Li-salt content. The higher interfacial resistances only influence the cycling performance at high C-rates (1 C, where set B PILel with high Li-salt content performs better, while the discharge capacities at the 0.1 C rate are comparable. Long-term cycling at 0.5 C, however, shows stable discharge capacities for 100 cycles, with the exception of the set B PILel with high Li-salt content. Altogether, the presence of both FSI and TFSI anions in the PILel results in lower ionic conductivities and decreased thermal stabilities, but also higher oxidation stabilities and reduced interfacial resistances and, in total, result in an improved rate capability, but compromised long-term capacity retention. Overall, these electrolytes open for novel designs of HT-LIBs.

Supramolecular Complexes Formed in Systems Bile Salt-Bilirubin-Silica

Science.gov (United States)

Vlasova, N. N.; Severinovskaya, O. V.; Golovkova, L. P.

The formation of supramolecular complexes between bilirubin and primary micelles of bile salts has been studied. The association constants of bile salts and binding of bilirubin with these associates have been determined. The adsorption of bilirubin and bile salts from individual and mixed aqueous solutions onto hydrophobic silica surfaces has been investigated. The interaction of bilirubin with primary bile salt micelles and the strong retention in mixed micelles, which are supramolecular complexes, result in the adsorption of bilirubin in free state only.

Deposition of niobium plate on niobium-titanium from molten salts

International Nuclear Information System (INIS)

Matychenko, Eh.S.; Shevyrev, A.A.; Stolyarova, L.A.; Sukhorzhevskaya, S.L.

1993-01-01

A possibility of using Nb-Ti alloys (50 and 34 mas.% of Ti) as substrates for deposition of niobium coating of chloride-fluoride and fluoride molten salts is studied. Corrosion behaviour of alloys indicates in the electrolytic bath within 970-1070 K interval, coating structure and state of coating-substrate boundary are investigated. Chloride-fluoride molten salt usefullness for making products with niobium coatings is shown

Gelled Electrolyte Containing Phosphonium Ionic Liquids for Lithium-Ion Batteries

Directory of Open Access Journals (Sweden)

Mélody Leclère

2018-06-01

Full Text Available In this work, new gelled electrolytes were prepared based on a mixture containing phosphonium ionic liquid (IL composed of trihexyl(tetradecylphosphonium cation combined with bis(trifluoromethanesulfonimide [TFSI] counter anions and lithium salt, confined in a host network made from an epoxy prepolymer and amine hardener. We have demonstrated that the addition of electrolyte plays a key role on the kinetics of polymerization but also on the final properties of epoxy networks, especially thermal, thermo-mechanical, transport, and electrochemical properties. Thus, polymer electrolytes with excellent thermal stability (>300 °C combined with good thermo-mechanical properties have been prepared. In addition, an ionic conductivity of 0.13 Ms·cm−1 at 100 °C was reached. Its electrochemical stability was 3.95 V vs. Li0/Li+ and the assembled cell consisting in Li|LiFePO4 exhibited stable cycle properties even after 30 cycles. These results highlight a promising gelled electrolyte for future lithium ion batteries.

Hydrate-melt electrolytes for high-energy-density aqueous batteries

Science.gov (United States)

Yamada, Yuki; Usui, Kenji; Sodeyama, Keitaro; Ko, Seongjae; Tateyama, Yoshitaka; Yamada, Atsuo

2016-10-01

Aqueous Li-ion batteries are attracting increasing attention because they are potentially low in cost, safe and environmentally friendly. However, their low energy density (water and the limited selection of suitable negative electrodes, is problematic for their future widespread application. Here, we explore optimized eutectic systems of several organic Li salts and show that a room-temperature hydrate melt of Li salts can be used as a stable aqueous electrolyte in which all water molecules participate in Li+ hydration shells while retaining fluidity. This hydrate-melt electrolyte enables a reversible reaction at a commercial Li4Ti5O12 negative electrode with a low reaction potential (1.55 V versus Li+/Li) and a high capacity (175 mAh g-1). The resultant aqueous Li-ion batteries with high energy density (>130 Wh kg-1) and high voltage (˜2.3-3.1 V) represent significant progress towards performance comparable to that of commercial non-aqueous batteries (with energy densities of ˜150-400 Wh kg-1 and voltages of ˜2.4-3.8 V).

Towards Renewable Iodide Sources for Electrolytes in Dye-Sensitized Solar Cells

Directory of Open Access Journals (Sweden)

Iryna Sagaidak

2016-03-01

Full Text Available A novel family of iodide salts and ionic liquids based on different carbohydrate core units is herein described for application in dye-sensitized solar cell (DSC. The influence of the molecular skeleton and the cationic structure on the electrolyte properties, device performance and on interfacial charge transfer has been investigated. In combination with the C106 polypyridyl ruthenium sensitizer, power conversion efficiencies lying between 5.0% and 7.3% under standard Air Mass (A.M. 1.5G conditions were obtained in association with a low volatile methoxypropionitrile (MPN-based electrolyte.

Wide-Temperature Electrolytes for Lithium-Ion Batteries.

Science.gov (United States)

Li, Qiuyan; Jiao, Shuhong; Luo, Langli; Ding, Michael S; Zheng, Jianming; Cartmell, Samuel S; Wang, Chong-Min; Xu, Kang; Zhang, Ji-Guang; Xu, Wu

2017-06-07

Formulating electrolytes with solvents of low freezing points and high dielectric constants is a direct approach to extend the service-temperature range of lithium (Li)-ion batteries (LIBs). In this study, we report such wide-temperature electrolyte formulations by optimizing the ethylene carbonate (EC) content in the ternary solvent system of EC, propylene carbonate (PC), and ethyl methyl carbonate (EMC) with LiPF 6 salt and CsPF 6 additive. An extended service-temperature range from -40 to 60 °C was obtained in LIBs with lithium nickel cobalt aluminum oxide (LiNi 0.80 Co 0.15 Al 0.05 O 2 , NCA) as cathode and graphite as anode. The discharge capacities at low temperatures and the cycle life at room temperature and elevated temperatures were systematically investigated together with the ionic conductivity and phase-transition behaviors. The most promising electrolyte formulation was identified as 1.0 M LiPF 6 in EC-PC-EMC (1:1:8 by wt) with 0.05 M CsPF 6 , which was demonstrated in both coin cells of graphite∥NCA and 1 Ah pouch cells of graphite∥LiNi 1/3 Mn 1/3 Co 1/3 O 2 . This optimized electrolyte enables excellent wide-temperature performances, as evidenced by the high capacity retention (68%) at -40 °C and C/5 rate, significantly higher than that (20%) of the conventional LIB electrolyte, and the nearly identical stable cycle life as the conventional LIB electrolyte at room temperature and elevated temperatures up to 60 °C.

τ - hydrogen phosphate of zirconia in sodium salt form and some of its properties

International Nuclear Information System (INIS)

Fernandez V, S.M.; Ordonez R, E.

2004-01-01

It is reported the obtaining and characterization in the sodium salt form of the τ-hydrogen phosphate of zirconium in sodium form, this compound it was synthesized, for a new technique developed in the laboratory of Dept. of Chemistry of the ININ. The characterization was carried out for XRD, IR, Sem and EDS the thermal gravimetric analysis is also reported. (Author)

Performance limitations of polymer electrolytes based on ethylene oxide polymers

International Nuclear Information System (INIS)

Buriez, Olivier; Han, Yong Bong; Hou, Jun; Kerr, John B.; Qiao, Jun; Sloop, Steven E.; Tian, Minmin; Wang, Shanger

1999-01-01

Studies of polymer electrolyte solutions for lithium-polymer batteries are described. Two different salts, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium trifluoromethanesulfonate (LiTf), were dissolved in a variety of polymers. The structures were all based upon the ethylene oxide unit for lithium ion solvation and both linear and comb-branch polymer architectures have been examined. Conductivity, salt diffusion coefficient and transference number measurements demonstrate the superior transport properties of the LiTFSI salt over LiTf. Data obtained on all of these polymers combined with LiTFSI salts suggest that there is a limit to the conductivity achievable at room temperature, at least for hosts containing ethylene oxide units. The apparent conductivity limit is 5 x 10-5 S/cm at 25 C. Providing that the polymer chain segment containing the ethylene oxide units is at least 5-6 units long there appears to be little influence of the polymer framework to which the solvating groups are attached. To provide adequate separator function, the mechanical properties may be disconnected from the transport properties by selection of an appropriate architecture combined with an adequately long ethylene oxide chain. For both bulk and interfacial transport of the lithium ions, conductivity data alone is insufficient to understand the processes that occur. Lithium ion transference numbers and salt diffusion coefficients also play a major role in the observed behavior and the transport properties of these polymer electrolyte solutions appear to be quite inadequate for ambient temperature performance. At present, this restricts the use of such systems to high temperature applications. Several suggestions are given to overcome these obstacles

A hybrid lithium oxalate-phosphinate salt.

Science.gov (United States)

Shaffer, Andrew R; Deligonul, Nihal; Scherson, Daniel A; Protasiewicz, John D

2010-12-06

The novel organophosphorus-containing lithium salt Li(THF)[(C(2)O(4))B(O(2)PPh(2))(2)] (1; THF = tetrahydrofuran) was synthesized and characterized using a variety of spectroscopic techniques. An X-ray structural analysis on crystals of 1 grown from THF reveals a dimeric structure [Li(THF)(C(2)O(4))B(O(2)PPh(2))(2)](2)·THF, whereby the two units of 1 are bridged via P-O···Li interactions. Compound 1 displays high air and water stability and is also thermally robust, properties needed of electrolytes for their possible use as electrolytes and/or additives in lithium-ion battery applications.

Hybrid Metal/Electrolyte Monolithic Low Temperature SOFCs

National Research Council Canada - National Science Library

Cochran, Joe

2004-01-01

The program objective is to develop SOFCs, operating in the 500-700 degrees C range, based on Metal/Electrolyte square cell honeycomb formed by simultaneous powder extrusion of electrolyte and metal...

Uranium metal production by molten salt electrolysis

International Nuclear Information System (INIS)

Takasawa, Yutaka

1999-01-01

Atomic vapor laser isotope separation (AVLIS) is a promising uranium enrichment technology in the next generation. Electrolytic reduction of uranium oxides into uranium metal is proposed for the preparation of uranium metal as a feed material for AVLIS plant. Considering economical performance, continuos process concept and minimizing the amount of radioactive waste, an electrolytic process for producing uranium metal directly from uranium oxides will offer potential advantages over the existing commercial process. Studies of uranium metal by electrolysis in fluoride salts (BaF 2 -LiF-UF 4 (74-11-15 w/o) at 1150-1200degC, using both a laboratory scale apparatus and an engineering scale one, and continuous casting of uranium metal were carried out in order to decide the optimum operating conditions and the design of the industrial electrolytic cells. (author)

Influence of electrolyte ion-solvent interactions on the performances of supercapacitors porous carbon electrodes

Science.gov (United States)

Decaux, C.; Matei Ghimbeu, C.; Dahbi, M.; Anouti, M.; Lemordant, D.; Béguin, F.; Vix-Guterl, C.; Raymundo-Piñero, E.

2014-10-01

The development of advanced and safe electrochemical supercapacitors or hybrid supercapacitors combining a battery electrode material such as graphite and a porous carbon electrode implies the use of new electrolytes containing a tetra-alkylammonium or lithium salt dissolved preferentially in a safe and environmentally friendly solvent such as alkylcarbonates. In those systems, the carbon porosity of the activated carbon electrode controls the electrochemical behavior of the whole device. In this work, it is demonstrated that electrolytes containing highly polarizing ions such as Li+ dissolved in polar solvents such as alkylcarbonates do not completely loss their solvation shell at the opposite of what is observed for poorly solvated cations like TEABF4. As a consequence, the optimal carbon pore size for obtaining the largest energy density, while keeping a high power density, is wider when strongly solvated cations, like Li+ are used than for conventional organic electrolytes using acetonitrile as solvent and TEA+ as salt cations. TEA+ cations are easily desolvated and hence are able to penetrate in small pores matching the dimensions of bare ions. The dissimilarity of behavior of alkylcarbonates and acetonitrile based electrolytes highlights the importance of ion-solvent interactions when searching the optimal porous texture for the electrode material.

Influences of Electrolytes on the Soap-free Emulsion Copolymerization of St-MMA-AA

Institute of Scientific and Technical Information of China (English)

Rong Long LI; Cheng You KAN; Yi DU; Ze Ping LI

2006-01-01

Monodisperse functional polymer microspheres with different particle size and with clean surface were prepared by batch soap-free emulsion polymerization of styrene, methyl methacrylate and acrylic acid in the presence of salts, and the influences of type and amount of electrolytes on polymerization process and particle morphology were investigated. Results showed that there was a critical concentration for different electrolyte to make polymerization process and the resultant emulsion stable, and the particle size increased with the increase of electrolyte concentration. The effect of metal ions was Ca2+＞＞K+＞Na+＞Li+, and the effect of haloids was Br-＞Cl-＞F-.

Synthesis of Ca(PF$_6$)$_2$, formed $\\textit{via}$ nitrosonium oxidation of calcium

OpenAIRE

Keyzer, Evan; Matthews, PD; Liu, Zigeng; Bond, Andrew David; Grey, Clare Philomena; Wright, Dominic Simon

2017-01-01

The development of rechargeable Ca-ion batteries as an alternative to Li systems has been limited by the availability of suitable electrolyte salts. We present the synthesis of complexes of Ca(PF$_6$)$_2$ (a key potential Ca battery electrolyte salt) $\\textit{via}$ the treatment of Ca metal with NOPF$_6$, and explore their conversion to species containing PO$_2$F$_2$$^{-}$ under the reaction conditions. NSERC of Canada PGSD; Gonville and Caius College; Cambridge Commonwealth, European, and...

Comparative Study of Ether-Based Electrolytes for Application in Lithium-Sulfur Battery.

Science.gov (United States)

Carbone, Lorenzo; Gobet, Mallory; Peng, Jing; Devany, Matthew; Scrosati, Bruno; Greenbaum, Steve; Hassoun, Jusef

2015-07-01

Herein, we report the characteristics of electrolytes using various ether-solvents with molecular composition CH3O[CH2CH2O]nCH3, differing by chain length, and LiCF3SO3 as the lithium salt. The electrolytes, considered as suitable media for lithium-sulfur batteries, are characterized in terms of thermal properties (TGA, DSC), lithium ion conductivity, lithium interface stability, cyclic voltammetry, self-diffusion properties of the various components, and lithium transference number measured by NMR. Furthermore, the electrolytes are characterized in lithium cells using a sulfur-carbon composite cathode by galvanostatic charge-discharge tests. The results clearly evidence the influence of the solvent chain length on the species mobility within the electrolytes that directly affects the behavior in lithium sulfur cell. The results may effectively contribute to the progress of an efficient, high-energy lithium-sulfur battery.

Similarity of salt influences on the pH of buffers, polyelectrolytes, and proteins.

Science.gov (United States)

Voinescu, Alina E; Bauduin, Pierre; Pinna, M Cristina; Touraud, Didier; Ninham, Barry W; Kunz, Werner

2006-05-04

Changes in pH induced by the addition of electrolytes to buffers, polyelectrolytes (a polycarboxy polymethylene and a polyethyleneimine), and proteins (casein, whey, and lysozyme) solutions are explored systematically. The two buffer systems are triethanolamine/triethanolammonium chloride and citric acid/sodium citrate. These are chosen because of the similarity of their acid-base equilibria with those of amino acids predominant in most proteins, that is, amino acids that include carboxylate or ammonium groups in their structures. The pH of triethanolamine and of citrate buffers respectively increases and decreases when salt is added. At low electrolyte concentrations (buffer solutions. It is even possible to qualitatively predict these changes in protein solutions simply from the primary protein structure. At least in the systems considered here, the specific ion effects on pH seem to correlate with the bulk activity coefficients of the added electrolytes, at least at moderate salt concentrations.

Ultra-long-term human salt balance studies reveal interrelations between sodium, potassium, and chloride intake and excretion.

Science.gov (United States)

Birukov, Anna; Rakova, Natalia; Lerchl, Kathrin; Engberink, Rik Hg Olde; Johannes, Bernd; Wabel, Peter; Moissl, Ulrich; Rauh, Manfred; Luft, Friedrich C; Titze, Jens

2016-07-01

The intake of sodium, chloride, and potassium is considered important to healthy nutrition and cardiovascular disease risk. Estimating the intake of these electrolytes is difficult and usually predicated on urine collections, commonly for 24 h, which are considered the gold standard. We reported on data earlier for sodium but not for potassium or chloride. We were able to test the value of 24-h urine collections in a unique, ultra-long-term balance study conducted during a simulated trip to Mars. Four healthy men were observed while ingesting 12 g salt/d, 9 g salt/d, and 6 g salt/d, while their potassium intake was maintained at 4 g/d for 105 d. Six healthy men were studied while ingesting 12 g salt/d, 9 g salt/d, and 6 g salt/d, with a re-exposure of 12 g/d, while their potassium intake was maintained at 4 g/d for 205 d. Food intake and other constituents were recorded every day for each subject. All urine output was collected daily. Long-term urine recovery rates for all 3 electrolytes were very high. Rather than the expected constant daily excretion related to daily intake, we observed remarkable daily variation in excretion, with a 7-d infradian rhythm at a relatively constant intake. We monitored 24-h aldosterone excretion in these studies and found that aldosterone appeared to be the regulator for all 3 electrolytes. We report Bland-Altman analyses on the value of urine collections to estimate intake. A single 24-h urine collection cannot predict sodium, potassium, or chloride intake; thus, multiple collections are necessary. This information is important when assessing electrolyte intake in individuals. © 2016 American Society for Nutrition.

Impedance Spectroscopy and FTIR Studies of PEG - Based Polymer Electrolytes

Directory of Open Access Journals (Sweden)

Anji Reddy Polu

2011-01-01

Full Text Available Ionic conductivity of poly(ethylene glycol (PEG - ammonium chloride (NH4Cl based polymer electrolytes can be enhanced by incorporating ceramic filler TiO2 into PEG-NH4Cl matrix. The electrolyte samples were prepared by solution casting technique. FTIR studies indicates that the complex formation between the polymer, salt and ceramic filler. The ionic conductivity was measured using impedance spectroscopy technique. It was observed that the conductivity of the electrolyte varies with TiO2 concentration and temperature. The highest room temperature conductivity of the electrolyte of 7.72×10−6 S cm-1 was obtained at 15% by weight of TiO2 and that without TiO2 filler was found to be 9.58×10−7 S cm−1. The conductivity has been improved by 8 times when the TiO2 filler was introduced into the PEG–NH4Cl electrolyte system. The conductance spectra shows two distinct regions: a dc plateau and a dispersive region. The temperature dependence of the conductivity of the polymer electrolytes seems to obey the VTF relation. The conductivity values of the polymer electrolytes were reported and the results were discussed. The imaginary part of dielectric constant (εi decreases with increase in frequency in the low frequency region whereas frequency independent behavior is observed in the high frequency region.

Electrolyte solutions including a phosphoranimine compound, and energy storage devices including same

Science.gov (United States)

Klaehn, John R.; Dufek, Eric J.; Rollins, Harry W.; Harrup, Mason K.; Gering, Kevin L.

2017-09-12

An electrolyte solution comprising at least one phosphoranimine compound and a metal salt. The at least one phosphoranimine compound comprises a compound of the chemical structure ##STR00001## where X is an organosilyl group or a tert-butyl group and each of R.sup.1, R.sup.2, and R.sup.3 is independently selected from the group consisting of an alkyl group, an aryl group, an alkoxy group, or an aryloxy group. An energy storage device including the electrolyte solution is also disclosed.

Improvement of the stability of TiSnSb anode under lithiation using SEI forming additives and room temperature ionic liquid/DMC mixed electrolyte

International Nuclear Information System (INIS)

Zhang, W.; Ghamouss, F.; Mery, A.; Lemordant, D.; Dedryvère, R.; Monconduit, L.; Martinez, H.

2015-01-01

Highlights: • Lithiation and delithiation of TiSnSb conversion anode material • Room temperature ionic liquid based electrolyte • Fluoroethylene carbonate SEI builder additives • XPS and electrochemical analysis of the anode/electrolyte interface -- Abstract: The electrochemical behavior and the stability under cycling of TiSnSb anode for Li-ion batteries were investigated in room temperature ionic liquids based electrolyte. X-ray photoelectron spectroscopy (XPS), cyclic voltammetry, and electrochemical impedance (EIS) measurements have been performed to study the formation of surface film on the TiSnSb anode. Surface analysis was performed by a combined XPS core peaks and quantification data analysis, to establish the main components of the solid electrolyte interphase film (SEI). The key observation is that the thickness and the chemical nature of the SEI layer is strongly related to the electrolyte formulation and the addition of SEI layer forming additives. Vinylene carbonate (VC) and fluoroethylene carbonate (FEC) were applied in order to improve the anode/electrolyte interface. From XPS, EIS results and galvanostatic cycling the role of additives and ionic liquids as an effective stability improver has been highlighted

Waste form dissolution in bedded salt

International Nuclear Information System (INIS)

Kaufman, A.M.

1980-01-01

A model was devised for waste dissolution in bedded salt, a hydrologically tight medium. For a typical Spent UnReprocessed Fuel (SURF) emplacement, the dissolution rate wll be diffusion limited and will rise to a steady state value after t/sub eq/ approx. = 250 (1+(1-epsilon 0 ) K/sub D//epsilon 0 ) (years) epsilon 0 is the overpack porosity and K/sub d/ is the overpack sorption coefficient. The steady state dissolution rate itself is dominated by the solubility of UO 2 . Steady state rates between 5 x 10 -5 and .5 (g/year) are achievable by SURF emplacements in bedded salt without overpack, and rates between 5 x 10 -7 and 5 x 10 -3 (g/year) with an overpack having porosity of 10 -2

Conductivity of liquid lithium electrolytes with dispersed mesoporous silica particles

International Nuclear Information System (INIS)

Sann, K.; Roggenbuck, J.; Krawczyk, N.; Buschmann, H.; Luerßen, B.; Fröba, M.; Janek, J.

2012-01-01

Highlights: ► The conductivity of disperse lithium electrolytes with mesoporous fillers is studied. ► In contrast to other investigations in literature, no conductivity enhancement could be observed for standard battery electrolytes and typical mesoporous fillers in various combinations. ► Disperse electrolytes can become relevant in terms of battery safety. ► Dispersions of silicas and electrolyte with LiPF 6 as conducting salt are not stable, although the silicas were dried prior to preparation and the electrolyte water content was controlled. Surface modification of the fillers improved the stability. ► The observed conductivity decrease varied considerably for various fillers. - Abstract: The electrical conductivity of disperse electrolytes was systematically measured as a function of temperature (0 °C to 60 °C) and filler content for different types of fillers with a range of pore geometry, pore structure and specific surface area. As fillers mesoporous silicas SBA-15, MCM-41 and KIT-6 with pore ranges between 3 nm and 15 nm were dispersed in commercially available liquid lithium electrolytes. As electrolytes 1 M of lithium hexafluorophosphate (LiPF 6 ) in a mixture of ethylene carbonate (EC) and diethylene carbonate (DEC) at the ratio 3:7 (wt/wt) and the same solvent mixture with 0.96 M lithium bis(trifluoromethanesulfon)imide (LiTFSI) were used. No conductivity enhancement could be observed, but with respect to safety aspects the highly viscous disperse pastes might be useful. The conductivity decrease varied considerably for the different fillers.

Corrosion behavior of Ni-based structural materials for electrolytic reduction in lithium molten salt

International Nuclear Information System (INIS)

Cho, Soo Haeng; Park, Sung Bin; Lee, Jong Hyeon; Hur, Jin Mok; Lee, Han Soo

2011-01-01

In this study, the corrosion behavior of new Ni-based structural materials was studied for electrolytic reduction after exposure to LiCl-Li 2 O molten salt at 650 deg. C for 24-216 h under an oxidizing atmosphere. The new alloys with Ni, Cr, Al, Si, and Nb as the major components were melted at 1700 deg. C under an inert atmosphere. The melt was poured into a preheated metallic mold to prepare an as-cast alloy. The corrosion products and fine structures of the corroded specimens were characterized by scanning electron microscope (SEM), Energy Dispersive X-ray Spectroscope (EDS), and X-ray diffraction (XRD). The corrosion products of as cast and heat treated low Si/high Ti alloys were Cr 2 O 3 , NiCr 2 O 4 , Ni, NiO, and (Al,Nb,Ti)O 2 ; those of as cast and heat treated high Si/low Ti alloys were Cr 2 O 3 , NiCr 2 O 4 , Ni, and NiO. The corrosion layers of as cast and heat treated low Si/high Ti alloys were continuous and dense. However, those of as cast and heat treated high Si/low Ti alloys were discontinuous and cracked. Heat treated low Si/high Ti alloy showed the highest corrosion resistance among the examined alloys. The superior corrosion resistance of the heat treated low Si/high Ti alloy was attributed to the addition of an appropriate amount of Si, and the metallurgical evaluations were performed systematically.

A New All-Solid-State Hyperbranched Star Polymer Electrolyte for Lithium Ion Batteries: Synthesis and Electrochemical Properties

International Nuclear Information System (INIS)

Wang, Ailian; Xu, Hao; Zhou, Qian; Liu, Xu; Li, Zhengyao; Gao, Rui; Wu, Na; Guo, Yuguo; Li, Huayi; Zhang, Liaoyun

2016-01-01

Highlights: • A new hyperbranched multi-arm star polymer was successfully synthesized. • The star polymer electrolyte has good thermal stability and forming-film property. • The ion conductivity electrolyte can reach 8.3 × 10"−"5 S cm"−"1 at room temperature. • The star polymer electrolyte has wide electrochemical windows of 4.7 V. - Abstract: A new hyperbranched multi-arm star polymer with hyperbranched polystyrene (HBPS) as core and polymethyl methacrylate-block-poly(ethylene glycol) methyl ether methacrylate(PMMA-b-PPEGMA) as arms was firstly synthesized by atom transfer radical polymerization. The obtained hyperbranched multi-arm star polymer (HBPS-(PMMA-b-PPEGMA)_x) exhibited good thermal stability with a thermal decomposition temperature of 372 °C. The transparent, free-standing, flexible polymer electrolyte film of the blending of HBPS-(PMMA-b-PPEGMA)_x and lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) was successfully fabricated by a solution casting method. The ionic conductivity of the hyperbranched star polymer electrolyte with a molar ratio of [EO]/[Li] of 30 could reach 8.3 × 10"−"5 S cm"−"1 at 30 °C (with the content of PPEGMA of 83.7%), and 2.0 × 10"−"4 S cm"−"1 at 80 °C (with the content of PPEGMA of 51.6%). The effect of the concentration of lithium salts on ionic conductivity was also investigated. The obtained all-solid-state polymer electrolyte possessed a wide electrochemical stability window of 4.7 V (vs. Li"+/Li), and a lithium-ion transference number (t_L_i"+) up to 0.31. The interfacial impedance of the fabricated LiÔöépolymer electrolyteÔöéLi symmetric cell based on hyperbranched star multi-arm polymer electrolyte exhibited good interfacial compatibility between all-solid-state polymer electrolyte and electrodes. The excellent properties of the hyperbranched star polymer electrolyte made it attractive as solid-state polymer electrolyte for lithium-ion batteries.

Immobilization of IFR salt wastes in mortar

International Nuclear Information System (INIS)

Fisher, D.F.; Johnson, T.R.

1988-01-01

Portland cement-base mortars are being considered for immobilizing chloride salt wastes from the fuel cycle of an integral fast reactor (IFR). The IFR is a sodium-cooled fast reactor with metal fuel. It has a close-coupled fuel cycle in which fission products are separated from the actinides in an electrochemical cell operating at 500 degrees C. This cell has a cadmium anode and a liquid salt electrolyte. The salt will be a low-melting mixture of alkaline and alkaline earth chlorides. This paper discusses one method being considered for immobilizing this treated salt, to disperse it in a portland cement-base motar, which would then be sealed in corrosion-resistant containers. For this application, the grout must be sufficiently fluid that it can be pumped into canisters where it will solidify into a strong, leach-resistant material

Fission Product Separation from Pyrochemical Electrolyte by Cold Finger Melt Crystallization

Energy Technology Data Exchange (ETDEWEB)

Versey, Joshua R. [Univ. of Idaho, Moscow, ID (United States)

2013-08-01

This work contributes to the development of pyroprocessing technology as an economically viable means of separating used nuclear fuel from fission products and cladding materials. Electrolytic oxide reduction is used as a head-end step before electrorefining to reduce oxide fuel to metallic form. The electrolytic medium used in this technique is molten LiCl-Li2O. Groups I and II fission products, such as cesium (Cs) and strontium (Sr), have been shown to partition from the fuel into the molten LiCl-Li2O. Various approaches of separating these fission products from the salt have been investigated by different research groups. One promising approach is based on a layer crystallization method studied at the Korea Atomic Energy Research Institute (KAERI). Despite successful demonstration of this basic approach, there are questions that remain, especially concerning the development of economical and scalable operating parameters based on a comprehensive understanding of heat and mass transfer. This research explores these parameters through a series of experiments in which LiCl is purified, by concentrating CsCl in a liquid phase as purified LiCl is crystallized and removed via an argon-cooled cold finger.

Development and characterization of new high-level waste form containing LiCl KCl eutectic salts for achieving waste minimization from pyroprocessing

International Nuclear Information System (INIS)

Cho, Yong Zun; Kim, In Tae; Park, Hwan Seo; Ahn, Byeung Gil; Eun, Hee Chul; Son, Seock Mo; Ah, Su Na

2011-12-01

The purpose of this project is to develop new high level waste (HLW) forms and fabrication processes to dispose of active metal fission products that are removed from electrorefiner salts in the pyroprocessing based fuel cycle. The current technology for disposing of active metal fission products in pyroprocessing involves non selectively discarding of fission product loaded salt in a glass-bonded sodalite ceramic waste form. Selective removal of fission products from the molten salt would greatly minimize the amount of HLW generated and methods were developed to achieve selective separation of fission products during a previous I NERI research project (I NERI 2006 002 K). This I NERI project proceeds from the previous project with the development of suitable waste forms to immobilize the separated fission products. The Korea Atomic Energy Research Institute (KAERI) has focused primarily on developing these waste forms using surrogate waste materials, while the Idaho National Laboratory (INL) has demonstrated fabrication of these waste forms using radioactive electrorefiner salts in hot cell facilities available at INL. Testing and characterization of these radioactive materials was also performed to determine the physical, chemical, and durability properties of the waste forms

Salt-specific effects in lysozyme solutions

Directory of Open Access Journals (Sweden)

T. Janc

2016-03-01

Full Text Available The effects of additions of low-molecular-mass salts on the properties of aqueous lysozyme solutions are examined by using the cloud-point temperature, T_{cloud}, measurements. Mixtures of protein, buffer, and simple salt in water are studied at pH=6.8 (phosphate buffer and pH=4.6 (acetate buffer. We show that an addition of buffer in the amount above I_{buffer} = 0.6 mol dm^{-3} does not affect the T_{cloud} values. However, by replacing a certain amount of the buffer electrolyte by another salt, keeping the total ionic strength constant, we can significantly change the cloud-point temperature. All the salts de-stabilize the solution and the magnitude of the effect depends on the nature of the salt. Experimental results are analyzed within the framework of the one-component model, which treats the protein-protein interaction as highly directional and of short-range. We use this approach to predict the second virial coefficients, and liquid-liquid phase diagrams under conditions, where T_{cloud} is determined experimentally.

Electroviscous dissipation in aqueous electrolyte films with overlapping electric double layers

NARCIS (Netherlands)

Liu, Fei; Klaassen, Aram Harold; Zhao, Cunlu; Mugele, Friedrich Gunther; van den Ende, Henricus T.M.

2018-01-01

We use dynamic atomic force microscopy (AFM) to investigate the forces involved in squeezing out thin films of aqueous electrolyte between an AFM tip and silica substrates at variable pH and salt concentration. From amplitude and phase of the AFM signal we determine both conservative and dissipative

Passivation behavior of Type 304 stainless steel in a non-aqueous alkyl carbonate solution containing LiPF6 salt

International Nuclear Information System (INIS)

Myung, Seung-Taek; Sasaki, Yusuke; Saito, Takamitsu; Sun, Yang-Kook; Yashiro, Hitoshi

2009-01-01

Passivation behavior of type 304 stainless steel in a non-aqueous alkyl carbonate solution containing LiPF 6 salt was studied using electrochemical polarization, X-ray photoelectron spectroscopy (XPS) and time of flight-secondary ion mass spectroscopy (ToF-SIMS). Cathodic polarization to 0 V vs. Li/Li + resulted in most but not complete reduction of the air-formed film from oxides to metal on the stainless steel, as confirmed by XPS. For complete elimination of the air-formed film, the surface of the stainless steel was scratched under anodic polarization conditions. At 3 V vs. Li/Li + where an anodic current peak appeared, only an indistinct layer was recognized on the newly scratched surface, according to ToF-SIMS analysis. Above 4 V vs. Li/Li + , substantial passive films were formed, which were composed of oxides and fluorides of iron and chromium. The origin of oxide was due to water contained in the non-aqueous alkyl carbonate solution, and that of fluorides were the result of the decomposition of electrolytic salt, LiPF 6 , especially at higher potential. The resultant passive films were stable in the non-aqueous alkyl carbonate solution containing LiPF 6 salt.

Nanocomposite polymer electrolyte based on whisker or microfibrils polyoxyethylene nanocomposites

Energy Technology Data Exchange (ETDEWEB)

Alloin, Fannie, E-mail: fannie.alloin@lepmi.grenoble-inp.f [LEPMI, Laboratoire d' Electrochimie et de Physicochimie des Materiaux et des Interfaces, Grenoble-INP-UJF-CNRS, UMR 5631, BP 75, 38041 Grenoble Cedex 9 (France); D' Aprea, Alessandra [Laboratoire de Rheologie, Grenoble-INP-UJF, UMR 5520, BP 53, 38041 Grenoble Cedex 9 (France); LEPMI, Laboratoire d' Electrochimie et de Physicochimie des Materiaux et des Interfaces, Grenoble-INP-UJF-CNRS, UMR 5631, BP 75, 38041 Grenoble Cedex 9 (France); Ecole Internationale du Papier, de la communication imprimee et des Biomateriaux, PAGORA- Grenoble-INP, BP 65, 38402 Saint Martin d' Heres Cedex (France); Kissi, Nadia El [Laboratoire de Rheologie, Grenoble-INP-UJF, UMR 5520, BP 53, 38041 Grenoble Cedex 9 (France); Dufresne, Alain [Ecole Internationale du Papier, de la communication imprimee et des Biomateriaux, PAGORA- Grenoble-INP, BP 65, 38402 Saint Martin d' Heres Cedex (France); Bossard, Frederic [Laboratoire de Rheologie, Grenoble-INP-UJF, UMR 5520, BP 53, 38041 Grenoble Cedex 9 (France)

2010-07-15

Nanocomposite polymer electrolytes composed of high molecular weight poly(oxyethylene) PEO as a matrix, LiTFSI as lithium salt and ramie, cotton and sisal whiskers with high aspect ratio and sisal microfibrils (MF), as reinforcing phase were prepared by casting-evaporation. The morphology of the composite electrolytes was investigated by scanning electron microscopy and their thermal behavior (characteristic temperatures, degradation temperature) were investigated by thermogravimetric analysis and differential scanning calorimetry. Nanocomposite electrolytes based on PEO reinforced by whiskers and MF sisal exhibited very high mechanical performance with a storage modulus of 160 MPa at high temperature. A weak decrease of the ionic conductivity was observed with the incorporation of 6 wt% of whiskers. The addition of microfibrils involved a larger decrease of the conductivity. This difference may be associated to the more restricted PEO mobility due to the addition of entangled nanofibers.

Association constants of telluronium salts; Konstanty assotsiatsii telluronievykh solej

Energy Technology Data Exchange (ETDEWEB)

Kovach, N A; Rivkin, B B; Sadekov, T D; Shvajka, O P

1997-12-31

Association constants in acetonitrile of triphenyl telluronium salts, which are dilute electrolytes, are determined through the conductometry method. Satisfactory correlation dependence of constants of interion association and threshold molar electroconductivity on the Litvinenko-Popov constants for depositing groups is identified. 6 refs.

Ultra-long–term human salt balance studies reveal interrelations between sodium, potassium, and chloride intake and excretion12

Science.gov (United States)

Birukov, Anna; Rakova, Natalia; Lerchl, Kathrin; Engberink, Rik HG Olde; Johannes, Bernd; Wabel, Peter; Moissl, Ulrich; Rauh, Manfred; Luft, Friedrich C; Titze, Jens

2016-01-01

Background: The intake of sodium, chloride, and potassium is considered important to healthy nutrition and cardiovascular disease risk. Estimating the intake of these electrolytes is difficult and usually predicated on urine collections, commonly for 24 h, which are considered the gold standard. We reported on data earlier for sodium but not for potassium or chloride. Objective: We were able to test the value of 24-h urine collections in a unique, ultra-long–term balance study conducted during a simulated trip to Mars. Design: Four healthy men were observed while ingesting 12 g salt/d, 9 g salt/d, and 6 g salt/d, while their potassium intake was maintained at 4 g/d for 105 d. Six healthy men were studied while ingesting 12 g salt/d, 9 g salt/d, and 6 g salt/d, with a re-exposure of 12 g/d, while their potassium intake was maintained at 4 g/d for 205 d. Food intake and other constituents were recorded every day for each subject. All urine output was collected daily. Results: Long-term urine recovery rates for all 3 electrolytes were very high. Rather than the expected constant daily excretion related to daily intake, we observed remarkable daily variation in excretion, with a 7-d infradian rhythm at a relatively constant intake. We monitored 24-h aldosterone excretion in these studies and found that aldosterone appeared to be the regulator for all 3 electrolytes. We report Bland–Altman analyses on the value of urine collections to estimate intake. Conclusions: A single 24-h urine collection cannot predict sodium, potassium, or chloride intake; thus, multiple collections are necessary. This information is important when assessing electrolyte intake in individuals. PMID:27225435

Stainless steel-zirconium alloy waste forms

International Nuclear Information System (INIS)

McDeavitt, S.M.; Abraham, D.P.; Keiser, D.D. Jr.; Park, J.Y.

1996-01-01

An electrometallurgical treatment process has been developed by Argonne National Laboratory to convert various types of spent nuclear fuels into stable storage forms and waste forms for repository disposal. The first application of this process will be to treat spent fuel alloys from the Experimental Breeder Reactor-II. Three distinct product streams emanate from the electrorefining process: (1) refined uranium; (2) fission products and actinides extracted from the electrolyte salt that are processed into a mineral waste form; and (3) metallic wastes left behind at the completion of the electrorefining step. The third product stream (i.e., the metal waste stream) is the subject of this paper. The metal waste stream contains components of the chopped spent fuel that are unaffected by the electrorefining process because of their electrochemically ''noble'' nature; this includes the cladding hulls, noble metal fission products (NMFP), and, in specific cases, zirconium from metal fuel alloys. The selected method for the consolidation and stabilization of the metal waste stream is melting and casting into a uniform, corrosion-resistant alloy. The waste form casting process will be carried out in a controlled-atmosphere furnace at high temperatures with a molten salt flux. Spent fuels with both stainless steel and Zircaloy cladding are being evaluated for treatment; thus, stainless steel-rich and Zircaloy-rich waste forms are being developed. Although the primary disposition option for the actinides is the mineral waste form, the concept of incorporating the TRU-bearing product into the metal waste form has enough potential to warrant investigation

Electrolytic destruction of oxalate ions in plutonium oxalate supernatant

International Nuclear Information System (INIS)

Michael, K.M.; Talnikar, S.G.; Jambunathan, U.; Kapoor, S.C.; Ramanujam, A.; Venkataraman, N.

1996-01-01

A simple and efficient electrolytic method is described for the destruction of the oxalate ions present in plutonium oxalate supernatant. Using platinum electrode and very little KMnO 4 , in situ generation of Mn 3+ ions is achieved which in turn destroys the oxalate. The use of lower current density helps in achieving maximum current efficiency. The end point is easily detectable by the pink colour of permanganate. By reversing the current, this slight excess of permanganate can be destroyed, thus avoiding the use of hydrogen peroxide. By this simple electrolytic method, the corrosive oxalate ion is completely destroyed and the salt content of the waste solution is considerably reduced. (author). 4 refs., 1 fig., 6 tabs

Investigation of an Alternative Fuel Form for the Liquid Salt Cooled Very High Temperature Reactor (LS-VHTR)

International Nuclear Information System (INIS)

Casino, William A. Jr.

2006-01-01

Much of the recent studies investigating the use of liquid salts as reactor coolants have utilized a core configuration of graphite prismatic fuel block assemblies with TRISO particles embedded into cylindrical fuel compacts arranged in a triangular pitch lattice. Although many calculations have been performed for this fuel form in gas cooled reactors, it would be instructive to investigate whether an alternative fuel form may yield improved performance for the liquid salt-cooled Very High Temperature Reactor (LS-VHTR). This study investigates how variations in the fuel form will impact the performance of the LS-VHTR during normal and accident conditions and compares the results with a similar analysis that was recently completed for a LS-VHTR core made up of prismatic block fuel. (author)

Organic electrolytes for sodium batteries. Final report, 1 April 1990-31 March 1992

Energy Technology Data Exchange (ETDEWEB)

Vestergaard, B.

1992-09-01

This final report for the project 'Organic Electrolytes for Sodium Batteries' contains a summary of earlier given status reports in connection with the project. The aim of the investigations was to develop new room temperature molten salts electrolytes mainly with radical substituted heterocyclic organic chlorides mixed with aluminum chloride. The new electrolytes should have an ionic conductivity comparable with MEIC1:AlCl3 or better. A computer model program MOPAC (Molecular Orbital Package) was to be included to calculate theoretically reduction potentials for a variety of organic cations. Furthermore, MOPAC could be utilized to predict the electron densities, and then give a prediction of the stability of the organic cation.

NMR studies of Na+-anion association effects in polymer electrolytes

International Nuclear Information System (INIS)

Greenbaum, S.G.; Pak, Y.S.; Wintergill, M.C.; Fontanella, J.J.

1988-01-01

23 Na nuclear magnetic resonance (NMR) measurements on poly (propylene oxide) (PPO) and siloxane based polymer electrolytes containing various sodium salts at a single nominal concentration are reported. In addition, differential scanning calorimetry (DSC) and electrical conductivity studies were carried out on the PPO materials. The NMR-determined mobile Na + concentrations and DSC results provide evidence for ionic aggregation effects which, for some samples, result in salt precipitation at elevated temperatures. 23 Na chemical shifts observed in solid state NMR due to mobile Na + -anion interactions influence ionic transport as well as the number of available carriers. (author). 19 refs.; 7 figs

Quantitative Analysis of Oxygen Gas Exhausted from Anode through In Situ Measurement during Electrolytic Reduction

Directory of Open Access Journals (Sweden)

Eun-Young Choi

2017-01-01

Full Text Available Quantitative analysis by in situ measurement of oxygen gas evolved from an anode was employed to monitor the progress of electrolytic reduction of simulated oxide fuel in a molten Li2O–LiCl salt. The electrolytic reduction of 0.6 kg of simulated oxide fuel was performed in 5 kg of 1.5 wt.% Li2O–LiCl molten salt at 650°C. Porous cylindrical pellets of simulated oxide fuel were used as the cathode by loading a stainless steel wire mesh cathode basket. A platinum plate was employed as the anode. The oxygen gas evolved from the anode was exhausted to the instrumentation for in situ measurement during electrolytic reduction. The instrumentation consisted of a mass flow controller, pump, wet gas meter, and oxygen gas sensor. The oxygen gas was successfully measured using the instrumentation in real time. The measured volume of the oxygen gas was comparable to the theoretically calculated volume generated by the charge applied to the simulated oxide fuel.

Synthesis And Characterization of PVDF-LiBOB Electrolyte Membrane With ZrO2 As Additives

Directory of Open Access Journals (Sweden)

Etty Wigayati

2017-09-01

Full Text Available The electrolyte membrane serves as ions medium transport and as a separator between the anode and cathode in lithium ion battery. The polymer used for the electrolyte membrane must have sufficiently high mechanical strength to withstand the pressure between the anode and cathode, a thin size and has a chemical and thermal stability. Polymer electrolyte membrane of Lithium bisoxalate Borate(LiBOB salt with PVdF as matrix polymer and the additive is ZrO2 has been fabricated. The method used is a doctor blade. The concentration of the additive is varied. The membranes were characterized using FT-IR, XRD, SEM and EIS. XRD analysis showed that the crystallinity index increases with the addition of ZrO2. The presence of functional groups bewteen Lithium salts and polymer interaction shown by FTIR analysis. The morphology of the membrane surface was shown by SEM analysis. SEM image and mapping show the morphology of the membrane have typical porous layer. The electrical conductivity increases with additions of ZrO2.

Electron transfer through solid-electrolyte-interphase layers formed on Si anodes of Li-ion batteries

International Nuclear Information System (INIS)

Benitez, L.; Cristancho, D.; Seminario, J.M.; Martinez de la Hoz, J.M.; Balbuena, P.B.

2014-01-01

Solid-electrolyte interphase (SEI) films are formed on the electrode surfaces due to aggregation of products of reduction or oxidation of the electrolyte. These films may grow to thicknesses in the order of 50-100 nm and contain a variety of organic and inorganic products but their structure is not well defined. Although in some cases the films exert a passivating role, this is not always the case, and these phenomena are particularly more complex on Silicon anodes due to swelling and cracking of the electrode during lithiation and delithiation. Since the driving force for SEI growth is electron transfer, it is important to understand how electron transfer may keep occurring through the heterogeneous film once the bare electron surface is covered. Here we introduce a novel approach for studying electron transfer through model films and show preliminary results for the analysis of electron transfer through model composite interfacial systems integrated by electrode/SEI layer/electrolyte. Ab initio molecular dynamics simulations are used to identify deposition of SEI components, and a density functional theory/Green's function approach is utilized for characterizing electron transfer. Three degrees of lithiation are modeled for the electrodes, the SEI film is composed by LiF or Li 2 O, and the ethylene carbonate reduction is studied. An applied potential is used as driving force for the leakage current, which is evaluated as a function of the applied potential. Comparative analyses are done for LiF and Li 2 O model SEI layers

Nanostructured electrolytes for stable lithium electrodeposition in secondary batteries.

Science.gov (United States)

Tu, Zhengyuan; Nath, Pooja; Lu, Yingying; Tikekar, Mukul D; Archer, Lynden A

2015-11-17

modulus and stability requirements have to date proven to be insurmountable obstacles to progress. In this Account, we first review recent advances in continuum theory for dendrite growth and proliferation during metal electrodeposition. We show that the range of options for designing electrolytes and separators that stabilize electrodeposition is now substantially broader than one might imagine from previous literature accounts. In particular, separators designed at the nanoscale to constrain ion transport on length scales below a theory-defined cutoff, and structured electrolytes in which a fraction of anions are permanently immobilized to nanoparticles, to a polymer network or ceramic membrane are considered particularly promising for their ability to stabilize electrodeposition of lithium metal without compromising ionic conductivity or room temperature battery operation. We also review recent progress in designing surface passivation films for metallic lithium that facilitate fast deposition of lithium at the electrolyte/electrode interface and at the same time protect the lithium from parasitic side reactions with liquid electrolytes. A promising finding from both theory and experiment is that simple film-forming halide salt additives in a conventional liquid electrolyte can substantially extend the lifetime and safety of LMBs.

Methods of enhancing conductivity of a polymer-ceramic composite electrolyte

Science.gov (United States)

Kumar, Binod

2003-12-02

Methods for enhancing conductivity of polymer-ceramic composite electrolytes are provided which include forming a polymer-ceramic composite electrolyte film by a melt casting technique and uniaxially stretching the film from about 5 to 15% in length. The polymer-ceramic composite electrolyte is also preferably annealed after stretching such that it has a room temperature conductivity of from 10.sup.-4 S cm.sup.-1 to 10.sup.-3 S cm.sup.-1. The polymer-ceramic composite electrolyte formed by the methods of the present invention may be used in lithium rechargeable batteries.

Nanosized {alpha}-LiFeO{sub 2} as electrochemical supercapacitor electrode in neutral sulfate electrolytes

Energy Technology Data Exchange (ETDEWEB)

Santos-Pena, J., E-mail: iq2sanpe@uco.e [Departamento de Quimica Inorganica e Ingenieria Quimica, Edificio Marie Curie, Campus de Rabanales, Universidad de Cordoba, 14071 Cordoba (Spain); Crosnier, O.; Brousse, T. [Laboratoire de Genie des Materiaux et Procedes Associes, Ecole Polytechnique de l' Universite de Nantes, Site de la Chantrerie, rue Christian Pauc s/n, 44376 Nantes Cedex 3 (France)

2010-10-30

In this work we have explored the electrochemical properties of two lithiated iron oxide powders for supercapacitor purposes. These samples mainly consisted of {alpha}-LiFeO{sub 2} in nanosized or micrometric form. Electrolyte was an aqueous 0.5 M Li{sub 2}SO{sub 4} solution and voltage range studied was between 0 and -0.7 V vs. a Ag/AgCl reference electrode. As expected, electrochemical performance was dependent on the particle size. When electrolyte was deaerated a stable capacitance of {approx}50 F g{sup -1} is provided by the nanosized sample for several hundred cycles. Other sulfate based salts (Na{sub 2}SO{sub 4}, K{sub 2}SO{sub 4}, Cs{sub 2}SO{sub 4}) were investigated as electrolytes but only Li{sub 2}SO{sub 4} leads to a stable capacitance upon cycling, probably due to lithium intercalation. An hybrid cell consisting of this sample and MnO{sub 2} as negative and positive electrodes, respectively, delivered 0.3 F cm{sup -2} (10 F g{sup -1}). Although these values are lower than reported for other aqueous hybrid cell, {alpha}-LiFeO{sub 2}/MnO{sub 2} asymmetric capacitor is interesting from both, an economic and an environmental point of view.

Effect of electrolyte temperature on the formation of self-organized anodic niobium oxide microcones in hot phosphate-glycerol electrolyte

Science.gov (United States)

Yang, S.; Aoki, Y.; Habazaki, H.

2011-07-01

Nanoporous niobium oxide films with microcone-type surface morphology were formed by anodizing at 10 V in glycerol electrolyte containing 0.6 mol dm -3 K 2HPO 4 and 0.2 mol dm -3 K 3PO 4 in a temperature range of 428-453 K. The microcones appeared after prolonged anodizing, but the required time was largely reduced by increasing electrolyte temperature. The anodic oxide was initially amorphous at all temperatures, but crystalline oxide nucleated during anodizing. The anodic oxide microcones, which were crystalline, appeared on surface as a consequence of preferential chemical dissolution of initially formed amorphous oxide. The chemical dissolution of an initially formed amorphous layer was accelerated by increasing the electrolyte temperature, with negligible influence of the temperature on the morphology of microcones up to 448 K.

Self-Healable and Cold-Resistant Supercapacitor Based on a Multifunctional Hydrogel Electrolyte.

Science.gov (United States)

Tao, Feng; Qin, Liming; Wang, Zhikui; Pan, Qinmin

2017-05-10

Excellent self-healability and cold resistance are attractive properties for a portable/wearable energy-storage device. However, achieving the features is fundamentally dependent on an intrinsically self-healable electrolyte with high ionic conduction at low temperature. Here we report such a hydrogel electrolyte comprising sodium alginate cross-linked by dynamic catechol-borate ester bonding. Since its dynamically cross-linked alginate network can tolerate high-content inorganic salts, the electrolyte possesses excellent healing efficiency/cyclability but also high ionic conduction at both room temperature and low temperature. A supercapacitor with the multifunctional hydrogel electrolyte completely restores its capacitive properties even after breaking/healing for 10 cycles without external stimulus. At a low temperature of -10 °C, the capacitor is even able to maintain at least 80% of its room-temperature capacitance. Our investigations offer a strategy to assemble self-healable and cold-resistant energy storage devices by using a multifunctional hydrogel electrolyte with rationally designed polymeric networks, which has potential application in portable/wearable electronics, intelligent apparel or flexible robot, and so on.

Solid polymer electrolytes based on alternating copolymers of vinyl ethers with methoxy oligo(ethyleneoxy)ethyl groups and vinylene carbonate

International Nuclear Information System (INIS)

Itoh, Takahito; Fujita, Katsuhito; Inoue, Kentaro; Iwama, Hiroki; Kondoh, Kensaku; Uno, Takahiro; Kubo, Masataka

2013-01-01

Graphical abstract: - Highlights: • Synthesis of alternating copolymers of vinyl ethers and vinylene carbonate. • Preparation of polymer electrolytes based on the alternating copolymers with LiTFSI. • Structure-property relationship for alternating copolymers-based electrolytes. • Interfacial stability between polymer electrolytes with lithium metal electrode. - Abstract: Alternating copolymers (poly(1a-g-alt-VC)) of vinyl ethers with various methoxy oligo(ethyleneoxy)ethyl groups and vinylene carbonate (VC) were prepared, and the thermal and electrochemical properties of their polymer electrolytes with LiTFSI and interfacial stability between the polymer electrolyte and Li metal electrode were investigated. T g 's increased linearly with salt contents, and decreased with an increase in the chain length of methoxy oligo(ethyleneoxy)ethyl groups in the vinyl ethers at constant salt concentration. The slopes of T g vs. [Li]/[O] were identical, independent of the polymer structure. The ionic conductivities of the polymer electrolytes increased with increasing the side-chain ethyleneoxy (EO) unit length of the vinyl ether unit in the alternating copolymers, and also their temperature dependences became relatively smaller in the polymer electrolytes having longer EO units in the vinyl ethers. The highest ionic conductivity, 1.2 × 10 −4 S/cm at 30 °C, was obtained in the alternating copolymer with a side-chain EO unit length of 23.5 in the vinyl ether unit. Ion transport coupled with the segmental motion of the polymer is dominant in these polymer electrolytes. Interfacial resistance increased gradually with contact time, indicative of the formation of passivation films on the Li metal electrode. These polymer electrolytes are thermally stable and have large electrochemical windows of use

CONDUCTIVITY STUDIES OF (PEO +KHCO3 SOLID ELECTROLYTE SYSTEM AND ITS APPLICATION AS AN ELECTROCHEMICAL CELL

Directory of Open Access Journals (Sweden)

K. VIJAY KUMAR

2010-06-01

Full Text Available Solid polymer electrolyte system, polyethylene oxide (PEO complexed with potassium bicarbonate (KHCO3 salt was prepared by solution-cast technique. Several experimental techniques such as infrared radiation (IR, differential scanning calorimeter (DSC, and composition dependence conductivity, temperature dependence conductivity in the temperature range of 308–368 K and transport number measurements were employed to characterize this polymer electrolyte system. The conductivity of the (PEO+KHCO3 electrolyte was found to be about 3 times larger than that of pure PEO at room temperature. The transference data indicated that the charge transport in these polymer electrolyte systems is predominantly due to K+ ions. Using this polymer electrolyte an electrochemical cell with configuration K+/(PEO+KHCO3/(I2+C+electrolyte was fabricated and its discharge characteristics are studied. A number of other cell parameters associated with the cell were evaluated and are reported in this paper.

Composite Polymer Electrolytes: Nanoparticles Affect Structure and Properties

Directory of Open Access Journals (Sweden)

Wei Wang

2016-11-01

Full Text Available Composite polymer electrolytes (CPEs can significantly improve the performance in electrochemical devices such as lithium-ion batteries. This review summarizes property/performance relationships in the case where nanoparticles are introduced to polymer electrolytes. It is the aim of this review to provide a knowledge network that elucidates the role of nano-additives in the CPEs. Central to the discussion is the impact on the CPE performance of properties such as crystalline/amorphous structure, dielectric behavior, and interactions within the CPE. The amorphous domains of semi-crystalline polymer facilitate the ion transport, while an enhanced mobility of polymer chains contributes to high ionic conductivity. Dielectric properties reflect the relaxation behavior of polymer chains as an important factor in ion conduction. Further, the dielectric constant (ε determines the capability of the polymer to dissolve salt. The atom/ion/nanoparticle interactions within CPEs suggest ways to enhance the CPE conductivity by generating more free lithium ions. Certain properties can be improved simultaneously by nanoparticle addition in order to optimize the overall performance of the electrolyte. The effects of nano-additives on thermal and mechanical properties of CPEs are also presented in order to evaluate the electrolyte competence for lithium-ion battery applications.

Changes in Sea Salt Emissions Enhance ENSO Variability

Energy Technology Data Exchange (ETDEWEB)

Yang, Yang; Russell, Lynn M.; Lou, Sijia; Lamjiri, Maryam A.; Liu, Ying; Singh, Balwinder; Ghan, Steven J.

2016-11-15

Two 150-year pre-industrial simulations with and without interactive sea salt emissions from the Community Earth System Model (CESM) are performed to quantify the interactions between sea salt emissions and El Niño–Southern Oscillation (ENSO). Variations in sea salt emissions over the tropical Pacific Ocean are affected by changing wind speed associated with ENSO variability. ENSO-induced interannual variations in sea salt emissions result in decreasing (increasing) aerosol optical depth (AOD) by 0.03 over the equatorial central-eastern (western) Pacific Ocean during El Niño events compared to those during La Niña events. These changes in AOD further increase (decrease) radiative fluxes into the atmosphere by +0.2 W m^-2 (-0.4 W m^-2) over the tropical eastern (western) Pacific. Thereby, sea surface temperature increases (decreases) by 0.2–0.4 K over the tropical eastern (western) Pacific Ocean during El Niño compared to La Niña events and enhances ENSO variability by 10%. The increase in ENSO amplitude is a result of systematic heating (cooling) during the warm (cold) phase, of ENSO in the eastern Pacific. Interannual variations in sea salt emissions then produce the anomalous ascent (subsidence) over the equatorial eastern (western) Pacific between El Niño and La Niña events, which is a result of heating anomalies. Due to variations in sea salt emissions, the convective precipitation is enhanced by 0.6–1.2 mm day^-1 over the tropical central-eastern Pacific Ocean and weakened by 0.9–1.5 mm day^-1 over the Maritime Continent during El Niño compared to La Niña events, enhancing the precipitation variability over the tropical Pacific.

Transparent hydrogel with enhanced water retention capacity by introducing highly hydratable salt

OpenAIRE

Bai, Yuanyuan; Chen, Baohong; Xiang, Feng; Zhou, Jinxiong; Wang, Hong; Suo, Zhigang

2014-01-01

Polyacrylamide hydrogels containing salt as electrolyte have been used as highly stretchable transparent electrodes in flexible electronics, but those hydrogels are easy to dry out due to water evaporation. Targeted, we try to enhance water retention capacity of polyacrylamide hydrogel by introducing highly hydratable salts into the hydrogel. These hydrogels show enhanced water retention capacity in different level. Specially, polyacrylamide hydrogel containing high content of lithium chlorid...

Water purification using organic salts

Science.gov (United States)

Currier, Robert P.

2004-11-23

Water purification using organic salts. Feed water is mixed with at least one organic salt at a temperature sufficiently low to form organic salt hydrate crystals and brine. The crystals are separated from the brine, rinsed, and melted to form an aqueous solution of organic salt. Some of the water is removed from the aqueous organic salt solution. The purified water is collected, and the remaining more concentrated aqueous organic salt solution is reused.

Corrosion behavior of Ni-based structural materials for electrolytic reduction in lithium molten salt

Energy Technology Data Exchange (ETDEWEB)

Cho, Soo Haeng, E-mail: nshcho1@kaeri.re.kr [Korea Atomic Energy Research Institute, 1045 Daedeokdaero Yuseong-gu, Daejeon 305-353 (Korea, Republic of); Park, Sung Bin [Korea Atomic Energy Research Institute, 1045 Daedeokdaero Yuseong-gu, Daejeon 305-353 (Korea, Republic of); Lee, Jong Hyeon, E-mail: jonglee@cnu.ac.kr [Graduate School of Green Energy Technology, Chungnam National University, 79 Daehak-ro, Yuseong-gu, Daejeon 305-764 (Korea, Republic of); Hur, Jin Mok; Lee, Han Soo [Korea Atomic Energy Research Institute, 1045 Daedeokdaero Yuseong-gu, Daejeon 305-353 (Korea, Republic of)

2011-05-01

In this study, the corrosion behavior of new Ni-based structural materials was studied for electrolytic reduction after exposure to LiCl-Li{sub 2}O molten salt at 650 deg. C for 24-216 h under an oxidizing atmosphere. The new alloys with Ni, Cr, Al, Si, and Nb as the major components were melted at 1700 deg. C under an inert atmosphere. The melt was poured into a preheated metallic mold to prepare an as-cast alloy. The corrosion products and fine structures of the corroded specimens were characterized by scanning electron microscope (SEM), Energy Dispersive X-ray Spectroscope (EDS), and X-ray diffraction (XRD). The corrosion products of as cast and heat treated low Si/high Ti alloys were Cr{sub 2}O{sub 3}, NiCr{sub 2}O{sub 4}, Ni, NiO, and (Al,Nb,Ti)O{sub 2}; those of as cast and heat treated high Si/low Ti alloys were Cr{sub 2}O{sub 3}, NiCr{sub 2}O{sub 4}, Ni, and NiO. The corrosion layers of as cast and heat treated low Si/high Ti alloys were continuous and dense. However, those of as cast and heat treated high Si/low Ti alloys were discontinuous and cracked. Heat treated low Si/high Ti alloy showed the highest corrosion resistance among the examined alloys. The superior corrosion resistance of the heat treated low Si/high Ti alloy was attributed to the addition of an appropriate amount of Si, and the metallurgical evaluations were performed systematically.

Elucidating the Solvation Structure and Dynamics of Lithium Polysulfides Resulting from Competitive Salt and Solvent Interactions

Energy Technology Data Exchange (ETDEWEB)

Rajput, Nav Nidhi; Murugesan, Vijayakumar; Shin, Yongwoo; Han, Kee Sung; Lau, Kah Chun; Chen, Junzheng; Liu, Jun; Curtiss, Larry A.; Mueller, Karl T.; Persson, Kristin A.

2017-04-10

Fundamental molecular level understanding of functional properties of liquid solutions provides an important basis for designing optimized electrolytes for numerous applica-tions. In particular, exhaustive knowledge of solvation structure, stability and transport properties is critical for developing stable electrolytes for fast charging and high energy density next-generation energy storage systems. Here we report the correlation between solubility, solvation structure and translational dynamics of a lithium salt (Li-TFSI) and polysulfides species using well-benchmarked classical molecular dynamics simulations combined with nuclear magnetic resonance (NMR). It is observed that the polysulfide chain length has a significant effect on the ion-ion and ion-solvent interaction as well as on the diffusion coefficient of the ionic species in solution. In particular, extensive cluster formation is observed in lower order poly-sulfides (Sx2-; x≤4), whereas the longer polysulfides (Sx2-; x>4) show high solubility and slow dynamics in the solu-tion. It is observed that optimal solvent/salt ratio is essen-tial to control the solubility and conductivity as the addi-tion of Li salt increases the solubility but decreases the mo-bility of the ionic species. This work provides a coupled theoretical and experimental study of bulk solvation struc-ture and transport properties of multi-component electro-lyte systems, yielding design metrics for developing optimal electrolytes with improved stability and solubility.

Electrolytes for Low Impedance, Wide Operating Temperature Range Lithium-Ion Battery Module

Science.gov (United States)

Hallac, Boutros (Inventor); Krause, Frederick C. (Inventor); Jiang, Junwei (Inventor); Smart, Marshall C. (Inventor); Metz, Bernhard M. (Inventor); Bugga, Ratnakumar V. (Inventor)

2018-01-01

A lithium ion battery cell includes a housing, a cathode disposed within the housing, wherein the cathode comprises a cathode active material, an anode disposed within the housing, wherein the anode comprises an anode active material, and an electrolyte disposed within the housing and in contact with the cathode and anode. The electrolyte consists essentially of a solvent mixture, a lithium salt in a concentration ranging from approximately 1.0 molar (M) to approximately 1.6 M, and an additive mixture. The solvent mixture includes a cyclic carbonate, an non-cyclic carbonate, and a linear ester. The additive mixture consists essentially of lithium difluoro(oxalato)borate (LiDFOB) in an amount ranging from approximately 0.5 weight percent to approximately 2.0 weight percent based on the weight of the electrolyte, and vinylene carbonate (VC) in an amount ranging from approximately 0.5 weight percent to approximately 2.0 weight percent based on the weight of the electrolyte.

A high-voltage and non-corrosive ionic liquid electrolyte used in rechargeable aluminum battery.

Science.gov (United States)

Wang, Huali; Gu, Sichen; Bai, Ying; Chen, Shi; Wu, Feng; Wu, Chuan

2016-10-03

As a promising post-lithium battery, rechargeable aluminum battery has the potential to achieve a three-electron reaction with fully use of metal aluminum. Alternative electrolytes are strongly needed for further development of rechargeable aluminum batteries, since typical AlCl3-contained imidazole-based ionic liquids are moisture sensitive, corrosive, and with low oxidation voltage. In this letter, a kind of non-corrosive and water-stable ionic liquid obtained by mixing 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([BMIM]OTF) with the corresponding aluminum salt (Al(OTF)3) is studied. This ionic liquid electrolyte has a high oxidation voltage (3.25V vs Al3+/Al) and high ionic conductivity, and a good electrochemical performance is also achieved. A new strategy, which first use corrosive AlCl3-based electrolyte to construct a suitable passageway on the Al anode for Al3+, and then use non-corrosive Al(OTF)3-based electrolyte to get stable Al/electrolyte interface, is put forward.

Degradation of the corrosion resistance of anodic oxide films through immersion in the anodising electrolyte

Energy Technology Data Exchange (ETDEWEB)

Garcia-Rubio, M. [Departamento de Quimica-Fisica Aplicada, Universidad Autonoma de Madrid, 28049-Madrid (Spain); Department of Surface Technologies, Engineering of Materials and Processes, Airbus Spain, Av. John Lennon s/n 28906-Getafe (Spain); Ocon, P., E-mail: pilar.ocon@uam.e [Departamento de Quimica-Fisica Aplicada, Universidad Autonoma de Madrid, 28049-Madrid (Spain); Curioni, M.; Thompson, G.E.; Skeldon, P. [Corrosion and Protection Center, School of Materials, The University of Manchester, M60 1QD England (United Kingdom); Lavia, A. [Department of Surface Technologies, Engineering of Materials and Processes, Airbus Spain, Av. John Lennon s/n 28906-Getafe (Spain); Garcia, I. [Department of Surface Technologies, Engineering of Materials and Processes, Airbus Spain, Av. John Lennon s/n 28906-Getafe (Spain); Department of Corrosion and Protection, National Center for Metallurgical Research CENIM-CSIC, Av. Gregorio del Amo 8, 28040-Madrid (Spain)

2010-07-15

The deterioration of AA2024, AA6061 and AA7475 anodised in an environmentally-compliant tartaric acid/sulphuric acid electrolyte has been examined as a function of the immersion time in the electrolyte after termination of anodising. By transmission electron microscopy and scanning electron microscopy, degradation of the porous oxide film was qualitatively observed on AA2024. Electrochemical impedance spectroscopy revealed that AA2024 and AA7075 were more sensitive to prolonged immersion in the anodising electrolyte compared with AA6061, due to increased barrier layer thinning rates and increased susceptibility to localized corrosion. Salt spray tests confirmed the previous, indicating decay of anticorrosion performance for AA2024 and AA7075.

Degradation of the corrosion resistance of anodic oxide films through immersion in the anodising electrolyte

International Nuclear Information System (INIS)

Garcia-Rubio, M.; Ocon, P.; Curioni, M.; Thompson, G.E.; Skeldon, P.; Lavia, A.; Garcia, I.

2010-01-01

The deterioration of AA2024, AA6061 and AA7475 anodised in an environmentally-compliant tartaric acid/sulphuric acid electrolyte has been examined as a function of the immersion time in the electrolyte after termination of anodising. By transmission electron microscopy and scanning electron microscopy, degradation of the porous oxide film was qualitatively observed on AA2024. Electrochemical impedance spectroscopy revealed that AA2024 and AA7075 were more sensitive to prolonged immersion in the anodising electrolyte compared with AA6061, due to increased barrier layer thinning rates and increased susceptibility to localized corrosion. Salt spray tests confirmed the previous, indicating decay of anticorrosion performance for AA2024 and AA7075.

Salt Separation from Uranium Deposits in Integrated Crucible

Energy Technology Data Exchange (ETDEWEB)

Kwon, S. W.; Park, K. M.; Chang, J. H.; Kim, J. G.; Park, S. B. [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

2014-05-15

The solid cathode processing is necessary to separate the salt from the cathode since the uranium deposit in a solid cathode contains electrolyte salt. A physical separation process, such as distillation separation, is more attractive than a chemical or dissolution process because physical processes generate much less secondary process. Distillation process was employed for the cathode processsing due to the advantages of minimal generation of secondary waste, compact unit process, simple and low cost equipment. The basis for vacuum distillation separation is the difference in vapor pressures between salt and uranium. A solid cathode deposit is heated in a heating region and salt vaporizes, while non-volatile uranium remains behind. It is very important to increase the throughput of the salt separation system due to the high uranium content of spent nuclear fuel and high salt fraction of uranium dendrites. The evaporation rate of the LiCl-KCl eutectic salt in vacuum distiller is not so high to come up with the generation capacity of uranium dendrites in electro-refiner. Therefore, wide evaporation area or high distillation temperature is necessary for the successful salt separation. The adhered salt in the uranium deposits was removed successfully. The salt content in the deposits was below 0.1 wt% after the sequential operation of the liquid salt separation - salt distillation.

Effect of electrolyte temperature on the formation of self-organized anodic niobium oxide microcones in hot phosphate-glycerol electrolyte

Energy Technology Data Exchange (ETDEWEB)

Yang, S.; Aoki, Y. [Division of Materials Chemistry, Faculty of Engineering, Hokkaido University, Sapporo 060-8628 (Japan); Habazaki, H., E-mail: habazaki@eng.hokudai.ac.jp [Division of Materials Chemistry, Faculty of Engineering, Hokkaido University, Sapporo 060-8628 (Japan)

2011-07-15

Nanoporous niobium oxide films with microcone-type surface morphology were formed by anodizing at 10 V in glycerol electrolyte containing 0.6 mol dm{sup -3} K{sub 2}HPO{sub 4} and 0.2 mol dm{sup -3} K{sub 3}PO{sub 4} in a temperature range of 428-453 K. The microcones appeared after prolonged anodizing, but the required time was largely reduced by increasing electrolyte temperature. The anodic oxide was initially amorphous at all temperatures, but crystalline oxide nucleated during anodizing. The anodic oxide microcones, which were crystalline, appeared on surface as a consequence of preferential chemical dissolution of initially formed amorphous oxide. The chemical dissolution of an initially formed amorphous layer was accelerated by increasing the electrolyte temperature, with negligible influence of the temperature on the morphology of microcones up to 448 K.

Active Mechanism of the Interphase Film-Forming Process for an Electrolyte Based on a Sulfolane Solvent and a Chelato-Borate Complexe.

Science.gov (United States)

Li, Chunlei; Wang, Peng; Li, Shiyou; Zhao, Dongni; Zhao, Qiuping; Liu, Haining; Cui, Xiao-Ling

2018-06-14

Electrolytes based on sulfolane (SL) solvents and lithium bis(oxalato)borate (LiBOB) chelato-borate complexes have been reported many times for use in advanced lithium-ion batteries due to their many advantages. This study aims to clarify the active mechanism of the interphase film-forming process to optimize the properties of these batteries by experimental analysis and theoretical calculations. The results indicate that the self-repairing film-forming process during the first cycle is divided into three stages: the initial film formation with an electric field force of ~1.80 V, the further growth of the preformation solid electrolyte interface (SEI) film at ~1.73 V, and the final formation of a complete SEI film at a potential below 0.7 V. Additionally, we can deduce that the decomposition of LiBOB and SL occurs throughout nearly the entire process of the formation of the SEI film. The decomposition product of BOB- anions tends to form films with an irregular structure, while the decomposition product of SL is in favor of the formation of a uniform SEI film.

Solid-state electric double layer capacitors fabricated with plastic crystal based flexible gel polymer electrolytes: Effective role of electrolyte anions

International Nuclear Information System (INIS)

Suleman, Mohd; Kumar, Yogesh; Hashmi, S.A.

2015-01-01

Flexible gel polymer electrolyte (GPE) thick films incorporated with solutions of lithium trifluoromethanesulfonate (Li-triflate or LiTf) and lithium bis trifluoromethane-sulfonimide (LiTFSI) in a plastic crystal succinonitrile (SN), entrapped in poly(vinylidine fluoride-co-hexafluoropropylene) (PVdF-HFP) have been prepared and characterized. The films have been used as electrolytes in the electrical double layer capacitors (EDLCs). Coconut-shell derived activated carbon with high specific surface area (∼2100 m 2 g −1 ) and mixed (micro- and meso-) porosity has been used as EDLC electrodes. The structural, thermal, and electrochemical characterization of the GPEs have been performed using scanning electron microscopy (SEM), X-ray diffraction (XRD), differential scanning calorimetry (DSC), impedance measurements and cyclic voltammetry. The high ionic conductivity (∼10 −3 S cm −1 at 25 °C), good electrochemical stability window (>4.0 V) and flexible nature of the free-standing films of GPEs show their competence in the fabrication of EDLCs. The EDLCs have been tested using electrochemical impedance spectroscopy, cyclic voltammetry, and charge–discharge studies. The EDLCs using LiTf based electrolyte have been found to give higher values of specific capacitance, specific energy, power density (240–280 F g −1 , ∼39 Wh kg −1 and ∼19 kW kg −1 , respectively) than the EDLC cell with LiTFSI based gel electrolyte. EDLCs have been found to show stable performance for ∼10 4 charge–discharge cycles. The comparative studies indicate the effective role of electrolyte anions on the capacitive performance of the solid-state EDLCs. - Graphical abstract: Display Omitted - Highlights: • Flexible EDLCs with succinonitrile based gel electrolyte membranes are reported. • Anionic size of salts in gel electrolytes plays important role on capacitive performance. • Li-triflate incorporated gel electrolyte shows better performance over LiTFSI-based gel. �

Solid-state electric double layer capacitors fabricated with plastic crystal based flexible gel polymer electrolytes: Effective role of electrolyte anions

Energy Technology Data Exchange (ETDEWEB)

Suleman, Mohd; Kumar, Yogesh; Hashmi, S.A., E-mail: sahashmi@physics.du.ac.in

2015-08-01

Flexible gel polymer electrolyte (GPE) thick films incorporated with solutions of lithium trifluoromethanesulfonate (Li-triflate or LiTf) and lithium bis trifluoromethane-sulfonimide (LiTFSI) in a plastic crystal succinonitrile (SN), entrapped in poly(vinylidine fluoride-co-hexafluoropropylene) (PVdF-HFP) have been prepared and characterized. The films have been used as electrolytes in the electrical double layer capacitors (EDLCs). Coconut-shell derived activated carbon with high specific surface area (∼2100 m{sup 2} g{sup −1}) and mixed (micro- and meso-) porosity has been used as EDLC electrodes. The structural, thermal, and electrochemical characterization of the GPEs have been performed using scanning electron microscopy (SEM), X-ray diffraction (XRD), differential scanning calorimetry (DSC), impedance measurements and cyclic voltammetry. The high ionic conductivity (∼10{sup −3} S cm{sup −1} at 25 °C), good electrochemical stability window (>4.0 V) and flexible nature of the free-standing films of GPEs show their competence in the fabrication of EDLCs. The EDLCs have been tested using electrochemical impedance spectroscopy, cyclic voltammetry, and charge–discharge studies. The EDLCs using LiTf based electrolyte have been found to give higher values of specific capacitance, specific energy, power density (240–280 F g{sup −1}, ∼39 Wh kg{sup −1} and ∼19 kW kg{sup −1}, respectively) than the EDLC cell with LiTFSI based gel electrolyte. EDLCs have been found to show stable performance for ∼10{sup 4} charge–discharge cycles. The comparative studies indicate the effective role of electrolyte anions on the capacitive performance of the solid-state EDLCs. - Graphical abstract: Display Omitted - Highlights: • Flexible EDLCs with succinonitrile based gel electrolyte membranes are reported. • Anionic size of salts in gel electrolytes plays important role on capacitive performance. • Li-triflate incorporated gel electrolyte shows better

How do salt withdrawal minibasins form? Insights from forward modelling, and implications for hydrocarbon migration

Science.gov (United States)

Peel, Frank J.

2014-09-01

Existing models for the initiation of salt withdrawal minibasins focus on the role of triggers that exist within the minibasin, either stratigraphic (e.g. differential deposition) or tectonic (extension, translation or contraction). Existing studies tend to focus on complex settings, such as continental margins, which contain many different potential triggering mechanisms. It can be difficult in these settings to identify which process is responsible for minibasin initiation, or the influence of individual factors on their subsequent development. Salt withdrawal minibasins also exist in simpler settings, without any obvious intrinsic trigger; the region of the North German Basin used by Trusheim (1960) in the classic definition of salt withdrawal geometries was of this nature. There is no overall basal or surface slope, no major lateral movement, and there is no depositional heterogeneity. Previously recognized trigger processes for minibasin initiation do not apply in this benign setting, suggesting that other, potentially more fundamental, influences may be at work. A simple forward-modelling approach shows how, in the absence of any other mechanism, a new minibasin can develop as the consequence of salt movement driven by its neighbour, and families of withdrawal minibasins can propagate across a region from a single seed point. This new mechanism may explain how some minibasins appear to initiate before the sediment density has exceeded that of the underlying salt. The forward modelling also indicates that some minibasins begin to invert to form turtle anticlines before the underlying salt has been evacuated, so that the timing of turtle formation may not be diagnostic of weld formation. This mechanism may also give rise to salt-cored turtles that have a lens of salt trapped beneath their cores. These new findings have implications for hydrocarbon migration and trapping.

Development of an Electrolyte CPA Equation of state for Applications in the Petroleum and Chemical Industries

DEFF Research Database (Denmark)

Maribo-Mogensen, Bjørn

to the CPA EoS in the absence of electrolytes, making it possible to extend the applicability of the CPA EoS while retaining backwards compatibility and resuing the parameters for non-electrolyte systems . There are many challenges related to thermodynamic modeling of mixtures containing electrolytes......This thesis extends the Cubic Plus Association (CPA) equation of state (EoS) to handle mixtures containing ions from fully dissociated salts. The CPA EoS has during the past 18 years been applied to thermodynamic modeling of a wide range of industrially important chemicals, mainly in relation...... rarely been applied to all types of thermodynamic equilibrium calculations relevant to electrolyte solutions. This project has aimed to determine the best recipe to deliver a complete thermodynamic model capable of handling electrolytes in mixed solvents and at a wide range of temperature and pressure...

Nitric oxide mitigates salt stress by regulating levels of osmolytes and antioxidant enzymes in chickpea

Directory of Open Access Journals (Sweden)

Parvaiz eAhmad

2016-03-01

Full Text Available This work was designed to evaluate whether external application of nitric oxide (NO in the form of its donor S-nitroso-N-acetylpenicillamine (SNAP could mitigate the deleterious effects of NaCl stress on chickpea (Cicer arietinum L. plants. SNAP (50 μM was applied to chickpea plants grown under non-saline and saline conditions (50 and 100 mM NaCl. Salt stress negatively affected growth and biomass yield, leaf relative water content (LRWC and chlorophyll content of chickpea plants. High salinity increased electrolyte leakage, carotenoid content and the levels of osmolytes (proline, glycine betaine, soluble proteins and soluble sugars, hydrogen peroxide (H2O2 and malondialdehyde (MDA, as well as the activities of antioxidant enzymes, such as superoxide dismutase (SOD, catalase (CAT, ascorbate peroxidase (APX, and glutathione reductase (GR in chickpea plants. Expression of the representative SOD, CAT and APX genes examined was also up-regulated in chickpea plants by salt stress. On the other hand, exogenous application of NO to salinized plants enhanced the growth parameters, LRWC, photosynthetic pigment production and levels of osmolytes, as well as the activities of examined antioxidant enzymes which is correlated with up-regulation of the examined SOD, CAT and APX genes, in comparison with plants treated with NaCl only. Furthermore, electrolyte leakage, H2O2 and MDA contents showed decline in salt-stressed plants supplemented with NO as compared with those in NaCl-treated plants alone. Thus, the exogenous application of NO protected chickpea plants against salt-induced oxidative damage by enhancing the biosynthesis of antioxidant enzymes, thereby improving plant growth under saline stress. Taken together, our results demonstrate that NO has capability to mitigate the adverse effects of high salinity on chickpea plants by improving LRWC, photosynthetic pigment biosyntheses, osmolyte accumulation and antioxidative defense system.

Formation of Reversible Solid Electrolyte Interface on Graphite Surface from Concentrated Electrolytes

Energy Technology Data Exchange (ETDEWEB)

Lu, Dongping; Tao, Jinhui; Yan, Pengfei; Henderson, Wesley A.; Li, Qiuyan; Shao, Yuyan; Helm, Monte L.; Borodin, Oleg; Graff, Gordon L.; Polzin, Bryant; Wang, Chong-Min; Engelhard, Mark; Zhang, Ji-Guang; De Yoreo, James J.; Liu, Jun; Xiao, Jie

2017-02-10

Interfacial phenomena have always been key determinants for the performance of energy storage technologies. The solid electrolyte interfacial (SEI) layer, pervasive on the surfaces of battery electrodes for numerous chemical couples, directly affects the ion transport, charge transfer and lifespan of the entire energy system. Almost all SEI layers, however, are unstable resulting in the continuous consumption of the electrolyte. Typically, this leads to the accumulation of degradation products on/restructuring of the electrode surface and thus increased cell impedance, which largely limits the long-term operation of the electrochemical reactions. Herein, a completely new SEI formation mechanism has been discovered, in which the electrolyte components reversibly self-assemble into a protective surface coating on a graphite electrode upon changing the potential. In contrast to the established wisdom regarding the necessity of employing the solvent ethylene carbonate (EC) to form a protective SEI layer on graphite, a wide range of EC-free electrolytes are demonstrated for the reversible intercalation/deintercalation of Li+ cations within a graphite lattice, thereby providing tremendous flexibility in electrolyte tailoring for battery couples. This novel finding is broadly applicable and provides guidance for how to control interfacial reactions through the relationship between ion aggregation and solvent decomposition at polarized interfaces.

Electrochemical Model for Ionic Liquid Electrolytes in Lithium Batteries

International Nuclear Information System (INIS)

Yoo, Kisoo; Deshpande, Anirudh; Banerjee, Soumik; Dutta, Prashanta

2015-01-01

ABSTRACT: Room temperature ionic liquids are considered as potential electrolytes for high performance and safe lithium batteries due to their very low vapor pressure and relatively wide electrochemical and thermal stability windows. Unlike organic electrolytes, ionic liquid electrolytes are molten salts at room temperature with dissociated cations and anions. These dissociated ions interfere with the transport of lithium ions in lithium battery. In this study, a mathematical model is developed for transport of ionic components to study the performance of ionic liquid based lithium batteries. The mathematical model is based on a univalent ternary electrolyte frequently encountered in ionic liquid electrolytes of lithium batteries. Owing to the very high concentration of components in ionic liquid, the transport of lithium ions is described by the mutual diffusion phenomena using Maxwell-Stefan diffusivities, which are obtained from atomistic simulation. The model is employed to study a lithium-ion battery where the electrolyte comprises ionic liquid with mppy + (N-methyl-N-propyl pyrrolidinium) cation and TFSI − (bis trifluoromethanesulfonyl imide) anion. For a moderate value of reaction rate constant, the electric performance results predicted by the model are in good agreement with experimental data. We also studied the effect of porosity and thickness of separator on the performance of lithium-ion battery using this model. Numerical results indicate that low rate of lithium ion transport causes lithium depleted zone in the porous cathode regions as the porosity decreases or the length of the separator increases. The lithium depleted region is responsible for lower specific capacity in lithium-ion cells. The model presented in this study can be used for design of optimal ionic liquid electrolytes for lithium-ion and lithium-air batteries

Based on the Theory of TRIZ Solving the Problem of 18650 Battery Electrolyte Filling

Science.gov (United States)

Shao-hua, Cui; Jiang-ping, Mei; Ling-hua, Zhang; Xiao, Du

2017-12-01

As a type of standardized battery cylindrical 18650 lithium-ion battery is widely used in new energy vehicle industry, It can be produced in large quantities without changing type. Because of its special advantages than others. But due to the pressure of rising capacity, electrolyte filling (which is short for E/L) process has become more and more difficult. While reducing the production efficiency eases the problem of E/L, it also poses performance and security problems. So the issue cannot be solved using the common knowledge of the industry. In this paper, This article does not use lean manufacturing or 6Sigma methods, we use TRIZ theory to analyze the E/L difficulty problem in detail (using causal analysis, technical contradiction analysis, substance - field analysis, physical contradiction analysis and other tools). By creating an atmosphere of vacuum and pressure replace the existing E/L tooling for single cell mechanical structure, through blowing hot air method to increase the temperature of electrolyte, Dissolving the J/R into a electrolyte tank which is full of 0.3Mpa nitrogen. Under the premise of not reducing the production efficiency, at the same time ensuring performance and safety, we try to find out a method to solve the E/L difficulty problem, and would get better application in the construction of new production lines in the new factory.

Kinetics Tuning the Electrochemistry of Lithium Dendrites Formation in Lithium Batteries through Electrolytes

International Nuclear Information System (INIS)

Tao, Ran; Bi, Xuanxuan; The Ohio State University, Columbus, OH; Li, Shu; Yao, Ying

2017-01-01

Lithium batteries are one of the most advance energy storage devices in the world and have attracted extensive research interests. However, lithium dendrite growth was a safety issue which handicapped the application of pure lithium metal in the negative electrode. In this paper, two solvents, propylene carbonate (PC) and 2-methyl-tetrahydrofuran (2MeTHF), and four Li"+ salts, LiPF_6, LiAsF_6, LiBF_4 and LiClO_4 were investigated in terms of their effects on the kinetics of lithium dendrite formation in eight electrolyte solutions. The kinetic parameters of charge transfer step (exchange current density, j_0, transfer coefficient, α) of Li"+/Li redox system, the mass transfer parameters of Li"+ (transfer number of Li"+, t_L_i_+, diffusion coefficient of Li"+, D_L_i_+), and the conductivity (κ) of each electrolyte were studied separately. The results demonstrate that the solvents play a critical role in the measured j_0, t_L_i_+, D_L_i_+, and κ of the electrolyte, while the choice of Li"+ salts only slightly affect the measured parameters. Finally, the understanding of the kinetics will gain insight into the mechanism of lithium dendrite formation and provide guidelines to the future application of lithium metal.

Characterization of coatings formed on AZX magnesium alloys by plasma electrolytic oxidation

Science.gov (United States)

Anawati, Anawati; Gumelar, Muhammad Dikdik

2018-05-01

Plasma Electrolytic Oxidation (PEO) is an electrochemical anodization process which involves the application of a high voltage to create intense plasma on a metal surface to form a ceramic type of oxide. The resulted coating exhibits high wear resistance and good corrosion barrier which are suitable to enhance the performance of biodegradable Mg alloys. In this work, the role of alloying element Ca in modifying the characteristics of PEO layer formed on AZ61 series magnesium alloys was investigated. PEO treatment was conducted on AZ61, AZX611, and AZX612 alloys in 0.5 M Na3PO4 solution at a constant current of 200 A/m2 at 25°C for 8 min. The resulted coatings were characterized by field emission-scanning electron microscope (FESEM), X-ray diffraction spectroscopy (XRD), and X-ray fluorescence spectroscopy (XRF), as well as hardness test. The presence of alloying element Ca in the AZ61 alloys accelerated the PEO coatings formation without altering the coating properties significantly. The coating formed on AZX specimen was slightly thicker ( 14-17 µm) than that of formed onthe AZ specimens ( 13 µm). Longer exposure time to plasma discharge was the reason for faster thickening of the coating layer on AZX specimen. XRD detected a similar crystalline oxide phase of Mg3(PO4)2 in the oxide formed on all of the specimens. Zn was highly incorporated in the coatings with a concentration in the range 24-30 wt%, as analyzed by XRF. Zn compound might exist in amorphous phases. The microhardness test on the coatings revealed similar average hardness 124 HVon all of the specimens.

Comparison of starch and gelatin hydrogels for non-toxic supercapacitor electrolytes

Science.gov (United States)

Railanmaa, Anna; Lehtimäki, Suvi; Lupo, Donald

2017-06-01

Starch and gelatin are two of the most abundantly available natural polymers. Their non-toxicity, low cost, and compatibility with aqueous solvents make them ideal for use in ubiquitous, environmentally friendly electronics systems. This work presents the results of conductivity measurements through impedance spectroscopy for gelatin- and starch-based aqueous gel electrolytes. The NaCl-based gels were physically cross-linked. The conductivity values were 84.6 mS/cm at 1.5 mol L-1 and 71.5 mS/cm at 2 mol L-1 for gelatin and starch, respectively. The mechanical properties of gelatin were found preferable to those of starch, although they deteriorated significantly when the salt concentration exceeded 2 mol L-1. The ability of the gels to successfully act as a supercapacitor electrolyte was demonstrated with printed electrodes on plastic substrate. The devices were characterized through cyclic voltammetry measurements. The results imply that these polymer gel electrolytes are very promising for replacing the traditional aqueous liquid electrolytes in supercapacitors in applications where, for example, user and environmental safety is essential.

Presence and Impact of Surface Films formed on Mg in Chloroaluminate Electrolytes.

Energy Technology Data Exchange (ETDEWEB)

Hahn, Nathan [Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Kotula, Paul G. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Wetzel, David J. [Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Univ. of Illinois, Urbana-Champaign, IL (United States); Malone, Marvin A. [Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Univ. of Illinois, Urbana-Champaign, IL (United States); Nuzzo, Ralph G. [Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Univ. of Illinois, Urbana-Champaign, IL (United States); Zavadil, Kevin R. [Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

2015-09-01

The impact of surface film formation on Mg is explored during electrodeposition and electrodissolution in two high activity, aprotic electrolytes: the all phenyl complex (APC) and the magnesium aluminum chloride complex (MACC). Where past studies have argued such films are benign, results show that interfacial films are responsible for controlling the Mg deposit structure when deposition and dissolution are conducted at the rates required for practical Mg batteries. Chronopotentiometry is shown to provide clear signatures of the impact of interfacial films on deposition and dissolution. The particular combination of cycling punctuated by periods of open circuit equilibration is shown to yield a noticeable decrease in coulombic efficiency over a 50 cycle sequence. High resolution electron imaging shows that cycling results in porosity development and accumulation of electrolyte constituents within the deposit. Reduced coulombic efficiency signaling Mg loss appears related to progressive isolation of a fraction of the deposit. Mg and electrolyte loss must be compensated for in a practical cell through the introduction of excess inventory and resulting in a reduced energy density of the system.

Salt Induced Decay of Masonry and Electrokinetic Repair

DEFF Research Database (Denmark)

Ottosen, Lisbeth M.; Rörig-Dalgaard, Inge

in brick depending on its water content and salts may be precipitated on the outer wall or concentrated under paint layers covering the surface of the brick. Different types of damage may appear in masonry walls due to these concentrating phenomena. Bricks themselves can be destroyed and the mortar can...... of bricks without increased salt content is very low compared to soils in general. Furthermore in a masonry wall there are boundaries with different chemistry (e.g. pH) that the ions must pass, brick-mortar boundaries. From initial experiments with electrokinetic removal of Ca2+ ions from bricks good......Salt induced decay of bricks is caused when salts exert internal pressures, which exceed the strength of the stone. The presence of aqueous electrolyte solutions in the capillary pores of brick materials can under changing climate conditions cause deterioration of wall structures. Ions move...

Corrosion Behavior of a Surface Modified Inconel 713LC in a Hot Lithium Molten Salt

International Nuclear Information System (INIS)

Cho, Soo Haeng; Lim, Jong Ho; Seo, Chung Seok; Jung, Ki Jung; Park, Seoung Won

2005-01-01

The Li-reduction process involves the chemical reduction of spent fuel oxides by liquid lithium metal in a molten LiCl salt bath at 650 .deg. C followed by a separate electrochemical reduction of the lithium oxide (Li 2 O), which builds up in the salt bath. This process requires a high purity inert gas atmosphere inside a remote hot cell nuclear facility to prevent an unwanted Li oxidation and fires during the handling of the chemically active Li metal. In light of the limitations of the Li-reduction process, a direct electrolytic reduction technology is being developed by KAERI to enhance the process safety and economic viability. The electrolytic reduction of spent oxide fuel involves the liberation of the oxygen in a molten LiCl electrolyte, which results in a chemically aggressive environment that is too corrosive for typical structural materials. Even so, the electrochemical process vessel must be resilient at 650 .deg. C in the presence of oxygen to enable high processing rates and an extended service life. But, the mechanism and the rate of the corrosion of the metals in a LiCl-Li 2 O molten salt under an oxidation condition are not clear. In the present work, the corrosion behavior and corrosion mechanism of a surface modified Inconel 713LC have been studied in the molten salt of LiCl-Li 2 O under an oxidation condition

Ion-conductive properties of polyether-based composite electrolytes filled with mesoporous silica, alumina and titania

International Nuclear Information System (INIS)

Tominaga, Yoichi; Endo, Masanori

2013-01-01

Composite polymer electrolytes were prepared consisting of amorphous polyether, Li salt and mesoporous inorganic filler, and we investigated their ion-conductive properties. We synthesized three types of filler, mesoporous silica, alumina and titania (MP-Si, Al, Ti), and characterized their structural and physicochemical properties using SEM, TEM, SAXS and BET surface area measurements. From these measurements, we confirmed that MP fillers have well-defined arrays of mesoporous and hexagonal structures. Dependence on the MP filler content of the glass transition temperature (T g ) revealed that the addition of filler to original polyether-salt electrolyte causes T g decrease, to due to the dissociation of aggregated ions such as triples or crystalline complex domains. The MP-Ti composites had the greatest ionic conductivity (1.4 × 10 −5 S/cm, 7.5 wt% at 30 °C) of all samples, and the values were more than double that of the original. The addition of MP-Ti also increased the lithium transference number, because the electrolyte/filler interface provided active sites that increase mobile Li ions and conducting paths so as to enhance the mobility

Phosphorus Enrichment as a New Composition in the Solid Electrolyte Interphase of High-Voltage Cathodes and Its Effects on Battery Cycling

Energy Technology Data Exchange (ETDEWEB)

Yan, Pengfei; Zheng, Jianming; Kuppan, Saravanan; Li, Qiuyan; Lv, Dongping; Xiao, Jie; Chen, Guoying; Zhang, Jiguang; Wang, Chong M.

2015-11-10

Immersion of a solid into liquid often leads to the modification of both the structure and chemistry of surface of the solid, which subsequently affects the chemical and physical properties of the system. For the case of the rechargeable lithium ion battery, such a surface modification is termed as solid electrolyte interphase (SEI) layer, which has been perceived to play critical role for the stable operation of the batteries. However, the structure and chemical composition of SEI layer and its spatial distribution and dependence on the battery operating condition remain unclear. By using aberration corrected scanning transmission electron microscopy coupled with ultra-high sensitive energy dispersive x-ray spectroscopy, we probed the structure and chemistry of SEI layer on several high voltage cathodes. We show that layer-structured cathodes, when cycled at a high cut off voltage, can form a P-rich SEI layer on their surface, which is a direct evidence of Li-salt (LiPF6) decomposition. Our systematical investigations indicate such cathode/Li-salt side reaction shows strong dependence on structure of the cathode materials, operating voltage and temperature, indicating the feasibility of SEI engineering. These findings provide us valuable insights into the complex interface between the high-voltage cathode and the electrolyte.

Fused salt electrolysis

International Nuclear Information System (INIS)

Ares, Osvaldo; Botbol, Jose.

1989-01-01

Working conditions for zirconium preparation by fused salt electrolysis were studied. For such purpose, a cell was built for operation under argon atmosphere. A graphite crucible served as anode, with steel cathodes. Proper design allowed cathode rechange under the inert atmosphere. Cathodic deposits of zirconium powder occluded salts from the bath. After washing with both water and hydrochloric acid, the metallic powder was consolidated by fusion. Optimum operating conditions were found to arise from an electrolyte of 12% potassium hexafluorzirconate -88% sodium chloride, at 820 deg C and 5 A/cm 2 cathodic current density. Deposits contained 35% of metal and current efficiency reached 66%. The powder contained up to 600 ppm of chlorine and 1.700 ppm of fluorine; after fusion, those amounts decreased to 2 ppm and 3 ppm respectively, with low proportion of metallic impurities. Though oxygen proportion was 4.500 ppm, it should be lowered by improving working conditions, as well as working on an ampler scale. (Author)

Nanostructured Electrolytes for Stable Lithium Electrodeposition in Secondary Batteries

KAUST Repository

Tu, Zhengyuan

2015-11-17

of ceramic electrolytes that meet the modulus and stability requirements have to date proven to be insurmountable obstacles to progress. In this Account, we first review recent advances in continuum theory for dendrite growth and proliferation during metal electrodeposition. We show that the range of options for designing electrolytes and separators that stabilize electrodeposition is now substantially broader than one might imagine from previous literature accounts. In particular, separators designed at the nanoscale to constrain ion transport on length scales below a theory-defined cutoff, and structured electrolytes in which a fraction of anions are permanently immobilized to nanoparticles, to a polymer network or ceramic membrane are considered particularly promising for their ability to stabilize electrodeposition of lithium metal without compromising ionic conductivity or room temperature battery operation. We also review recent progress in designing surface passivation films for metallic lithium that facilitate fast deposition of lithium at the electrolyte/electrode interface and at the same time protect the lithium from parasitic side reactions with liquid electrolytes. A promising finding from both theory and experiment is that simple film-forming halide salt additives in a conventional liquid electrolyte can substantially extend the lifetime and safety of LMBs.