Electrode-electrolyte BIMEVOX system for moderate temperature oxygen separation

Energy Technology Data Exchange (ETDEWEB)

Boivin, J.C.; Pirovano, C.; Nowogrocki, G.; Mairesse, G. [Laboratoire de Cristallochimie et Physicochimie du Solide, URA CNRS 452, USTL-ENSCL BP 108, 59652 Villeneuve d`Ascq (France); Labrune, Ph.; Lagrange, G. [Centre de recherches Claude Delorme, Air Liquide, Jouy en Josas (France)

1998-12-01

Electrochemical separation of oxygen from air is a promising application for oxide conductor solid electrolytes. However, several important specifications are required in order to obtain an efficient separation device. First of all, the electrolyte material must exhibit a high conductivity at moderate temperature. From this point of view, a new family of materials called BIMEVOX ideally fulfils this condition. Secondly, a typical separation device must comport two electrodes on opposite faces of the electrolyte. These electrodes must act as electronic collectors but also, at the cathodic side, as an oxygen dissociation catalyst. BIMEVOX electrolytes exhibit ionic conductivity values that can allow work at temperature below 500C. The classical electrode approach, like in solid oxide fuel cells, consists in using a specific mixed oxide, for instance strontium lanthanum manganite or cobaltite. However, the lower the temperature, the lower the efficiency of these electrodes which quickly appears as the limiting factor. In previous work on bismuth lead oxide electrolytes, we proposed a new approach that consists of using the surface of the bismuth-based electrolyte itself as the catalyst, the electron collection being then performed by a co-sintered metallic grid. This `in-situ` electrode system provides many advantages, particularly it eliminates the problem of the chemical compatibility between electrode and electrolyte materials. Taking into account the presence of both catalytic vanadium and bismuth cations in BIMEVOX, we checked under these conditions the separation of oxygen from air for different electrolytes (BICOVOX, BICUVOX, BIZNVOX) at various temperatures in the range 430-600C. For instance, using a BICOVOX pellet with a gold grid inserted on each side makes it possible to separate oxygen with nearly 100% efficiency for current density values up to 1000 mA/cm{sup -2}. For higher intensity values, the faradic efficiency progressively but reversibly decreases

Nafion/silane nanocomposite membranes for high temperature polymer electrolyte membrane fuel cell.

Science.gov (United States)

Ghi, Lee Jin; Park, Na Ri; Kim, Moon Sung; Rhee, Hee Woo

2011-07-01

The polymer electrolyte membrane fuel cell (PEMFC) has been studied actively for both potable and stationary applications because it can offer high power density and be used only hydrogen and oxygen as environment-friendly fuels. Nafion which is widely used has mechanical and chemical stabilities as well as high conductivity. However, there is a drawback that it can be useless at high temperatures (> or = 90 degrees C) because proton conducting mechanism cannot work above 100 degrees C due to dehydration of membrane. Therefore, PEMFC should be operated for long-term at high temperatures continuously. In this study, we developed nanocomposite membrane using stable properties of Nafion and phosphonic acid groups which made proton conducting mechanism without water. 3-Aminopropyl triethoxysilane (APTES) was used to replace sulfonic acid groups of Nafion and then its aminopropyl group was chemically modified to phosphonic acid groups. The nanocomposite membrane showed very high conductivity (approximately 0.02 S/cm at 110 degrees C, <30% RH).

Polybenzimidazole and sulfonated polyhedral oligosilsesquioxane composite membranes for high temperature polymer electrolyte membrane fuel cells

DEFF Research Database (Denmark)

Aili, David; Allward, Todd; Alfaro, Silvia Martinez

2014-01-01

Composite membranes based on poly(2,2′(m-phenylene)-5,5́bibenzimidazole) (PBI) and sulfonated polyhedral oligosilsesquioxane (S-POSS) with S-POSS contents of 5 and 10wt.% were prepared by solution casting as base materials for high temperature polymer electrolyte membrane fuel cells. With membranes...

A new modified-serpentine flow field for application in high temperature polymer electrolyte fuel cell

DEFF Research Database (Denmark)

Singdeo, Debanand; Dey, Tapobrata; Gaikwad, Shrihari

2017-01-01

field design is proposed and its usefulness for the fuel cell applications are evaluated in a high-temperature polymer electrolyte fuel cell. The proposed geometry retains some of the features of serpentine flow field such as multiple bends, while modifications are made in its in-plane flow path...

Gel polymer electrolyte lithium-ion cells with improved low temperature performance

Energy Technology Data Exchange (ETDEWEB)

Smart, M.C.; Ratnakumar, B.V.; Behar, A.; Whitcanack, L.D. [Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Drive, Pasadena, CA 91109 (United States); Yu, J.-S. [LG Chem/Research Park, P.O. Box 61Yu Song, Science Town, Daejon (Korea); Alamgir, M. [Compact Power, Inc., 1857 Technology Drive, Troy, MI 48083 (United States)

2007-03-20

For a number of NASA's future planetary and terrestrial applications, high energy density rechargeable lithium batteries that can operate at very low temperature are desired. In the pursuit of developing Li-ion batteries with improved low temperature performance, we have also focused on assessing the viability of using gel polymer systems, due to their desirable form factor and enhanced safety characteristics. In the present study we have evaluated three classes of promising liquid low-temperature electrolytes that have been impregnated into gel polymer electrolyte carbon-LiMn{sub 2}O{sub 4}-based Li-ion cells (manufactured by LG Chem. Inc.), consisting of: (a) binary EC + EMC mixtures with very low EC-content (10%), (b) quaternary carbonate mixtures with low EC-content (16-20%), and (c) ternary electrolytes with very low EC-content (10%) and high proportions of ester co-solvents (i.e., 80%). These electrolytes have been compared with a baseline formulation (i.e., 1.0 M LiPF{sub 6} in EC + DEC + DMC (1:1:1%, v/v/v), where EC, ethylene carbonate, DEC, diethyl carbonate, and DMC, dimethyl carbonate). We have performed a number of characterization tests on these cells, including: determining the rate capacity as a function of temperature (with preceding charge at room temperature and also at low temperature), the cycle life performance (both 100% DOD and 30% DOD low earth orbit cycling), the pulse capability, and the impedance characteristics at different temperatures. We have obtained excellent performance at low temperatures with ester-based electrolytes, including the demonstration of >80% of the room temperature capacity at -60 C using a C/20 discharge rate with cells containing 1.0 M LiPF{sub 6} in EC + EMC + MB (1:1:8%, v/v/v) (MB, methyl butyrate) and 1.0 M LiPF{sub 6} in EC + EMC + EB (1:1:8%, v/v/v) (EB, ethyl butyrate) electrolytes. In addition, cells containing the ester-based electrolytes were observed to support 5C pulses at -40 C, while still

Control and experimental characterization of a methanol reformer for a 350 W high temperature polymer electrolyte membrane fuel cell system

DEFF Research Database (Denmark)

Andreasen, Søren Juhl; Kær, Søren Knudsen; Sahlin, Simon Lennart

2013-01-01

is the water and methanol mixture fuel flow and the burner fuel/air ratio and combined flow. An experimental setup is presented capable of testing the methanol reformer used in the Serenergy H3 350 Mobile Battery Charger; a high temperature polymer electrolyte membrane (HTPEM) fuel cell system......This work presents a control strategy for controlling the methanol reformer temperature of a 350 W high temperature polymer electrolyte membrane fuel cell system, by using a cascade control structure for reliable system operation. The primary states affecting the methanol catalyst bed temperature....... The experimental system consists of a fuel evaporator utilizing the high temperature waste gas from the cathode air cooled 45 cell HTPEM fuel cell stack. The fuel cells used are BASF P1000 MEAs which use phosphoric acid doped polybenzimidazole membranes. The resulting reformate gas output of the reformer system...

Self-propagating high-temperature synthesis of La(Sr)Ga(Mg)O3-δ for electrolyte of solid oxide fuel cells

International Nuclear Information System (INIS)

Ishikawa, Hiroyuki; Enoki, Makiko; Ishihara, Tatsumi; Akiyama, Tomohiro

2007-01-01

This paper describes self-propagating high-temperature synthesis (SHS) of an electrolyte for solid oxide fuel (SOFC), in comparison to a conventional solid-state reaction method (SRM). Doped-lanthanum gallate: La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3-δ (LSGM9182) and LSGM9173 as the SOFC electrolyte, was prepared by the SHS and sintered at different temperatures, for measuring the electrical conductivity of the sintered LSGM and the power generating performance at 1073 K, in comparison to the SRM. In the SHS, the LSGM powders with smaller size were obtained and easily sintered at the 100 K-lower temperature, 1673 K, than in the SRM. Most significantly, the electrical conductivity of the sintered LSGM9182 was as high as 0.11 S cm -1 and its maximum power density was a value of 245 mW cm -2 in the cell configuration of Ni/LSGM9182 (0.501 mm in thickness)/Sm 0.5 Sr 0.5 CoO 3 . The conclusion was that the proposed SHS-sintering method with many benefits of minimizing the energy requirement and the processing time in the production, easing temperature restriction for the sintering, and improving the electrolyte performance up to a conventional level is practicable for producing the LSGM-electrolyte of SOFC at an intermediate-temperature application

Influence of temperature and electrolyte on the performance of activated-carbon supercapacitors

Science.gov (United States)

Liu, Ping; Verbrugge, Mark; Soukiazian, Souren

For hybrid electric vehicle traction applications, energy storage devices with high power density and energy efficiency are required. A primary attribute of supercapacitors is that they retain their high power density and energy efficiency even at -30 °C, the lowest temperature at which unassisted starting must be provided to customers. More abuse-tolerant electrolytes are preferred to the high-conductivity acetonitrile-based systems commonly employed. Propylene carbonate based electrolytes are a promising alternative. In this work, we compare the electrochemical performance of two high-power density electrical double layer supercapacitors employing acetonitrile and propylene carbonate as solvents. From this study, we are able to elucidate phenomena that control the resistance of supercapacitor at lower temperatures, and quantify the difference in performance associated with the two electrolytes.

About the Compatibility between High Voltage Spinel Cathode Materials and Solid Oxide Electrolytes as a Function of Temperature.

Science.gov (United States)

Miara, Lincoln; Windmüller, Anna; Tsai, Chih-Long; Richards, William D; Ma, Qianli; Uhlenbruck, Sven; Guillon, Olivier; Ceder, Gerbrand

2016-10-12

The reactivity of mixtures of high voltage spinel cathode materials Li 2 NiMn 3 O 8 , Li 2 FeMn 3 O 8 , and LiCoMnO 4 cosintered with Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 and Li 6.6 La 3 Zr 1.6 Ta 0.4 O 12 electrolytes is studied by thermal analysis using X-ray-diffraction and differential thermoanalysis and thermogravimetry coupled with mass spectrometry. The results are compared with predicted decomposition reactions from first-principles calculations. Decomposition of the mixtures begins at 600 °C, significantly lower than the decomposition temperature of any component, especially the electrolytes. For the cathode + Li 6.6 La 3 Zr 1.6 Ta 0.4 O 12 mixtures, lithium and oxygen from the electrolyte react with the cathodes to form highly stable Li 2 MnO 3 and then decompose to form stable and often insulating phases such as La 2 Zr 2 O 7 , La 2 O 3 , La 3 TaO 7 , TiO 2 , and LaMnO 3 which are likely to increase the interfacial impedance of a cathode composite. The decomposition reactions are identified with high fidelity by first-principles calculations. For the cathode + Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 mixtures, the Mn tends to oxidize to MnO 2 or Mn 2 O 3 , supplying lithium to the electrolyte for the formation of Li 3 PO 4 and metal phosphates such as AlPO 4 and LiMPO 4 (M = Mn, Ni). The results indicate that high temperature cosintering to form dense cathode composites between spinel cathodes and oxide electrolytes will produce high impedance interfacial products, complicating solid state battery manufacturing.

Demonstration of high efficiency intermediate-temperature solid oxide fuel cell based on lanthanum gallate electrolyte

International Nuclear Information System (INIS)

Inagaki, Toru; Nishiwaki, Futoshi; Kanou, Jirou; Yamasaki, Satoru; Hosoi, Kei; Miyazawa, Takashi; Yamada, Masaharu; Komada, Norikazu

2006-01-01

The Kansai Electric Power Co., Inc. (KEPCO) and Mitsubishi Materials Corporation (MMC) have been jointly developing intermediate-temperature solid oxide fuel cells (SOFCs). The operation temperatures between 600 and 800 o C were set as the target, which enable SOFC to use less expensive metallic separators for cell-stacking and to carry out internal reforming of hydrocarbon fuels. The electrolyte-supported planar-type cells were fabricated using highly conductive lanthanum gallate-based electrolyte, La(Sr)Ga(Mg,Co)O 3-δ , Ni-(CeO 2 ) 1-x (SmO 1.5 ) x cermet anode, and Sm(Sr)CoO 3-δ cathode. The 1 kW-class power generation modules were fabricated using a seal-less stack of the cells and metallic separators. The 1 kW-class prototype power generation system with the module was developed with the high performance cell, which showed the thermally self-sustainability. The system included an SOFC module, a dc-ac inverter, a desulfurizer, and a heat recovery unit. It provided stable ac power output of 1 kW with the electrical efficiency of 45% LHV based on ac output by using city gas as a fuel, which was considered to be excellent for such a small power generation system. And the hot water of 90 o C was obtained using high temperature off-gas from SOFC

Demonstration of high efficiency intermediate-temperature solid oxide fuel cell based on lanthanum gallate electrolyte

Energy Technology Data Exchange (ETDEWEB)

Inagaki, Toru [Kansai Electric Power Co. Inc., Energy Use R and D Center, 11-20 Nakoji 3-chome, Amagasaki, Hyogo 661-0974 (Japan)]. E-mail: inagaki@rdd.kepco.co.jp; Nishiwaki, Futoshi [Kansai Electric Power Co. Inc., Energy Use R and D Center, 11-20 Nakoji 3-chome, Amagasaki, Hyogo 661-0974 (Japan); Kanou, Jirou [Kansai Electric Power Co. Inc., Energy Use R and D Center, 11-20 Nakoji 3-chome, Amagasaki, Hyogo 661-0974 (Japan); Yamasaki, Satoru [Kansai Electric Power Co. Inc., Energy Use R and D Center, 11-20 Nakoji 3-chome, Amagasaki, Hyogo 661-0974 (Japan); Hosoi, Kei [Mitsubishi Materials Corporation, Central Research Institute, 1002-14 Mukohyama, Naka-machi, Naka-gun, Ibaraki 311-0102 (Japan); Miyazawa, Takashi [Mitsubishi Materials Corporation, Central Research Institute, 1002-14 Mukohyama, Naka-machi, Naka-gun, Ibaraki 311-0102 (Japan); Yamada, Masaharu [Mitsubishi Materials Corporation, Central Research Institute, 1002-14 Mukohyama, Naka-machi, Naka-gun, Ibaraki 311-0102 (Japan); Komada, Norikazu [Mitsubishi Materials Corporation, Central Research Institute, 1002-14 Mukohyama, Naka-machi, Naka-gun, Ibaraki 311-0102 (Japan)

2006-02-09

The Kansai Electric Power Co., Inc. (KEPCO) and Mitsubishi Materials Corporation (MMC) have been jointly developing intermediate-temperature solid oxide fuel cells (SOFCs). The operation temperatures between 600 and 800 {sup o}C were set as the target, which enable SOFC to use less expensive metallic separators for cell-stacking and to carry out internal reforming of hydrocarbon fuels. The electrolyte-supported planar-type cells were fabricated using highly conductive lanthanum gallate-based electrolyte, La(Sr)Ga(Mg,Co)O{sub 3-{delta}}, Ni-(CeO{sub 2}){sub 1-x}(SmO{sub 1.5}) {sub x} cermet anode, and Sm(Sr)CoO{sub 3-{delta}} cathode. The 1 kW-class power generation modules were fabricated using a seal-less stack of the cells and metallic separators. The 1 kW-class prototype power generation system with the module was developed with the high performance cell, which showed the thermally self-sustainability. The system included an SOFC module, a dc-ac inverter, a desulfurizer, and a heat recovery unit. It provided stable ac power output of 1 kW with the electrical efficiency of 45% LHV based on ac output by using city gas as a fuel, which was considered to be excellent for such a small power generation system. And the hot water of 90 {sup o}C was obtained using high temperature off-gas from SOFC.

Self-propagating high-temperature synthesis of La(Sr)Ga(Mg)O{sub 3-{delta}} for electrolyte of solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Ishikawa, Hiroyuki [Center for Advanced Research of Energy Conversion Materials, Hokkaido University, Sapporo 060-8628 (Japan); Enoki, Makiko [Department of Applied Chemistry, Faculty of Engineering, Kyusyu University, Fukuoka 812-8581 (Japan); Ishihara, Tatsumi [Department of Applied Chemistry, Faculty of Engineering, Kyusyu University, Fukuoka 812-8581 (Japan); Akiyama, Tomohiro [Center for Advanced Research of Energy Conversion Materials, Hokkaido University, Sapporo 060-8628 (Japan)]. E-mail: takiyama@eng.hokudai.ac.jp

2007-03-14

This paper describes self-propagating high-temperature synthesis (SHS) of an electrolyte for solid oxide fuel (SOFC), in comparison to a conventional solid-state reaction method (SRM). Doped-lanthanum gallate: La{sub 0.9}Sr{sub 0.1}Ga{sub 0.8}Mg{sub 0.2}O{sub 3-{delta}} (LSGM9182) and LSGM9173 as the SOFC electrolyte, was prepared by the SHS and sintered at different temperatures, for measuring the electrical conductivity of the sintered LSGM and the power generating performance at 1073 K, in comparison to the SRM. In the SHS, the LSGM powders with smaller size were obtained and easily sintered at the 100 K-lower temperature, 1673 K, than in the SRM. Most significantly, the electrical conductivity of the sintered LSGM9182 was as high as 0.11 S cm{sup -1} and its maximum power density was a value of 245 mW cm{sup -2} in the cell configuration of Ni/LSGM9182 (0.501 mm in thickness)/Sm{sub 0.5}Sr{sub 0.5}CoO{sub 3}. The conclusion was that the proposed SHS-sintering method with many benefits of minimizing the energy requirement and the processing time in the production, easing temperature restriction for the sintering, and improving the electrolyte performance up to a conventional level is practicable for producing the LSGM-electrolyte of SOFC at an intermediate-temperature application.

Long-Term Degradation Testing of High-Temperature Electrolytic Cells

Energy Technology Data Exchange (ETDEWEB)

C.M. Stoots; J.E. O' Brien; J.S. Herring; G.K. Housley; D.G. Milobar; M.S. Sohal

2009-08-01

The Idaho National Laboratory (INL) has been researching the application of solid-oxide electrolysis cell for large-scale hydrogen production from steam over a temperature range of 800 to 900ºC. The INL has been testing various solid oxide cell designs to characterize their electrolytic performance operating in the electrolysis mode for hydrogen production. Some results presented in this report were obtained from cells, with an active area of 16 cm2 per cell. The electrolysis cells are electrode-supported, with ~10 µm thick yttria-stabilized zirconia (YSZ) electrolytes, ~1400 µm thick nickel-YSZ steam-hydrogen electrodes, and manganite (LSM) air-oxygen electrodes. The experiments were performed over a range of steam inlet mole fractions (0.1 to 0.6), gas flow rates, and current densities (0 to 0.6 A/cm2). Steam consumption rates associated with electrolysis were measured directly using inlet and outlet dewpoint instrumentation. On a molar basis, the steam consumption rate is equal to the hydrogen production rate. Cell performance was evaluated by performing DC potential sweeps at 800, 850, and 900°C. The voltage-current characteristics are presented, along with values of area-specific resistance as a function of current density. Long-term cell performance is also assessed to evaluate cell degradation. Details of the custom single-cell test apparatus developed for these experiments are also presented. NASA, in conjunction with the University of Toledo, has developed a new cell concept with the goals of reduced weight and high power density. This report presents results of the INL's testing of this new solid oxide cell design as an electrolyzer. Gas composition, operating voltage, and other parameters were varied during testing. Results to date show the NASA cell to be a promising design for both high power-to-weight fuel cell and electrolyzer applications.

Long-Term Degradation Testing of High-Temperature Electrolytic Cells

International Nuclear Information System (INIS)

Stoots, C.M.; O'Brien, J.E.; Herring, J.S.; Housley, G.K.; Milobar, D.G.; Sohal, M.S.

2009-01-01

The Idaho National Laboratory (INL) has been researching the application of solid-oxide electrolysis cell for large-scale hydrogen production from steam over a temperature range of 800 to 900 C. The INL has been testing various solid oxide cell designs to characterize their electrolytic performance operating in the electrolysis mode for hydrogen production. Some results presented in this report were obtained from cells, with an active area of 16 cm2 per cell. The electrolysis cells are electrode-supported, with ∼10 ∼m thick yttria-stabilized zirconia (YSZ) electrolytes, ∼1400 (micro)m thick nickel-YSZ steam-hydrogen electrodes, and manganite (LSM) air-oxygen electrodes. The experiments were performed over a range of steam inlet mole fractions (0.1 to 0.6), gas flow rates, and current densities (0 to 0.6 A/cm2). Steam consumption rates associated with electrolysis were measured directly using inlet and outlet dewpoint instrumentation. On a molar basis, the steam consumption rate is equal to the hydrogen production rate. Cell performance was evaluated by performing DC potential sweeps at 800, 850, and 900 C. The voltage-current characteristics are presented, along with values of area-specific resistance as a function of current density. Long-term cell performance is also assessed to evaluate cell degradation. Details of the custom single-cell test apparatus developed for these experiments are also presented. NASA, in conjunction with the University of Toledo, has developed a new cell concept with the goals of reduced weight and high power density. This report presents results of the INL's testing of this new solid oxide cell design as an electrolyzer. Gas composition, operating voltage, and other parameters were varied during testing. Results to date show the NASA cell to be a promising design for both high power-to-weight fuel cell and electrolyzer applications.

Composite electrolyte with proton conductivity for low-temperature solid oxide fuel cell

Energy Technology Data Exchange (ETDEWEB)

Raza, Rizwan, E-mail: razahussaini786@gmail.com [Department of Physics, COMSATS Institute of Information Technology, Lahore 54000 (Pakistan); Department of Energy Technology, Royal Institute of Technology, KTH, Stockholm 10044 (Sweden); Ahmed, Akhlaq; Akram, Nadeem; Saleem, Muhammad; Niaz Akhtar, Majid; Ajmal Khan, M.; Abbas, Ghazanfar; Alvi, Farah; Yasir Rafique, M. [Department of Physics, COMSATS Institute of Information Technology, Lahore 54000 (Pakistan); Sherazi, Tauqir A. [Department of Chemistry, COMSATS Institute of Information Technology, Abbotabad 22060 (Pakistan); Shakir, Imran [Sustainable Energy Technologies (SET) center, College of Engineering, King Saud University, PO-BOX 800, Riyadh 11421 (Saudi Arabia); Mohsin, Munazza [Department of Physics, Lahore College for Women University, Lahore, 54000 (Pakistan); Javed, Muhammad Sufyan [Department of Physics, COMSATS Institute of Information Technology, Lahore 54000 (Pakistan); Department of Applied Physics, Chongqing University, Chongqing 400044 (China); Zhu, Bin, E-mail: binzhu@kth.se, E-mail: zhubin@hubu.edu.cn [Department of Energy Technology, Royal Institute of Technology, KTH, Stockholm 10044 (Sweden); Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials, Faculty of Physics and Electronic Science/Faculty of Computer and Information, Hubei University, Wuhan, Hubei 430062 (China)

2015-11-02

In the present work, cost-effective nanocomposite electrolyte (Ba-SDC) oxide is developed for efficient low-temperature solid oxide fuel cells (LTSOFCs). Analysis has shown that dual phase conduction of O{sup −2} (oxygen ions) and H{sup +} (protons) plays a significant role in the development of advanced LTSOFCs. Comparatively high proton ion conductivity (0.19 s/cm) for LTSOFCs was achieved at low temperature (460 °C). In this article, the ionic conduction behaviour of LTSOFCs is explained by carrying out electrochemical impedance spectroscopy measurements. Further, the phase and structure analysis are investigated by X-ray diffraction and scanning electron microscopy techniques. Finally, we achieved an ionic transport number of the composite electrolyte for LTSOFCs as high as 0.95 and energy and power density of 90% and 550 mW/cm{sup 2}, respectively, after sintering the composite electrolyte at 800 °C for 4 h, which is promising. Our current effort toward the development of an efficient, green, low-temperature solid oxide fuel cell with the incorporation of high proton conductivity composite electrolyte may open frontiers in the fields of energy and fuel cell technology.

Composite electrolyte with proton conductivity for low-temperature solid oxide fuel cell

Science.gov (United States)

Raza, Rizwan; Ahmed, Akhlaq; Akram, Nadeem; Saleem, Muhammad; Niaz Akhtar, Majid; Sherazi, Tauqir A.; Ajmal Khan, M.; Abbas, Ghazanfar; Shakir, Imran; Mohsin, Munazza; Alvi, Farah; Javed, Muhammad Sufyan; Yasir Rafique, M.; Zhu, Bin

2015-11-01

In the present work, cost-effective nanocomposite electrolyte (Ba-SDC) oxide is developed for efficient low-temperature solid oxide fuel cells (LTSOFCs). Analysis has shown that dual phase conduction of O-2 (oxygen ions) and H+ (protons) plays a significant role in the development of advanced LTSOFCs. Comparatively high proton ion conductivity (0.19 s/cm) for LTSOFCs was achieved at low temperature (460 °C). In this article, the ionic conduction behaviour of LTSOFCs is explained by carrying out electrochemical impedance spectroscopy measurements. Further, the phase and structure analysis are investigated by X-ray diffraction and scanning electron microscopy techniques. Finally, we achieved an ionic transport number of the composite electrolyte for LTSOFCs as high as 0.95 and energy and power density of 90% and 550 mW/cm2, respectively, after sintering the composite electrolyte at 800 °C for 4 h, which is promising. Our current effort toward the development of an efficient, green, low-temperature solid oxide fuel cell with the incorporation of high proton conductivity composite electrolyte may open frontiers in the fields of energy and fuel cell technology.

High temperature fuel cell with ceria-based solid electrolyte

International Nuclear Information System (INIS)

Arai, H.; Eguchi, K.; Yahiro, H.; Baba, Y.

1987-01-01

Cation-doped ceria is investigated as an electrolyte for the solid oxide fuel cell. As for application to the fuel cells, the electrolyte are desired to have high ionic conductivity in deriving a large electrical power. A series of cation-doped ceria has higher ionic conductivity than zirconia-based oxides. In the present study, the basic electrochemical properties of cation-doped ceria were studied in relation to the application of fuel cells. The performance of fuel cell with yttria-doped ceria electrolyte was evaluated. Ceria-based oxides were prepared by calcination of oxide mixtures of the components or calcination of co-precipitated hydroxide mixtures from the metal nitrate solution. The oxide mixtures thus obtained were sintered at 1650 0 C for 15 hr in air into disks. Ionic transference number, t/sub i/, was estimated from emf of oxygen concentration cell. Electrical conductivities were measured by dc-4 probe method by varying the oxygen partial pressure. The fuel cell was operated by oxygen and hydrogen

Microwave assisted sintering of gadolinium doped barium cerate electrolyte for intermediate temperature solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Kumar, Arumugam Senthil, E-mail: senthu.ramp@gmail.com [Department of Physics, PSG College of Technology, Coimbatore, 641 004, Tamilnadu (India); Balaji, Ramamoorthy [Department of Physics, PSG College of Technology, Coimbatore, 641 004, Tamilnadu (India); Jayakumar, Srinivasalu [Department of Physics, PSG Institute of Technology and Applied Research, Coimbatore, 641 062, Tamilnadu (India); Pradeep, Chandran [Department of Physics, Indian Institute of Technology, Madras, 600 036, Tamilnadu (India)

2016-10-01

In Solid Oxide Fuel Cell (SOFC), electrolyte plays a vital role to increase the energy conversion efficiency. The main hurdle of such electrolyte in fuel cell is its higher operating temperature (1000 °C) which results in design limitation and higher fabrication cost. In order to reduce the operating temperature of SOFC, a suitable electrolyte has been prepared through co-precipitation method followed by microwave sintering of solid ceramic. The calcination temperature for the as-prepared powder was identified using Differential Scanning Calorimetry. The crystal structure of the sample was found to exhibit its orthorhombic perovskite structure. The particle size was determined using High-Resolution Transmission Electron Microscope with uniform in shape and size, match with XRD results and confirmed from structural analysis. Thus, the sample prepared via co-precipitation method and the solid ceramic sintered through microwave can be a promising electrolyte for fuel cells operated at intermediate temperature. - Highlights: • To synthesis the composite electrolyte by chemical method and sinter using microwave. • To reduce the operating temperature of electrolyte for high ionic conductivity in SOFC's. • To study the phase purity and to develop nanocomposite at reduced temperature.

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.

Oxidative degradation of polybenzimidazole membranes as electrolytes for high temperature proton exchange membrane fuel cells

DEFF Research Database (Denmark)

Liao, J.H.; Li, Qingfeng; Rudbeck, H.C.

2011-01-01

the oxidative degradation of the polymer membrane was studied under the Fenton test conditions by the weight loss, intrinsic viscosity, size exclusion chromatography, scanning electron microscopy and Fourier transform infrared spectroscopy. During the Fenton test, significant weight losses depending...... on the initial molecular weight of the polymer were observed. At the same time, viscosity and SEC measurements revealed a steady decrease in molecular weight. The degradation of acid doped PBI membranes under Fenton test conditions is proposed to start by the attack of hydroxyl radicals at the carbon atom......Polybenzimidazole membranes imbibed with acid are emerging as a suitable electrolyte material for high-temperature polymer electrolyte fuel cells. The oxidative stability of polybenzimidazole has been identified as an important issue for the long-term durability of such cells. In this paper...

Novel polybenzimidazole derivatives for high temperature polymer electrolyte membrane fuel cell applications

Science.gov (United States)

Xiao, Lixiang

Recent advances have made polymer electrolyte membrane fuel cells (PEMFCs) a leading alternative to internal combustion engines for both stationary and transportation applications. In particular, high temperature polymer electrolyte membranes operational above 120°C without humidification offer many advantages including fast electrode kinetics, high tolerance to fuel impurities and simple thermal and water management systems. A series of polybenzimidazole (PBI) derivatives including pyridine-based PBI (PPBI) and sulfonated PBI (SPBI) homopolymers and copolymers have been synthesized using polyphosphoric acid (PPA) as both solvent and polycondensation agent. High molecular weight PBI derivative polymers were obtained with well controlled backbone structures in terms of pyridine ring content, polymer backbone rigidity and degree of sulfonation. A novel process, termed the PPA process, has been developed to prepare phosphoric acid (PA) doped PBI membranes by direct-casting of the PPA polymerization solution without isolation or re-dissolution of the polymers. The subsequent hydrolysis of PPA to PA by moisture absorbed from the atmosphere usually induced a transition from the solution-like state to a gel-like state and produced PA doped PBI membranes with a desirable suite of physiochemical properties characterized by the PA doping levels, mechanical properties and proton conductivities. The effects of the polymer backbone structure on the polymer characteristics and membrane properties, i.e., the structure-property relationships of the PBI derivative polymers have been studied. The incorporation of additional basic nitrogen containing pyridine rings and sulfonic acid groups enhanced the polymer solubility in acid and dipolar solvents while retaining the inherently high thermal stability of the PBI heteroaromatic backbone. In particular, the degradation of the SPBI polymers with reasonable high molecular weights commenced above 450°C, notably higher than other

Operation Strategies Based on Carbon Corrosion and Lifetime Investigations for High Temperature Polymer Electrolyte Membrane Fuel Cell Stacks

DEFF Research Database (Denmark)

Kannan, A.; Kaczerowski, J.; Kabza, A.

2018-01-01

This paper is aimed to develop operation strategies or high temperature polymer electrolyte fuel cells (HT-PEMFCs) stacks in order to enhance the endurance by mitigating carbon oxidation reaction. The testing protocols are carefully designed to suit the operating cycle for the realistic application...

The Influence of Operation Temperature of the Characteristic of Sulfonated Polyether-Ether Ketone Electrolyte Membrane

International Nuclear Information System (INIS)

Sri Handayani; Eniya Listiani Dewi

2008-01-01

Recently, high temperature Direct Methanol Fuel Cell (DMFC) has been receiving great attention, because provide faster reaction kinetic, the enhance electrode kinetics, reduced size and reduce Pt-based catalyst poisoning by CO. But at high temperature, it will decrease the membrane performance i.e. low proton conductivity affected by humidification and high methanol crossover as happening to Nafion-117 membrane (commercial membrane). To solve this problems, sulfonated polyether-ether ketone and composite (silica additive) as electrolyte membrane at high temperature DMFC was tried to use. In this research, sPEEK with sulfonation degree (SD) 47 % and 68 % and addition silica 3 wt % were used as electrolyte membranes. Proton conductivity and methanol permeability of these membranes were measured at various temperatures (25, 50, 90 and 140 C ). Proton conductivity of membranes were measured by standard bridge impedance spectroscopy (LCR-meter, HIOKI 3522-50) and it was found about 0.01-0.04 S/cm. Methanol permeability of membranes were investigated by diffusion cell and gave the result about 10 - 6 - 10 - 7cm 2 /s. The best sPEEK membrane was sPEEK membrane with SD 68 % and the addition of silica 3 wt%, signed by highest selectivity value (ratio proton conductivity to methanol permeability). Therefore, electrolyte membrane based sulfonated polyether-ether ketone (SD 68 %) with silica could be used at high temperature which give promising as solid electrolyte membrane in application high temperature DMFC. (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.

A highly conductive, non-flammable polymer–nanoparticle hybrid electrolyte

KAUST Repository

Agrawal, Akanksha

2015-01-01

© 2015 The Royal Society of Chemistry. We report on the physical properties of lithium-ion conducting nanoparticle-polymer hybrid electrolytes created by dispersing bidisperse mixtures of polyethylene glycol (PEG)-functionalized silica nanoparticles in an aprotic liquid host. At high particle contents, we find that the ionic conductivity is a non-monotonic function of the fraction of larger particles xL in the mixtures, and that for the nearly symmetric case xL ≈ 0.5 (i.e. equal volume fraction of small and large particles), the room temperature ionic conductivity is nearly ten-times larger than in similar nanoparticle hybrid electrolytes comprised of the pure small (xL ≈ 0) or large (xL ≈ 1) particle components. Complementary trends are seen in the activation energy for ion migration and effective tortuosity of the electrolytes, which both exhibit minima near xL ≈ 0.5. Characterization of the electrolytes by dynamic rheology reveals that the maximum conductivity coincides with a distinct transition in soft glassy properties from a jammed to partially jammed and back to jammed state, as the fraction of large particles is increased from 0 to 1. This finding implies that the conductivity enhancement arises from purely entropic loss of correlation between nanoparticle centers arising from particle size dispersity. As a consequence of these physics, it is now possible to create hybrid electrolytes with MPa elastic moduli and mS cm-1 ionic conductivity levels at room temperature using common aprotic liquid media as the electrolyte solvent. Remarkably, we also find that even in highly flammable liquid media, the bidisperse nanoparticle hybrid electrolytes can be formulated to exhibit low or no flammability without compromising their favorable room temperature ionic conductivity and mechanical properties.

A polymer electrolyte membrane for high temperature fuel cells to fit vehicle applications

International Nuclear Information System (INIS)

Li Mingqiang; Scott, Keith

2010-01-01

Poly(tetrafluoroethylene) PTFE/PBI composite membranes doped with H 3 PO 4 were fabricated to improve the performance of high temperature polymer electrolyte membrane fuel cells (HT-PEMFC). The composite membranes were fabricated by immobilising polybenzimidazole (PBI) solution into a hydrophobic porous PTFE membrane. The mechanical strength of the membrane was good exhibiting a maximum load of 35.19 MPa. After doping with the phosphoric acid, the composite membrane had a larger proton conductivity than that of PBI doped with phosphoric acid. The PTFE/PBI membrane conductivity was greater than 0.3 S cm -1 at a relative humidity 8.4% and temperature of 180 deg. C with a 300% H 3 PO 4 doping level. Use of the membrane in a fuel cell with oxygen, at 1 bar overpressure gave a peak power density of 1.2 W cm -2 at cell voltages >0.4 V and current densities of 3.0 A cm -2 . The PTFE/PBI/H 3 PO 4 composite membrane did not exhibit significant degradation after 50 h of intermittent operation at 150 deg. C. These results indicate that the composite membrane is a promising material for vehicles driven by high temperature PEMFCs.

Synthesis, ionic conductivity, and thermal properties of proton conducting polymer electrolyte for high temperature fuel cell

Energy Technology Data Exchange (ETDEWEB)

Itoh, Takahito; Hamaguchi, Yohei; Uno, Takahiro; Kubo, Masataka [Department of Chemistry for Materials, Faculty of Engineering, Mie University, 1577 Kurima Machiya-cho, Tsu, Mie 514-8507 (Japan); Aihara, Yuichi; Sonai, Atsuo [Samsung Yokohama Research Institute, 2-7 Sugasawa-cho, Tsurumi-ku, Yokohama 230-0027 (Japan)

2006-01-16

Hyperbranched polymer (poly-1a) with sulfonic acid groups at the end of chains was successfully synthesized. Interpenetration reaction of poly-1a with a hyperbranched polymer with acryloyl groups at the end of chains (poly-1b) as a cross-linker afforded a tough electrolyte membrane. The poly-1a and the resulting electrolyte membrane showed the ionic conductivities of 7x10{sup -4} and 8x10{sup -5} S/cm, respectively, at 150C under dry condition. The ionic conductivities of the poly-1a and the electrolyte membrane exhibited the VTF type temperature dependence. And also, both poly-1a and the resulting electrolyte membrane were thermally stable up to 200C. (author)

Comparison of high-temperature and low-temperature polymer electrolyte membrane fuel cell systems with glycerol reforming process for stationary applications

International Nuclear Information System (INIS)

Authayanun, Suthida; Mamlouk, Mohamed; Scott, Keith; Arpornwichanop, Amornchai

2013-01-01

Highlights: • PEMFC systems with a glycerol steam reformer for stationary application are studied. • Performance of HT-PEMFC and LT-PEMFC systems is compared. • HT-PEMFC system shows good performance over LT-PEMFC system at a high current density. • HT-PEMFC system with water gas shift reactor shows the highest system efficiency. • Heat integration can improve the efficiency of HT-PEMFC system. - Abstract: A high-temperature polymer electrolyte membrane fuel cell (HT-PEMFC) has a major advantage over a low-temperature polymer electrolyte fuel cell (LT-PEMFC) demonstrated by a tolerance to a higher CO content in the hydrogen feed and thus a simpler fuel processing. In this study, a direct comparison between the performance of HT-PEMFC and LT-PEMFC systems integrated with a glycerol steam reformer with and without a water gas shift reactor is shown. Under pure hydrogen operation, the LT-PEMFC performance is superior to the HT-PEMFC. However, the HT-PEMFC system shows good performance over the LT-PEMFC system when operated under high current density and high pressure (3 atm) and using the reformate gas derived from the glycerol processor as fuel. At high current density, the high concentration of CO is the major limitation for the operation of HT-PEMFC system without water gas shift reactor, whereas the LT-PEMFC suffers from CO poisoning and restricted oxygen mass transport. Considering the system efficiency with co-heat and power generation, the HT-PEMFC system with water gas shift reactor shows the highest overall system efficiency (approximately 60%) and therefore one of the most suitable technologies for stationary applications

High elastic modulus polymer electrolytes suitable for preventing thermal runaway in lithium batteries

Science.gov (United States)

Mullin, Scott; Panday, Ashoutosh; Balsara, Nitash Pervez; Singh, Mohit; Eitouni, Hany Basam; Gomez, Enrique Daniel

2014-04-22

A polymer that combines high ionic conductivity with the structural properties required for Li electrode stability is useful as a solid phase electrolyte for high energy density, high cycle life batteries that do not suffer from failures due to side reactions and dendrite growth on the Li electrodes, and other potential applications. The polymer electrolyte includes a linear block copolymer having a conductive linear polymer block with a molecular weight of at least 5000 Daltons, a structural linear polymer block with an elastic modulus in excess of 1.times.10.sup.7 Pa and an ionic conductivity of at least 1.times.10.sup.-5 Scm.sup.-1. The electrolyte is made under dry conditions to achieve the noted characteristics. In another aspect, the electrolyte exhibits a conductivity drop when the temperature of electrolyte increases over a threshold temperature, thereby providing a shutoff mechanism for preventing thermal runaway in lithium battery cells.

An experimental and simulation study of novel channel designs for open-cathode high-temperature polymer electrolyte membrane fuel cells

DEFF Research Database (Denmark)

Thomas, Sobi; Bates, Alex; Park, Sam

2016-01-01

A minimum balance of plant (BOP) is desired for an open-cathode high temperature polymer electrolyte membrane (HTPEM) fuel cell to ensure low parasitic losses and a compact design. The advantage of an open-cathode system is the elimination of the coolant plate and incorporation of a blower for ox...

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....

Ionic liquids and ionic liquid acids with high temperature stability for fuel cell and other high temperature applications, method of making and cell employing same

Science.gov (United States)

Angell, C Austen [Mesa, AZ; Xu, Wu [Broadview Heights, OH; Belieres, Jean-Philippe [Chandler, AZ; Yoshizawa, Masahiro [Tokyo, JP

2011-01-11

Disclosed are developments in high temperature fuel cells including ionic liquids with high temperature stability and the storage of inorganic acids as di-anion salts of low volatility. The formation of ionically conducting liquids of this type having conductivities of unprecedented magnitude for non-aqueous systems is described. The stability of the di-anion configuration is shown to play a role in the high performance of the non-corrosive proton-transfer ionic liquids as high temperature fuel cell electrolytes. Performance of simple H.sub.2(g) electrolyte/O.sub.2(g) fuel cells with the new electrolytes is described. Superior performance both at ambient temperature and temperatures up to and above 200.degree. C. are achieved. Both neutral proton transfer salts and the acid salts with HSO.sup.-.sub.4 anions, give good results, the bisulphate case being particularly good at low temperatures and very high temperatures. The performance of all electrolytes is improved by the addition of a small amount of involatile base of pK.sub.a value intermediate between those of the acid and base that make the bulk electrolyte. The preferred case is the imidazole-doped ethylammonium hydrogensulfate which yields behavior superior in all respects to that of the industry standard phosphoric acid electrolyte.

Electrolyte bi-layering strategy to improve the performance of an intermediate temperature solid oxide fuel cell: A review

Science.gov (United States)

Shri Prakash, B.; Pavitra, R.; Senthil Kumar, S.; Aruna, S. T.

2018-03-01

Lowering of operation temperature has become one of the primary goals of solid oxide fuel (SOFC) research as reduced temperature improves the prospects for widespread commercialization of this energy system. Reduced operational temperature also mitigates the issues associated with high temperature SOFCs and paves way not only for the large scale stationary power generation but also makes SOFCs viable for portable and transport applications. However, there are issues with electrolyte and cathode materials at low temperatures, individually as well as in association with other components, which makes the performance of the SOFCs less satisfactory than expected at lowered temperatures. Bi-layering of electrolytes and impregnation of cathodes have emerged as two important strategies to overcome these issues and achieve higher performance at low temperatures. This review article provides the perspective on the strategy of bi-layering of electrolyte to achieve the desired high performance from SOFC at low to intermediate temperatures.

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.

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.

The electrolyte challenge for a direct methanol-air polymer electrolyte fuel cell operating at temperatures up to 200 C

Science.gov (United States)

Savinell, Robert; Yeager, Ernest; Tryk, Donald; Landau, Uziel; Wainright, Jesse; Gervasio, Dominic; Cahan, Boris; Litt, Morton; Rogers, Charles; Scherson, Daniel

1993-01-01

Novel polymer electrolytes are being evaluated for use in a direct methanol-air fuel cell operating at temperatures in excess of 100 C. The evaluation includes tests of thermal stability, ionic conductivity, and vapor transport characteristics. The preliminary results obtained to date indicate that a high temperature polymer electrolyte fuel cell is feasible. For example, Nafion 117 when equilibrated with phosphoric acid has a conductivity of at least 0.4 Omega(exp -1)cm(exp -1) at temperatures up to 200 C in the presence of 400 torr of water vapor and methanol vapor cross over equivalent to 1 mA/cm(exp 2) under a one atmosphere methanol pressure differential at 135 C. Novel polymers are also showing similar encouraging results. The flexibility to modify and optimize the properties by custom synthesis of these novel polymers presents an exciting opportunity to develop an efficient and compact methanol fuel cell.

High temperature mechanical properties of zirconia tapes used for electrolyte supported solid oxide fuel cells

Science.gov (United States)

Fleischhauer, Felix; Bermejo, Raul; Danzer, Robert; Mai, Andreas; Graule, Thomas; Kuebler, Jakob

2015-01-01

Solid-Oxide-Fuel-Cell systems are efficient devices to convert the chemical energy stored in fuels into electricity. The functionality of the cell is related to the structural integrity of the ceramic electrolyte, since its failure can lead to drastic performance losses. The mechanical property which is of most interest is the strength distribution at all relevant temperatures and how it is affected with time due to the environment. This study investigates the impact of the temperature on the strength and the fracture toughness of different zirconia electrolytes as well as the change of the elastic constants. 3YSZ and 6ScSZ materials are characterised regarding the influence of sub critical crack growth (SCCG) as one of the main lifetime limiting effects for ceramics at elevated temperatures. In addition, the reliability of different zirconia tapes is assessed with respect to temperature and SCCG. It was found that the strength is only influenced by temperature through the change in fracture toughness. SCCG has a large influence on the strength and the lifetime for intermediate temperature, while its impact becomes limited at temperatures higher than 650 °C. In this context the tetragonal 3YSZ and 6ScSZ behave quite different than the cubic 10Sc1CeSZ, so that at 850 °C it can be regarded as competitive compared to the tetragonal compounds.

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.

Control and experimental characterization of a methanol reformer for a 350W high temperature polymer electrolyte membrane fuel cell system

DEFF Research Database (Denmark)

Andreasen, Søren Juhl; Kær, Søren Knudsen; Jensen, Hans-Christian Becker

suited for reformer systems, where high CO tolerance is required. This enables the use fuels based on e.g. liquid alcohols. This work presents the control strategies of a methanol refoermer for a 350W HTPEM FC system. The system examined is the Serenergy H3-350 Mobile Battery Charger, an integrated......High temperature polymer electrolyte membrane(HTPEM) fuel cells offer many advantages due to their increased operating tempera-tures compared to similar Nafion-based membrane tech-nologies, that rely on the conductive abilities of liquid water. The polybenzimidazole (PBI) membranes are especially...

LOW TEMPERATURE CATHODE SUPPORTED ELECTROLYTES

Energy Technology Data Exchange (ETDEWEB)

Harlan U. Anderson

2000-03-31

This project has three main goals: Thin Films Studies, Preparation of Graded Porous Substrates and Basic Electrical Characterization and Testing of Planar Single Cells. During this time period substantial progress has been made in developing low temperature deposition techniques to produce dense, nanocrystalline yttrium-stabilized zirconia films on both dense oxide and polymer substrates. Progress has been made in the preparation and characterization of thin electrolytes and porous LSM substrates. Both of these tasks are essentially on or ahead of schedule. In our proposal, we suggested that the ZrO{sub 2}/Sc system needed to be considered as a candidate as a thin electrolyte. This was because microcrystalline ZrO{sub 2}/Sc has a significantly higher ionic conductivity than YSZ, particularly at the lower temperatures. As a result, some 0.5 micron thick film of ZrO{sub 2}/16% Sc on an alumina substrate (grain size 20nm) was prepared and the electrical conductivity measured as a function of temperature and oxygen activity. The Sc doped ZrO{sub 2} certainly has a higher conductivity that either 20nm or 2400nm YSZ, however, electronic conductivity dominates the conductivity for oxygen activities below 10{sup -15}. Whereas for YSZ, electronic conductivity is not a problem until the oxygen activity decreases below 10{sup -25}. These initial results show that the ionic conductivity of 20nm YSZ and 20nm ZrO{sub 2}/16% Sc are essentially the same and the enhanced conductivity which is observed for Sc doping in microcrystalline specimens is not observed for the same composition when it is nanocrystalline. In addition they show that the electronic conductivity of Sc doped ZrO{sub 2} is at least two orders of magnitude higher than that observed for YSZ. The conclusion one reaches is that for 0.5 to 1 micron thick nanocrystalline films, Sc doping of ZrO{sub 2} has no benefits compared to YSZ. As a result, electrolyte films of ZrO{sub 2}/Sc should not be considered as candidates

Synthesis and characterization of novel electrolyte materials for intermediate temperature solid oxide fuel cells

International Nuclear Information System (INIS)

Chaubey, Nityanand; Chattopadhyaya, M.C.; Wani, B.N.; Bharadwaj, S.R.

2008-01-01

The high operating temperature of SOFCs using zirconia based electrolyte have several restrictions on materials used as interconnect and sealing and also requires use of expensive ceramics. Lowering the operating temperature of SOFCs to 600-800 deg C will enable to use cheaper materials and reduce the cost of fabrication while keeping the high power density. Lanthanide gallates are considered to be very promising solid electrolytes for intermediate temperature (600-800 deg C) solid oxide fuel cells (IT-SOFCs) due to their high ionic conductivity at lower temperatures. Phase purity of this material is a concern for the researchers for a long time. These materials are prepared at very high temperature (∼1400 deg C), since it is known that at around 1100 deg C, solubilities of Sr and Mg in LaGaO 3 were close to zero. Hence in the present work perovskite oxides of Ln 1-x Sr x Ga 1-y Mg y O 3-δ (Ln= Sm, Gd and x = 0.10, y=0.20) have been prepared by different methods i.e. solid state reaction, gel combustion and co-precipitation methods

Concept of polymer alloy electrolytes: towards room temperature operation of lithium-polymer batteries

International Nuclear Information System (INIS)

Noda, Kazuhiro; Yasuda, Toshikazu; Nishi, Yoshio

2004-01-01

Polymer alloy technique is very powerful tool to tune the ionic conductivity and mechanical strength of polymer electrolyte. A semi-interpenetrating polymer network (semi-IPN) polymer alloy electrolyte, composed of non-cross-linkable siloxane-based polymer and cross-linked 3D network polymer, was prepared. Such polymer alloy electrolyte has quite high ionic conductivity (more than 10 -4 Scm -1 at 25 o C and 10 -5 Scm -1 at -10 o C) and mechanical strength as a separator film with a wide electrochemical stability window. A lithium metal/semi-IPN polymer alloy solid state electrolyte/LiCoO 2 cell demonstrated promising cycle performance with room temperature operation of the energy density of 300Wh/L and better rate performance than conventional PEO based lithium polymer battery ever reported

POLYMER ELECTROLYTE MEMBRANE FUEL CELLS

DEFF Research Database (Denmark)

2001-01-01

A method for preparing polybenzimidazole or polybenzimidazole blend membranes and fabricating gas diffusion electrodes and membrane-electrode assemblies is provided for a high temperature polymer electrolyte membrane fuel cell. Blend polymer electrolyte membranes based on PBI and various...... thermoplastic polymers for high temperature polymer electrolyte fuel cells have also been developed. Miscible blends are used for solution casting of polymer membranes (solid electrolytes). High conductivity and enhanced mechanical strength were obtained for the blend polymer solid electrolytes....... With the thermally resistant polymer, e.g., polybenzimidazole or a mixture of polybenzimidazole and other thermoplastics as binder, the carbon-supported noble metal catalyst is tape-cast onto a hydrophobic supporting substrate. When doped with an acid mixture, electrodes are assembled with an acid doped solid...

Crosslinked wholly aromatic polyether membranes based on quinoline derivatives and their application in high temperature polymer electrolyte membrane fuel cells

Science.gov (United States)

Kallitsis, K. J.; Nannou, R.; Andreopoulou, A. K.; Daletou, M. K.; Papaioannou, D.; Neophytides, S. G.; Kallitsis, J. K.

2018-03-01

An AB type difunctional quinoline based monomer bearing a pentafluorophenyl unit combined with a phenol functionality is being synthesized and homopolymerized to create linear aromatic polyethers as polymer electrolytes for HT-PEM FCs applications. Several conditions are tested for the optimized synthesis of the monomer and homopolymer. Additionally, covalent crosslinking through aromatic polyether bond formation enables the creation of wholly aromatic crosslinked polymeric electrolyte membranes. More specifically, the perfluorophenyl units are crosslinked with other hydroxyl end functionalized moieties, providing membranes with enhanced chemical and mechanical properties that are moreover easily doped with phosphoric acid even at ambient temperatures. All membranes are evaluated for their structural and thermal characteristics and their doping ability with phosphoric acid. Selected crosslinked membranes are further tested in terms of their single cell performance at the temperature range 160 °C-200 °C showing promising performance and high conductivity values even up to 0.2 S cm-1 in some cases.

Galvanic high temperature cell with solid negative electrode and an electrolyte melt. Galvanische Hochtemperaturzelle mit fester negativer Elektrode und einem Schmelzelektrolyten

Energy Technology Data Exchange (ETDEWEB)

Kappus, W; Borger, W

1987-01-08

The purpose of the invention is to make an electrolyte melt available for high temperature cells (e.g. LiFeS cells), which guarantees ion transport and also acts as a separator. The invention starts from the fact that binary melts of the LiCl/KCl type are only liquid (i.e. without solid components) at a certain temperature at certain concentrations. With suitable mixing conditions, which apart from a eutectic composition, are mainly on the side of one of the two components, one can ensure that this component is present in the solid phase. In this way, a solid framework of LiCl, for example, is formed between the electrode plates in situ as a separator, in the pores of which the excess melt (e.g. LiCl/KCl) can carry out ion conduction. The volumetric ratio of the electrolyte melt in which liquid and solid phases are present at the working temperature of the cell should preferably be in the range of 2:1 to 1:2.

Rapid Thermal Annealing of Cathode-Garnet Interface toward High-Temperature Solid State Batteries.

Science.gov (United States)

Liu, Boyang; Fu, Kun; Gong, Yunhui; Yang, Chunpeng; Yao, Yonggang; Wang, Yanbin; Wang, Chengwei; Kuang, Yudi; Pastel, Glenn; Xie, Hua; Wachsman, Eric D; Hu, Liangbing

2017-08-09

High-temperature batteries require the battery components to be thermally stable and function properly at high temperatures. Conventional batteries have high-temperature safety issues such as thermal runaway, which are mainly attributed to the properties of liquid organic electrolytes such as low boiling points and high flammability. In this work, we demonstrate a truly all-solid-state high-temperature battery using a thermally stable garnet solid-state electrolyte, a lithium metal anode, and a V 2 O 5 cathode, which can operate well at 100 °C. To address the high interfacial resistance between the solid electrolyte and cathode, a rapid thermal annealing method was developed to melt the cathode and form a continuous contact. The resulting interfacial resistance of the solid electrolyte and V 2 O 5 cathode was significantly decreased from 2.5 × 10 4 to 71 Ω·cm 2 at room temperature and from 170 to 31 Ω·cm 2 at 100 °C. Additionally, the diffusion resistance in the V 2 O 5 cathode significantly decreased as well. The demonstrated high-temperature solid-state full cell has an interfacial resistance of 45 Ω·cm 2 and 97% Coulombic efficiency cycling at 100 °C. This work provides a strategy to develop high-temperature all-solid-state batteries using garnet solid electrolytes and successfully addresses the high contact resistance between the V 2 O 5 cathode and garnet solid electrolyte without compromising battery safety or performance.

Flexible and Self-Healing Aqueous Supercapacitors for Low Temperature Applications: Polyampholyte Gel Electrolytes with Biochar Electrodes.

Science.gov (United States)

Li, Xinda; Liu, Li; Wang, Xianzong; Ok, Yong Sik; Elliott, Janet A W; Chang, Scott X; Chung, Hyun-Joong

2017-05-10

A flexible and self-healing supercapacitor with high energy density in low temperature operation was fabricated using a combination of biochar-based composite electrodes and a polyampholyte hydrogel electrolyte. Polyampholytes, a novel class of tough hydrogel, provide self-healing ability and mechanical flexibility, as well as low temperature operation for the aqueous electrolyte. Biochar is a carbon material produced from the low-temperature pyrolysis of biological wastes; the incorporation of reduced graphene oxide conferred mechanical integrity and electrical conductivity and hence the electrodes are called biochar-reduced-graphene-oxide (BC-RGO) electrodes. The fabricated supercapacitor showed high energy density of 30 Wh/kg with ~90% capacitance retention after 5000 charge-discharge cycles at room temperature at a power density of 50 W/kg. At -30 °C, the supercapacitor exhibited an energy density of 10.5 Wh/kg at a power density of 500 W/kg. The mechanism of the low-temperature performance excellence is likely to be associated with the concept of non-freezable water near the hydrophilic polymer chains, which can motivate future researches on the phase behaviour of water near polyampholyte chains. We conclude that the combination of the BC-RGO electrode and the polyampholyte hydrogel electrolyte is promising for supercapacitors for flexible electronics and for low temperature environments.

Novel composite membranes based on PBI and dicationic ionic liquids for high temperature polymer electrolyte membrane fuel cells

International Nuclear Information System (INIS)

Hooshyari, Khadijeh; Javanbakht, Mehran; Adibi, Mina

2016-01-01

Two types of innovative composite membranes based on polybenzimidazole (PBI) containing dicationic ionic liquid 1,3-di(3-methylimidazolium) propane bis (trifluoromethylsulfonyl) imide (PDC 3 ) and monocationic ionic liquid 1-hexyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide (PMC 6 ) are prepared as electrolyte for high temperature fuel cells applications under anhydrous conditions. The analyses of results display promising characteristics such as high proton conductivity and thermal stability. Moreover the fuel cell performance of PA doped PDC 3 composite membranes is enhanced in comparison with PA doped PMC 6 and PA doped PBI membranes at high temperatures. Dicationic ionic liquid with high number of charge carriers provides well-developed ionic channels which form facile pathways and considerably develop the anhydrous proton conductivity. The highest proton conductivity of 81 mS/cm is achieved for PA doped PDC 3 composite membranes with PBI/IL mole ratio: 4 at 180 °C. A power density of 0.44 W/cm 2 is obtained at 0.5 V and 180 °C for PA doped PDC 3 composite membranes, which proves that these developed composite membranes can be considered as most promising candidates for high temperature fuel cell applications with enhanced proton conductivity.

Surface properties of magnetite in high temperature aqueous electrolyte solutions: A review.

Science.gov (United States)

Vidojkovic, Sonja M; Rakin, Marko P

2017-07-01

Deposits and scales formed on heat transfer surfaces in power plant water/steam circuits have a significant negative impact on plant reliability, availability and performance, causing tremendous economic consequences and subsequent increases in electricity cost. Consequently, the improvement of the understanding of deposition mechanisms on power generating surfaces is defined as a high priority in the power industry. The deposits consist principally of iron oxides, which are steel corrosion products and usually present in colloidal form. Magnetite (Fe 3 O 4 ) is the predominant and most abundant compound found in water/steam cycles of all types of power plants. The crucial factor that governs the deposition process and influences the deposition rate of magnetite is the electrostatic interaction between the metal wall surfaces and the suspended colloidal particles. However, there is scarcity of data on magnetite surface properties at elevated temperatures due to difficulties in their experimental measurement. In this paper a generalized overview of existing experimental data on surface characteristics of magnetite at high temperatures is presented with particular emphasis on possible application in the power industry. A thorough analysis of experimental techniques, mathematical models and results has been performed and directions for future investigations have been considered. The state-of-the-art assessment showed that for the characterization of magnetite/aqueous electrolyte solution interface at high temperatures acid-base potentiometric titrations and electrophoresis were the most beneficial and dependable techniques which yielded results up to 290 and 200°C, respectively. Mass titrations provided data on magnetite surface charge up to 320°C, however, this technique is highly sensitive to the minor concentrations of impurities present on the surface of particle. Generally, fairly good correlation between the isoelectric point (pH iep ) and point of zero charge

Highly Quantitative Electrochemical Characterization of Non-Aqueous Electrolytes & Solid Electrolyte Interphases

Energy Technology Data Exchange (ETDEWEB)

Sergiy V. Sazhin; Kevin L. Gering; Mason K. Harrup; Harry W. Rollins

2012-10-01

The methods to measure solid electrolyte interphase (SEI) electrochemical properties and SEI formation capability of non-aqueous electrolyte solutions are not adequately addressed in the literature. And yet, there is a strong demand in new electrolyte generations that promote stabilized SEIs and have an influence to resolve safety, calendar life and other limitations of Li-ion batteries. To fill this gap, in situ electrochemical approach with new descriptive criteria for highly quantitative characterization of SEI and electrolytes is proposed. These criteria are: SEI formation capacity, SEI corrosion rate, SEI maintenance rate, and SEI kinetic stability. These criteria are associated with battery parameters like irreversible capacity, self-discharge, shelf-life, power, etc. Therefore, they are especially useful for electrolyte development and standard fast screening, allowing a skillful approach to narrow down the search for the best electrolyte. The characterization protocol also allows retrieving information on interfacial resistance for SEI layers and the electrochemical window of electrolytes, the other important metrics of characterization. The method validation was done on electrolyte blends containing phosphazenes, developed at Idaho National Laboratory, as 1.2M LiPF6 [80 % EC-MEC (2:8) (v/v) + 20% Phosphazene variety] (v/v), which were targeted for safer electrolyte variations.

High-performance electrodes for reduced temperature solid oxide fuel cells with doped lanthanum gallate electrolyte. II. La(Sr)CoO 3 cathode

Science.gov (United States)

Inagaki, Toru; Miura, Kazuhiro; Yoshida, Hiroyuki; Maric, Radenka; Ohara, Satoshi; Zhang, Xinge; Mukai, Kazuo; Fukui, Takehisa

The reduced temperature solid oxide fuel cell (SOFC) with 0.5 mm thick La 0.9Sr 0.1Ga 0.8Mg 0.2O 3- α (LSGM) electrolyte, La 0.6Sr 0.4CoO 3- δ (LSCo) cathode, and Ni-(CeO 2) 0.8(SmO 1.5) 0.2 (SDC) cermet anode showed an excellent initial performance, and high maximum power density, 0.47 W/cm 2, at 800°C. The results were comparable to those for the conventional SOFC with yttria-stabilized zirconia (YSZ) electrolyte, La(Sr)MnO 3-YSZ cathode and Ni-YSZ cermet anode at 1000°C. Using an LSCo powder prepared by spray pyrolysis, and selecting appropriate sintering temperatures, the lowest cathodic polarization of about 25 mV at 300 mA/cm 2 was measured for a cathode prepared by sintering at 1000°C. Life time cell test results, however, showed that the polarization of the LSCo cathode increased with operating time. From EPMA results, this behavior was considered to be related to the interdiffusion of the elements at the cathode/electrolyte interface. Calcination of LSCo powder could be a possible way to suppress this interdiffusion at the interface.

Room temperature rechargeable polymer electrolyte batteries

Energy Technology Data Exchange (ETDEWEB)

Alamgir, M. [EIC Labs., Inc., Norwood, MA (United States); Abraham, K.M. [EIC Labs., Inc., Norwood, MA (United States)

1995-03-01

Polyacrylonitrile (PAN)- and poly(vinyl chloride) (PVC)-based Li{sup +}-conductive thin-film electrolytes have been found to be suitable in rechargeable Li and Li-ion cells. Li/Li{sub x}Mn{sub 2}O{sub y} and carbon/LiNiO{sub 2} cells fabricated with these electrolytes have demonstrated rate capabilities greater than the C-rate and more than 375 full depth cycles. Two-cell carbon/LiNiO{sub 2} bipolar batteries could be discharged at pulse currents as high as 50 mA/cm{sup 2}. (orig.)

Investigation of electrolyte leaching in the performance degradation of phosphoric acid-doped polybenzimidazole membrane-based high temperature fuel cells

Science.gov (United States)

Jeong, Yeon Hun; Oh, Kyeongmin; Ahn, Sungha; Kim, Na Young; Byeon, Ayeong; Park, Hee-Young; Lee, So Young; Park, Hyun S.; Yoo, Sung Jong; Jang, Jong Hyun; Kim, Hyoung-Juhn; Ju, Hyunchul; Kim, Jin Young

2017-09-01

Precise monitoring of electrolyte leaching in high-temperature polymer electrolyte membrane fuel cell (HT-PEMFC) devices during lifetime tests is helpful in making a diagnosis of their quality changes and analyzing their electrochemical performance degradation. Here, we investigate electrolyte leaching in the performance degradation of phosphoric acid (PA)-doped polybenzimidazole (PBI) membrane-based HT-PEMFCs. We first perform quantitative analyses to measure PA leakage during cell operation by spectrophotometric means, and a higher PA leakage rate is detected when the current density is elevated in the cell. Second, long-term degradation tests under various current densities of the cells and electrochemical impedance spectroscopy (EIS) analysis are performed to examine the influence of PA loss on the membrane and electrodes during cell performance degradation. The combined results indicate that PA leakage affect cell performance durability, mostly due to an increase in charge transfer resistance and a decrease in the electrochemical surface area (ECSA) of the electrodes. Additionally, a three-dimensional (3-D) HT-PEMFC model is applied to a real-scale experimental cell, and is successfully validated against the polarization curves measured during various long-term experiments. The simulation results highlight that the PA loss from the cathode catalyst layer (CL) is a significant contributor to overall performance degradation.

Pyrrolidinium-based ionic liquid electrolyte with organic additive and LiTFSI for high-safety lithium-ion batteries

International Nuclear Information System (INIS)

Yang, Binbin; Li, Cuihua; Zhou, Junhui; Liu, Jianhong; Zhang, Qianling

2014-01-01

Highlights: • New ionic liquid electrolytes composed by PYR 13 TFSI and EC/DMC-5%VC. • Mixed electrolyte for use in high-safety lithium-ion batteries. • LiTFSI concentration in IL electrolyte greatly affects the rate capability of the cell. • The optimal mixed electrolyte is ideal for applications at high temperature. - Abstract: In this paper, we report on the physicochemical properties of mixed electrolytes based on an ionic liquid N-propyl-N-methylpyrrolidiniumbis (trifluoromethanesulfonyl) imide (PYR 13 TFSI), organic additives, and lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) for high safety lithium-ion batteries. The proposed optimal content of ionic liquid in the mixed electrolyte is 65 vol%, which results in non- flammability, high thermal stability, a wide electrochemical window of 4.8 V, low viscosity, low bulk resistance and the lowest interface resistance to lithium anode. The effects of the concentration of LiTFSI in the above electrolyte are critical to the rate performance of the LiFePO 4 -based battery. We have found the suitable LiTFSI concentration (0.3 M) for good capacity retention and rate capability

Designed synergetic effect of electrolyte additives to improve interfacial chemistry of MCMB electrode in propylene carbonate-based electrolyte for enhanced low and room temperature performance.

Science.gov (United States)

Wotango, Aselefech Sorsa; Su, Wei-Nien; Haregewoin, Atetegeb Meazah; Chen, Hung-Ming; Cheng, Ju-Hsiang; Lin, Ming-Hsien; Wang, Chia-Hsin; Hwang, Bing-Joe

2018-05-09

The performance of lithium ion batteries rapidly falls at lower temperatures due to decreasing conductivity of electrolytes and Solid Electrolyte Interphase (SEI) on graphite anode. Hence, it limits the practical use of lithium ion batteries at sub-zero temperatures and also affects the development of lithium ion batteries for widespread applications. The SEI formed on the graphite surface is very influential in determining the performance of the battery. Herein, a new electrolyte additive, 4-Chloromethyl-1,3,2-dioxathiolane-2-oxide (CMDO), is prepared to improve the properties of commonly used electrolyte constituents - ethylene carbonate (EC), and fluoroethylene carbonate (FEC). The formation of an efficient passivation layer in propylene carbonate (PC) -based electrolyte for MCMB electrode was investigated. The addition of CMDO resulted in a much less irreversible capacity loss and induces thin SEI formation. However, the combination of the three additives played a key role to enhance reversible capacity of MCMB electrode at lower or ambient temperature. The electrochemical measurement analysis showed that the SEI formed from a mixture of the three additives gave better intercalation-deintercalation of lithium ions.

Electrochemical Properties and Speciation in Mg(HMDS)2-Based Electrolytes for Magnesium Batteries as a Function of Ethereal Solvent Type and Temperature.

Science.gov (United States)

Merrill, Laura C; Schaefer, Jennifer L

2017-09-19

Magnesium batteries are a promising alternative to lithium-ion batteries due to the widespread abundance of magnesium and its high specific volumetric energy capacity. Ethereal solvents such as tetrahydrofuran (THF) are commonly used for magnesium-ion electrolytes due to their chemical compatibility with magnesium metal, but the volatile nature of THF is a concern for practical application. Herein, we investigate magnesium bis(hexamethyldisilazide) plus aluminum chloride (Mg(HMDS) 2 -AlCl 3 ) electrolytes in THF, diglyme, and tetraglyme at varying temperature. We find that, despite the higher thermal stability of the glyme-based electrolytes, THF-based electrolytes have better reversibility at room temperature. Deposition/stripping efficiency is found to be a strong function of temperature. Diglyme-based Mg(HMDS) 2 -AlCl 3 electrolytes are found to not exchange as quickly as THF and tetraglyme, stabilizing AlCl 2 + and facilitating undesired aluminum deposition. Raman spectroscopy, 27 Al NMR, and mass spectrometry are used to identify solution speciation.

Dextran based highly conductive hydrogel polysulfide electrolyte for efficient quasi-solid-state quantum dot-sensitized solar cells

International Nuclear Information System (INIS)

Chen, Hong-Yan; Lin, Ling; Yu, Xiao-Yun; Qiu, Kang-Qiang; Lü, Xian-Yong; Kuang, Dai-Bin; Su, Cheng-Yong

2013-01-01

Highlights: ► Dextran based hydrogel is first used to prepare quasi-solid-state polysulfide electrolyte for quantum dot-sensitized solar cells. ► The ion conductivity of hydrogel electrolyte shows almost the same value as the liquid electrolyte. ► The liquid state at elevated temperature of hydrogel electrolyte allows for a good contact between electrolyte and CdS/CdSe co-sensitized TiO 2 photoanode. ► The hydrogel electrolyte based cell exhibits slightly lower power conversion efficiency than that of liquid electrolyte based cell. ► The dynamic electron transfer mechanism in hydrogel electrolyte based cell is examined in detail by EIS and CIMPS/IMVS. -- Abstract: Highly conductive hydrogel polysulfide electrolyte is first fabricated using dextran as gelator and used as quasi-solid-state electrolyte for quantum dot-sensitized solar cells (QDSSCs). The hydrogel electrolyte with gelator concentration of 15 wt% shows almost the same conductivity as the liquid one. Moreover, its liquid state at elevated temperature allow for the well penetration into the pores in electrodeposited CdS/CdSe co-sensitized TiO 2 photoanode. This gel electrolyte based QDSSC exhibits power conversion efficiency (η) of 3.23% under AG 1.5 G one sun (100 mW cm −2 ) illumination, slightly lower than that of liquid electrolyte based cell (3.69%). The dynamic electron transfer mechanism of the gel and liquid electrolyte based QDSSC are examined by electrochemical impedance spectroscopy (EIS) and controlled intensity modulated photocurrent/photovoltage spectroscopy (CIMPS/IMVS). It is found that the electron transport in gel electrolyte based cell is much faster than the liquid electrolyte based cell but it tends to recombine more easily than the latter. However, these differences fade away with increasing the light intensity, showing declining electron collection efficiency at higher light intensity illumination. As a result, a conversion efficiency of 4.58% is obtained for the gel

Elastic modulus and internal friction of SOFC electrolytes at high temperatures under controlled atmospheres

Science.gov (United States)

Kushi, Takuto; Sato, Kazuhisa; Unemoto, Atsushi; Hashimoto, Shinichi; Amezawa, Koji; Kawada, Tatsuya

2011-10-01

Mechanical properties such as Young's modulus, shear modulus, Poisson's ratio and internal friction of conventional electrolyte materials for solid oxide fuel cells, Zr0.85Y0.15 O1.93 (YSZ), Zr0.82Sc0.18O1.91 (ScSZ), Zr0.81Sc0.18Ce0.01O2-δ (ScCeSZ), Ce0.9Gd0.1O2-δ (GDC), La0.8Sr0.2Ga0.8Mg0.15Co0.05O3-δ (LSGMC), La0.8Sr0.2Ga0.8Mg0.2O3-δ (LSGM), were evaluated by a resonance method at temperatures from room temperature to 1273 K in various oxygen partial pressures. The Young's modulus of GDC gradually decreased with increasing temperature in oxidizing conditions. The Young's moduli of the series of zirconia and lanthanum gallate based materials drastically decreased in an intermediate temperature range and increased slightly with increasing temperature at higher temperatures. The Young's modulus of GDC considerably decreased above 823 K in reducing atmospheres in response to the change of oxygen nonstoichiometry. However, temperature dependences of the Young's moduli of ScCeSZ and LSGMC in reducing atmospheres did not show any significant differences with those in oxidizing atmospheres.

Physicochemical, spectroscopic and electrochemical characterization of magnesium ion-conducting, room temperature, ternary molten electrolytes

Science.gov (United States)

Narayanan, N. S. Venkata; Ashok Raj, B. V.; Sampath, S.

Room temperature, magnesium ion-conducting molten electrolytes are prepared using a combination of acetamide, urea and magnesium triflate or magnesium perchlorate. The molten liquids show high ionic conductivity, of the order of mS cm -1 at 298 K. Vibrational spectroscopic studies based on triflate/perchlorate bands reveal that the free ion concentration is higher than that of ion-pairs and aggregates in the melt. Electrochemical reversibility of magnesium deposition and dissolution is demonstrated using cyclic voltammetry and impedance studies. The transport number of Mg 2+ ion determined by means of a combination of d.c. and a.c. techniques is ∼0.40. Preliminary studies on the battery characteristics reveal good capacity for the magnesium rechargeable cell and open up the possibility of using this unique class of acetamide-based room temperature molten electrolytes in secondary magnesium batteries.

High voltage AC/AC electrochemical capacitor operating at low temperature in salt aqueous electrolyte

Science.gov (United States)

Abbas, Qamar; Béguin, François

2016-06-01

We demonstrate that an activated carbon (AC)-based electrochemical capacitor implementing aqueous lithium sulfate electrolyte in 7:3 vol:vol water/methanol mixture can operate down to -40 °C with good electrochemical performance. Three-electrode cell investigations show that the faradaic contributions related with hydrogen chemisorption in the negative AC electrode are thermodynamically unfavored at -40 °C, enabling the system to work as a typical electrical double-layer (EDL) capacitor. After prolonged floating of the AC/AC capacitor at 1.6 V and -40°C, the capacitance, equivalent series resistance and efficiency remain constant, demonstrating the absence of ageing related with side redox reactions at this temperature. Interestingly, when temperature is increased back to 24 °C, the redox behavior due to hydrogen storage reappears and the system behaves as a freshly prepared one.

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).

High-performance supercapacitors of carboxylate-modified hollow carbon nanospheres coated on flexible carbon fibre paper: Effects of oxygen-containing group contents, electrolytes and operating temperature

International Nuclear Information System (INIS)

Phattharasupakun, Nutthaphon; Wutthiprom, Juthaporn; Suktha, Phansiri; Iamprasertkun, Pawin; Chanlek, Narong; Shepherd, Celine; Hadzifejzovic, Emina; Moloney, Mark G.; Foord, John S.; Sawangphruk, Montree

2017-01-01

Although functionalized carbon-based materials have been widely used as the supercapacitor electrodes, the optimum contents of the functional groups, the charge storage mechanisms, and the effects of electrolytes and operating temperature have not yet been clearly investigated. In this work, carboxylate-modified hollow carbon nanospheres (c-HCN) with different functional group contents synthesized by an oxidation process of carbon nanospheres with nitric acid were coated on flexible carbon fibre paper and used as the supercapacitor electrodes. An as-fabricated supercapacitor of the c-HCN with a finely tuned 6.2 atomic % of oxygen of the oxygen-containing groups in an ionic liquid electrolyte exhibits a specific capacitance of 390 F g"−"1, a specific energy of 115 Wh kg"−"1, and a maximum specific power of 13548 W kg"−"1 at 70 °C. The charge storage mechanism investigated is based on the chemical adsorption of the ionic liquid electrolyte on the c-HCN electrode. This process is highly reversible leading to high capacity retention. The supercapacitor in this work may be practically used in many high energy and power applications.

High performance direct methanol fuel cell with thin electrolyte membrane

Science.gov (United States)

Wan, Nianfang

2017-06-01

A high performance direct methanol fuel cell is achieved with thin electrolyte membrane. 320 mW cm-2 of peak power density and over 260 mW cm-2 at 0.4 V are obtained when working at 90 °C with normal pressure air supply. It is revealed that the increased anode half-cell performance with temperature contributes primarily to the enhanced performance at elevated temperature. From the comparison of iR-compensated cathode potential of methanol/air with that of H2/air fuel cell, the impact of methanol crossover on cathode performance decreases with current density and becomes negligible at high current density. Current density is found to influence fuel efficiency and methanol crossover significantly from the measurement of fuel efficiency at different current density. At high current density, high fuel efficiency can be achieved even at high temperature, indicating decreased methanol crossover.

Application of a Coated Film Catalyst Layer Model to a High Temperature Polymer Electrolyte Membrane Fuel Cell with Low Catalyst Loading Produced by Reactive Spray Deposition Technology

Directory of Open Access Journals (Sweden)

Timothy D. Myles

2015-10-01

Full Text Available In this study, a semi-empirical model is presented that correlates to previously obtained experimental overpotential data for a high temperature polymer electrolyte membrane fuel cell (HT-PEMFC. The goal is to reinforce the understanding of the performance of the cell from a modeling perspective. The HT-PEMFC membrane electrode assemblies (MEAs were constructed utilizing an 85 wt. % phosphoric acid doped Advent TPS® membranes for the electrolyte and gas diffusion electrodes (GDEs manufactured by Reactive Spray Deposition Technology (RSDT. MEAs with varying ratios of PTFE binder to carbon support material (I/C ratio were manufactured and their performance at various operating temperatures was recorded. The semi-empirical model derivation was based on the coated film catalyst layer approach and was calibrated to the experimental data by a least squares method. The behavior of important physical parameters as a function of I/C ratio and operating temperature were explored.

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.

Carbonate-linked poly(ethylene oxide) polymer electrolytes towards high performance solid state lithium batteries

International Nuclear Information System (INIS)

He, Weisheng; Cui, Zili; Liu, Xiaochen; Cui, Yanyan; Chai, Jingchao; Zhou, Xinhong; Liu, Zhihong; Cui, Guanglei

2017-01-01

The classic poly(ethylene oxide) (PEO) based solid polymer electrolyte suffers from poor ionic conductivity of ambient temperature, low lithium ion transference number and relatively narrow electrochemical window (<4.0 V vs. Li + /Li). Herein, the carbonate-linked PEO solid polymer such as poly(diethylene glycol carbonate) (PDEC) and poly(triethylene glycol carbonate) (PTEC) were explored to find out the feasibility of resolving above issues. It was proven that the optimized ionic conductivity of PTEC based electrolyte reached up to 1.12 × 10 −5 S cm −1 at 25 °C with a decent lithium ion transference number of 0.39 and a wide electrochemical window about 4.5 V vs. Li + /Li. In addition, the PTEC based Li/LiFePO 4 cell could be reversibly charged and discharged at 0.05 C-rates at ambient temperature. Moreover, the higher voltage Li/LiFe 0.2 Mn 0.8 PO 4 cell (cutoff voltage 4.35 V) possessed considerable rate capability and excellent cycling performance even at ambient temperature. Therefore, these carbonate-linked PEO electrolytes were demonstrated to be fascinating candidates for the next generation solid state lithium batteries simultaneously with high energy and high safety.

Intermediate temperature solid oxide fuel cell based on lanthanum gallate electrolyte

Science.gov (United States)

Inagaki, Toru; Nishiwaki, Futoshi; Yamasaki, Satoru; Akbay, Taner; Hosoi, Kei

The Kansai Electric Power Co. Inc. (KEPCO) and Mitsubishi Materials Corporation (MMC) have been developing intermediate temperature solid oxide fuel cells (IT-SOFCs) which are operable at a temperature range between 600 and 800 °C. There are some significant features in IT-SOFC of KEPCO-MMC: (1) highly conductive lanthanum gallate-based oxide is adopted as an electrolyte to realize high-performance disk-type electrolyte-supported cells; (2) the cell-stacks with seal-less structure using metallic separators allow residual fuel to burn around the stack and the combustion heat is utilized for thermally self-sustainable operation; (3) the separators have flexible arms by which separate compressive forces can be applied for manifold parts and interconnection parts. We are currently participating in the project by New Energy and Industrial Technology Development Organization (NEDO) to develop 10 kW-class combined heat and power (CHP) systems. In FY2006, a 10 kW-class module was developed, with which the electrical efficiency of 50%HHV was obtained based on DC 12.6 kW. In the first quarter of FY2007, the 10 kW-class CHP system using the module gave the electrical efficiency of 41%HHV on AC 10 kW and the overall efficiency of 82%HHV when exhaust heat was recovered as 60 °C hot water. Currently, the operation has been accumulated for about 2500 h to evaluate the long-term stability of the system.

Intermediate temperature solid oxide fuel cell based on lanthanum gallate electrolyte

Energy Technology Data Exchange (ETDEWEB)

Inagaki, Toru; Nishiwaki, Futoshi; Yamasaki, Satoru [The Kansai Electric Power Co. Inc., Energy Use R and D Center, 11-20 Nakoji 3-choume, Amagasaki, Hyogo 661-0974 (Japan); Akbay, Taner; Hosoi, Kei [Mitsubishi Materials Corporation, Corporate Technology and Development Division, 1002-14 Mukohyama, Naka, Ibaraki 311-0102 (Japan)

2008-07-01

The Kansai Electric Power Co. Inc. (KEPCO) and Mitsubishi Materials Corporation (MMC) have been developing intermediate temperature solid oxide fuel cells (IT-SOFCs) which are operable at a temperature range between 600 and 800 C. There are some significant features in IT-SOFC of KEPCO-MMC: (1) highly conductive lanthanum gallate-based oxide is adopted as an electrolyte to realize high-performance disk-type electrolyte-supported cells; (2) the cell-stacks with seal-less structure using metallic separators allow residual fuel to burn around the stack and the combustion heat is utilized for thermally self-sustainable operation; (3) the separators have flexible arms by which separate compressive forces can be applied for manifold parts and interconnection parts. We are currently participating in the project by New Energy and Industrial Technology Development Organization (NEDO) to develop 10 kW-class combined heat and power (CHP) systems. In FY2006, a 10 kW-class module was developed, with which the electrical efficiency of 50%HHV was obtained based on DC 12.6 kW. In the first quarter of FY2007, the 10 kW-class CHP system using the module gave the electrical efficiency of 41%HHV on AC 10 kW and the overall efficiency of 82%HHV when exhaust heat was recovered as 60 C hot water. Currently, the operation has been accumulated for about 2500 h to evaluate the long-term stability of the system. (author)

Improvement of lithium-ion battery performance at low temperature by adopting polydimethylsiloxane-based electrolyte additives

International Nuclear Information System (INIS)

Kim, Kwang Man; Ly, Nguyen Vu; Won, Jung Ha; Lee, Young-Gi; Cho, Won Il; Ko, Jang Myoun; Kaner, Richard B.

2014-01-01

Three kinds of polydimethylsiloxane (PDMS)-based grafted and ungrafted copolymers such as poly[dimethylsiloxane-co-(siloxane-g-acrylate)] (PDMS-A), poly(dimethylsiloxane-co-phenylsiloxane) (PDMS-P), and poly[dimethylsiloxane-co-(siloxane-g-ethylene oxide)] (PDMS-EO) are used as additives to standard liquid electrolyte solutions to enhance the lithium-ion battery performance at low temperatures. Liquid electrolyte solutions with PDMS-based additives are electrochemically stable under 5.0 V and have adequate ionic conductivities of 10 −4 S cm −1 at -20 °C. Particularly, liquid electrolytes with PDMS-P and PDMS-EO exhibit higher ionic conductivities of around 5 × 10 −4 S cm −1 at -20 °C, indicating a specific resisting property against the freezing of the liquid electrolyte components. As a result, the addition of PDMS-based additives to liquid electrolytes improves the capacity retention ratio and rate-capability of lithium-ion batteries at low temperatures

Study Progress of Physiological Responses in High Temperature Environment

Science.gov (United States)

Li, K.; Zheng, G. Z.; Bu, W. T.; Wang, Y. J.; Lu, Y. Z.

2017-10-01

Certain workers are exposed to high temperatures for a long time. Heat stress will result in a series of physiological responses, and cause adverse effects on the health and safety of workers. This paper summarizes the physiological changes of cardiovascular system, core temperature, skin temperature, water-electrolyte metabolism, alimentary system, neuroendocrine system, reaction time and thermal fatigue in high temperature environments. It can provide a theoretical guidance for labor safety in high temperature environment.

Electrolytes for solid oxide fuel cells

Science.gov (United States)

Fergus, Jeffrey W.

The high operating temperature of solid oxide fuel cells (SOFCs), as compared to polymer electrolyte membrane fuel cells (PEMFCs), improves tolerance to impurities in the fuel, but also creates challenges in the development of suitable materials for the various fuel cell components. In response to these challenges, intermediate temperature solid oxide fuel cells (IT-SOFCs) are being developed to reduce high-temperature material requirements, which will extend useful lifetime, improve durability and reduce cost, while maintaining good fuel flexibility. A major challenge in reducing the operating temperature of SOFCs is the development of solid electrolyte materials with sufficient conductivity to maintain acceptably low ohmic losses during operation. In this paper, solid electrolytes being developed for solid oxide fuel cells, including zirconia-, ceria- and lanthanum gallate-based materials, are reviewed and compared. The focus is on the conductivity, but other issues, such as compatibility with electrode materials, are also discussed.

Electrolytes for solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Fergus, Jeffrey W. [Auburn University, Materials Research and Education Center, 275 Wilmore Laboratories, Auburn, AL 36849 (United States)

2006-11-08

The high operating temperature of solid oxide fuel cells (SOFCs), as compared to polymer electrolyte membrane fuel cells (PEMFCs), improves tolerance to impurities in the fuel, but also creates challenges in the development of suitable materials for the various fuel cell components. In response to these challenges, intermediate temperature solid oxide fuel cells (IT-SOFCs) are being developed to reduce high-temperature material requirements, which will extend useful lifetime, improve durability and reduce cost, while maintaining good fuel flexibility. A major challenge in reducing the operating temperature of SOFCs is the development of solid electrolyte materials with sufficient conductivity to maintain acceptably low ohmic losses during operation. In this paper, solid electrolytes being developed for solid oxide fuel cells, including zirconia-, ceria- and lanthanum gallate-based materials, are reviewed and compared. The focus is on the conductivity, but other issues, such as compatibility with electrode materials, are also discussed. (author)

Non-aqueous electrolyte for high voltage rechargeable magnesium batteries

Science.gov (United States)

Doe, Robert Ellis; Lane, George Hamilton; Jilek, Robert E; Hwang, Jaehee

2015-02-10

An electrolyte for use in electrochemical cells is provided. The properties of the electrolyte include high conductivity, high Coulombic efficiency, and an electrochemical window that can exceed 3.5 V vs. Mg/Mg.sup.+2. The use of the electrolyte promotes the electrochemical deposition and dissolution of Mg without the use of any Grignard reagents, other organometallic materials, tetraphenyl borate, or tetrachloroaluminate derived anions. Other Mg-containing electrolyte systems that are expected to be suitable for use in secondary batteries are also described.

Novel proton conducting polymer electrolytes based on polyparabanic acid doped with H 3PO 4 for high temperature fuel cell

Science.gov (United States)

Aihara, Yuichi; Sonai, Atsuo

Three novel proton conducting polymer electrolytes based on polyparabanic acid doped with H 3PO 4 were synthesized and their use in high temperature fuel cells characterized. The precursor polymers, PMD-Im, POD-Im and PDMDP-Im, were synthesized by cyclization polymerization of diisocynanates. After doping with H 3PO 4, the ionic conductivity and the thermal degradation were studied by using the AC impedance method and thermal gravimetric analysis, respectively. These membranes showed high ionic conductivity of the order of 10 -2 S cm -1 at 423 K with good thermal stability. Their application to fuel cells was demonstrated and polarization curves were obtained at 423 K were obtained without humidification.

High-performance electrodes for reduced temperature solid oxide fuel cells with doped lanthanum gallate electrolyte. Pt. 2. La(Sr)CoO{sub 3} cathode

Energy Technology Data Exchange (ETDEWEB)

Inagaki, Toru; Yoshida, Hiroyuki [The Kansai Electric Power, Hyogo (Japan); Miura, Kazuhiro [Kanden Kakou, Hyogo (Japan); Maric, Radenka; Ohara, Satoshi; Zhang, Xinge; Mukai, Kazuo; Fukui, Takehisa [Japan Fine Ceramics Center, Nagoya (Japan)

2000-03-01

The reduced temperature solid oxide fuel cell (SOFC) with 0.5 mm thick La{sub 0.9}Sr{sub 0.1}Ga{sub 0.8}Mg{sub 0.2}O{sub 3-{alpha}} (LSGM) electrolyte, La{sub 0.6}Sr{sub 0.4}CoO{sub 3-{delta}} (LSCo) cathode, and Ni-(CeO{sub 2}){sub 0.8}(SmO{sub 1.5}){sub 0.2} (SDC) cermet anode showed an excellent initial performance, and high maximum power density, 0.47 W/cm{sup 2}, at 800 C. The results were comparable to those for the conventional SOFC with yttria-stabilized zirconia (YSZ) electrolyte, La(Sr)MnO{sub 3}-YSZ cathode and Ni-YSZ cermet anode at 1000 C. Using an LSCo powder prepared by spray pyrolysis, and selecting appropriate sintering temperatures, the lowest cathodic polarization of about 25 mV at 300 mA/cm{sup 2} was measured for a cathode prepared by sintering at 1000 C. Life time cell test results, however, showed that the polarization of the LSCo cathode increased with operating time. From EPMA results, this behavior was considered to be related to the interdiffusion of the elements at the cathode/electrolyte interface. Calcination of LSCo powder could be a possible way to suppress this interdiffusion at the interface. (orig.)

Thermostable gel polymer electrolyte based on succinonitrile and ionic liquid for high-performance solid-state supercapacitors

Science.gov (United States)

Pandey, Gaind P.; Liu, Tao; Hancock, Cody; Li, Yonghui; Sun, Xiuzhi Susan; Li, Jun

2016-10-01

A flexible, free-standing, thermostable gel polymer electrolyte based on plastic crystalline succinonitrile (SN) and ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (BMImBF4) entrapped in copolymer poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) is prepared and optimized for application in solvent-free solid-state supercapacitors. The synthesized gel polymer electrolyte exhibits a high ionic conductivity over a wide temperature range (from ∼5 × 10-4 S cm-1 at -30 °C up to ∼1.5 × 10-2 S cm-1 at 80 °C) with good electrochemical stability window (-2.9 to 2.5 V). Thermal studies confirm that the SN containing gel polymer electrolyte remains stable in the same gel phase over a wide temperature range from -30 to 90 °C. The electric double layer capacitors (EDLCs) have been fabricated using activated carbon as active materials and new gel polymer electrolytes. Electrochemical performance of the EDLCs is assessed through cyclic voltammetry, galvanostatic charge-discharge cycling and impedance spectroscopy. The EDLC cells with the proper SN-containing gel polymer electrolyte has been found to give high specific capacitance 176 F g-1 at 0.18 A g-1 and 138 F g-1 at 8 A g-1. These solid-state EDLC cells show good cycling stability and the capability to retain ∼80% of the initial capacitance after 10,000 cycles.

High temperature electrolysis for hydrogen production using nuclear energy

International Nuclear Information System (INIS)

Herring, J. Stephen; O'brien, James E.; Stoots, Carl M.; Hawkes, Grant L.; Hartvigsen, Joseph J.

2005-01-01

High-temperature nuclear reactors have the potential for substantially increasing the efficiency of hydrogen production from water splitting, which can be accomplished via high-temperature electrolysis (HTE) or thermochemical processes. In order to achieve competitive efficiencies, both processes require high-temperature operation (∼850degC). High-temperature electrolytic water splitting supported by nuclear process heat and electricity has the potential to produce hydrogen with overall system efficiencies of 45 to 55%. At the Idaho National Laboratory, we are developing solid-oxide cells to operate in the steam electrolysis mode. The research program includes both experimental and modeling activities. Experimental results were obtained from ten-cell and 22-cell planar electrolysis stacks, fabricated by Ceramatec, Inc. The electrolysis cells are electrolyte-supported, with scandia-stabilized zirconia electrolytes (∼200 μm thick, 64 cm 2 active area), nickel-cermet steam/hydrogen electrodes, and manganite air-side electrodes. The metallic interconnect plates are fabricated from ferritic stainless steel. The experiments were performed over a range of steam inlet mole fractions, gas glow rates, and current densities. Hydrogen production rates greater than 100 normal liters per hour for 196 hours have been demonstrated. In order to evaluate the performance of large-scale HTE operations, we have developed single-cell models, based on FLUENT, and a process model, using the systems-analysis code HYSYS. (author)

Contact Resistance of Tantalum Coatings in Fuel Cells and Electrolyzers using Acidic Electrolytes at Elevated Temperatures

DEFF Research Database (Denmark)

Jensen, Annemette Hindhede; Christensen, Erik; Barner, Jens H. Von

2014-01-01

stainless steel were found to be far below the US Department of Energy target value of 10mcm2. The good contact resistance of tantalum was demonstrated by simulating high temperature polymer electrolyte membrane electrolysis conditions by anodization performed in 85% phosphoric acid at 130◦C, followed...

Mechanistic Study of Electrolyte Additives to Stabilize High-Voltage Cathode–Electrolyte Interface in Lithium-Ion Batteries

Energy Technology Data Exchange (ETDEWEB)

Gao, Han [Chemical; Maglia, Filippo [BMW Group, Munich 80788, Germany; Lamp, Peter [BMW Group, Munich 80788, Germany; Amine, Khalil [Chemical; Chen, Zonghai [Chemical

2017-12-13

Current developments of electrolyte additives to stabilize electrode-electrolyte interface in Li-ion batteries highly rely on a trial-and-error search, which involves repetitive testing and intensive amount of resources. The lack of understandings on the fundamental protection mechanisms of the additives significantly increases the difficulty for the transformational development of new additives. In this study, we investigated two types of individual protection routes to build a robust cathode-electrolyte interphase at high potentials: (i) a direct reduction in the catalytic decomposition of the electrolyte solvent; and (ii) formation of a “corrosion inhibitor film” that prevents severely attack and passivation from protons that generated from the solvent oxidation, even the decomposition of solvent cannot not mitigated. Effect of three exemplary electrolyte additives: (i) lithium difluoro(oxalato)borate (LiDFOB); (ii) 3-hexylthiophene (3HT); and (iii) tris(hexafluoro-iso-propyl)phosphate (HFiP), on LiNi0.6Mn0.2Co0.2O2 (NMC 622) cathode were investigated to validate our hypothesis. It is demonstrated that understandings of both electrolyte additives and solvent are essential and careful balance between the cathode protection mechanism of additives and their side effects is critical to obtain optimum results. More importantly, this study opens up new directions of rational design of functional electrolyte additives for the next generation high-energy density lithium-ion chemistries.

Single-ion polymer electrolyte membranes enable lithium-ion batteries with a broad operating temperature range.

Science.gov (United States)

Cai, Weiwei; Zhang, Yunfeng; Li, Jing; Sun, Yubao; Cheng, Hansong

2014-04-01

Conductive processes involving lithium ions are analyzed in detail from a mechanistic perspective, and demonstrate that single ion polymeric electrolyte (SIPE) membranes can be used in lithium-ion batteries with a wide operating temperature range (25-80 °C) through systematic optimization of electrodes and electrode/electrolyte interfaces, in sharp contrast to other batteries equipped with SIPE membranes that display appreciable operability only at elevated temperatures (>60 °C). The performance is comparable to that of batteries using liquid electrolyte of inorganic salt, and the batteries exhibit excellent cycle life and rate performance. This significant widening of battery operation temperatures coupled with the inherent flexibility and robustness of the SIPE membranes makes it possible to develop thin and flexible Li-ion batteries for a broad range of applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Conductivity determination of electrolytes at high pressure and temperature

International Nuclear Information System (INIS)

Crovetto, Rosa; Gutierrez, Norberto; Petragalli, I.P

1981-01-01

An experimental layout is designed that would allow operation up to 350 deg C and 10 8 Pascal, thus facilitating measurements of conductivity in electrolytes with an accuracy of 0.1%. The unit was tested with ClK solutions at 25 deg C and pressures up to 6 x 10 7 Pascal, showing that under these conditions it yields results in good agreement with the electric conductivity data found in the bibliography. (M.E.L.) [es

Design of high quality doped CeO2 solid electrolytes with nanohetero structure

International Nuclear Information System (INIS)

Mori, T.; Ou, D.R.; Ye, F.; Drennan, J.

2006-01-01

Doped cerium (CeO 2 ) compounds are fluorite related oxides which show oxide ionic conductivity higher than yttria-stabilized zirconia in oxidizing atmosphere. As a consequence of this, a considerable interest has been shown in application of these materials for low (400-650 o C) temperature operation of solid oxide fuel cells (SOFCs). In this paper, our experimental data about the influence of microstructure at the atomic level on electrochemical properties were reviewed in order to develop high quality doped CeO 2 electrolytes in fuel cell applications. Using this data in the present paper, our original idea for a design of nanodomain structure in doped CeO 2 electrolytes was suggested. The nanosized powders and dense sintered bodies of M doped CeO 2 (M:Sm,Gd,La,Y,Yb, and Dy) compounds were fabricated. Also nanostructural features in these specimens were introduced for conclusion of relationship between electrolytic properties and domain structure in doped CeO 2 . It is essential that the electrolytic properties in doped CeO 2 solid electrolytes reflect in changes of microstructure even down to the atomic scale. Accordingly, a combined approach of nanostructure fabrication, electrical measurement and structure characterization was required to develop superior quality doped CeO 2 electrolytes in the fuel cells. (author)

High-temperature materials and structural ceramics

International Nuclear Information System (INIS)

1990-01-01

This report gives a survey of research work in the area of high-temperature materials and structural ceramics of the KFA (Juelich Nuclear Research Center). The following topics are treated: (1) For energy facilities: ODS materials for gas turbine blades and heat exchangers; assessment of the remaining life of main steam pipes, material characterization and material stress limits for First-Wall components; metallic and graphitic materials for high-temperature reactors. (2) For process engineering plants: composites for reformer tubes and cracking tubes; ceramic/ceramic joints and metal/ceramic and metal/metal joints; Composites and alloys for rolling bearing and sliding systems up to application temperatures of 1000deg C; high-temperature corrosion of metal and ceramic material; porous ceramic high-temperature filters and moulding coat-mix techniques; electrically conducting ceramic material (superconductors, fuel cells, solid electrolytes); high-temperature light sources (high-temperature chemistry); oil vapor engines with caramic components; ODS materials for components in diesel engines and vehicle gas turbines. (MM) [de

Temperature dependence of electrochemical properties of cross-linked poly(ethylene oxide)–lithium bis(trifluoromethanesulfonyl)imide–N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide solid polymer electrolytes for lithium batteries

International Nuclear Information System (INIS)

Wetjen, Morten; Kim, Guk-Tae; Joost, Mario; Winter, Martin; Passerini, Stefano

2013-01-01

Highlights: ► Solid-state electrolyte for lithium batteries. ► Polymer electrolyte with improved mechanical properties by cross-linking. ► Enhanced performance of polymer electrolytes using water- and air-stable ionic liquids as co-salts. ► Polymer electrolyte with high rate capability at moderate temperatures. - Abstract: An advanced electrochemical characterization of cross-linked ternary solid polymer electrolytes (SPEs), prepared by a solvent-free hot-pressing process, is reported. Ionic conductivity, electrochemical stability window and limiting current measurements were performed as a function of the temperature by using both potentiodynamic and galvanostatic techniques. Additionally, the lithium cycleability was evaluated with respect to its dependence on both the operating temperature and the current density by using a new multi-rate Li-stripping-plating procedure. The results clearly indicate the beneficial effect of higher operating temperatures on the rate-capability, without major degradation of the electrochemical stability of the SPE. All-solid-state lithium metal polymer batteries (LMPBs), comprising a lithium metal anode, the cross-linked ternary solid polymer electrolyte and a LiFePO 4 composite cathode, were manufactured and investigated in terms of the interdependencies of the delivered capacity, operating temperature and discharge rate. The results prove quite exceptional delivered capacities both at medium current densities at ambient temperatures and even more impressive capacities above 160 mAh g −1 at high discharge rates (1 C) and temperatures above 60 °C.

High temperature sealing method : induction brazing for SOFCs

Energy Technology Data Exchange (ETDEWEB)

Heo, Y.H.; Lee, S.B.; Song, R.H.; Shin, D.R. [Korea Inst. of Energy Research, Daejeon (Korea, Republic of); Lim, T.H. [Korea Inst. of Energy Research, Daejeon (Korea, Republic of). Advanced Fuel Cell Research Center

2009-07-01

This study examined the use of induction brazing as a high temperature sealing method for solid oxide fuel cells (SOFCs). Nickel-based brazing alloys were modified using reactive titanium-hydride (TiH2). The gas sealing properties of the induction brazing process on anode-supported tubular SOFCs and ferritic stainless steel were evaluated. Brazing alloys BNi-2 and BNi-4 were not wetted in a yttria-silica-zircon (YSZ) electrolyte. The brazing alloy with added TiH2 showed good wettability with the YSZ electrolyte as a result of the formation of a TiOX layer. Only the BNi-4 alloy joined with the YSZ electrolyte. An open circuit voltage (OCV) value was used to estimate the gas tightness of the brazed cell. It was concluded that the BNi-4 TiH2 modified alloy is a suitable sealing material for SOFCs operating in temperatures up to 750 degrees C.

Curious Case of Positive Current Collectors: Corrosion and Passivation at High Temperature.

Science.gov (United States)

Sayed, Farheen N; Rodrigues, Marco-Tulio F; Kalaga, Kaushik; Gullapalli, Hemtej; Ajayan, P M

2017-12-20

In the evaluation of compatibility of different components of cell for high-energy and extreme-conditions applications, the highly focused are positive and negative electrodes and their interaction with electrolyte. However, for high-temperature application, the other components are also of significant influence and contribute toward the total health of battery. In present study, we have investigated the behavior of aluminum, the most common current collector for positive electrode materials for its electrochemical and temperature stability. For electrochemical stability, different electrolytes, organic and room temperature ionic liquids with varying Li salts (LiTFSI, LiFSI), are investigated. The combination of electrochemical and spectroscopic investigations reflects the varying mechanism of passivation at room and high temperature, as different compositions of decomposed complexes are found at the surface of metals.

High voltage rechargeable magnesium batteries having a non-aqueous electrolyte

Science.gov (United States)

Doe, Robert Ellis; Lane, George Hamilton; Jilek, Robert E.; Hwang, Jaehee

2016-03-22

A rechargable magnesium battery having an non-aqueous electrolyte is provided. The properties of the electrolyte include high conductivity, high Coulombic efficiency, and an electrochemical window that can exceed 3.5 V vs. Mg/Mg.sup.+2. The use of the electrolyte promotes the electrochemical deposition and dissolution of Mg without the use of any Grignard reagents, other organometallic materials, tetraphenyl borate, or tetrachloroaluminate derived anions. Other Mg-containing electrolyte systems that are expected to be suitable for use in secondary batteries are also described.

HYFIRE: a tokamak/high-temperature electrolysis system

International Nuclear Information System (INIS)

Fillo, J.A.; Powell, J.P.; Benenati, R.; Varljen, T.C.; Chi, J.W.H.; Karbowski, J.S.

1981-01-01

The HYFIRE studies to date have investigated a number of technical approaches for using the thermal energy produced in a high-temperature Tokamak blanket to provide the electrical and thermal energy required to drive a high-temperature (> 1000 0 C) water electrolysis process. Current emphasis is on two design points, one consistent with electrolyzer peak inlet temperatures of 1400 0 C, which is an extrapolation of present experience, and one consistent with a peak electrolyzer temperature of 1100 0 C. This latter condition is based on current laboratory experience with high-temperature solid electrolyte fuel cells. Our major conclusion to date is that the technical integration of fusion and high-temperature electrolysis appears to be feasible and that overall hydrogen production efficiencies of 50 to 55% seem possible

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.

High flash point electrolyte for use in lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Isken, P.; Dippel, C.; Schmitz, R.; Schmitz, R.W.; Kunze, M.; Passerini, S.; Winter, M. [Institute of Physical Chemistry, Westfaelische Wilhelms-University Muenster, Corrensstrasse 28/30, 48149 Muenster (Germany); Lex-Balducci, A., E-mail: a.lex-balducci@uni-muenster.de [Institute of Physical Chemistry, Westfaelische Wilhelms-University Muenster, Corrensstrasse 28/30, 48149 Muenster (Germany)

2011-09-01

Highlights: > Substitution of linear carbonates in conventional electrolytes with adiponitrile allows the realization of high flash point electrolytes. > EC:ADN based electrolytes display a higher anodic stability than a conventional electrolyte based on EC:DEC. > Graphite and NCM electrodes used in combination with the EC:ADN based electrolyte display a performance comparable with that of conventional electrolytes. - Abstract: The high flash point solvent adiponitrile (ADN) was investigated as co-solvent with ethylene carbonate (EC) for use as lithium-ion battery electrolyte. The flash point of this solvent mixture was more than 110 deg. C higher than that of conventional electrolyte solutions involving volatile linear carbonate components, such as diethyl carbonate (DEC) or dimethyl carbonate (DMC). The electrolyte based on EC:ADN (1:1 wt) with lithium tetrafluoroborate (LiBF{sub 4}) displayed a conductivity of 2.6 mS cm{sup -1} and no aluminum corrosion. In addition, it showed higher anodic stability on a Pt electrode than the standard electrolyte 1 M lithium hexafluorophosphate (LiPF{sub 6}) in EC:DEC (3:7 wt). Graphite/Li half cells using this electrolyte showed excellent rate capability up to 5C and good cycling stability (more than 98% capacity retention after 50 cycles at 1C). Additionally, the electrolyte was investigated in NCM/Li half cells. The cells were able to reach a capacity of 104 mAh g{sup -1} at 5C and capacity retention of more than 97% after 50 cycles. These results show that an electrolyte with a considerably increased flash point with respect to common electrolyte systems comprising linear carbonates, could be realized without any negative effects on the electrochemical performance in Li-half cells.

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.

Plasma electrolytic oxidation of Titanium Aluminides

International Nuclear Information System (INIS)

Morgenstern, R; Sieber, M; Lampke, T; Grund, T; Wielage, B

2016-01-01

Due to their outstanding specific mechanical and high-temperature properties, titanium aluminides exhibit a high potential for lightweight components exposed to high temperatures. However, their application is limited through their low wear resistance and the increasing high-temperature oxidation starting from about 750 °C. By the use of oxide ceramic coatings, these constraints can be set aside and the possible applications of titanium aluminides can be extended. The plasma electrolytic oxidation (PEO) represents a process for the generation of oxide ceramic conversion coatings with high thickness. The current work aims at the clarification of different electrolyte components’ influences on the oxide layer evolution on alloy TNM-B1 (Ti43.5Al4Nb1Mo0.1B) and the creation of compact and wear resistant coatings. Model experiments were applied using a ramp-wise increase of the anodic potential in order to show the influence of electrolyte components on the discharge initiation and the early stage of the oxide layer growth. The production of PEO layers with technically relevant thicknesses close to 100 μm was conducted in alkaline electrolytes with varying amounts of Na 2 SiO 3 ·5H 2 O and K 4 P 2 O 7 under symmetrically pulsed current conditions. Coating properties were evaluated with regard to morphology, chemical composition, hardness and wear resistance. The addition of phosphates and silicates leads to an increasing substrate passivation and the growth of compact oxide layers with higher thicknesses. Optimal electrolyte compositions for maximum coating hardness and thickness were identified by statistical analysis. Under these conditions, a homogeneous inner layer with low porosity can be achieved. The frictional wear behavior of the compact coating layer is superior to a hard anodized layer on aluminum. (paper)

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).

Niobium phosphates as an intermediate temperature proton conducting electrolyte for fuel cells

DEFF Research Database (Denmark)

Huang, Yunjie; Li, Qingfeng; Jensen, Annemette Hindhede

2012-01-01

A new proton conductor based on niobium phosphates was synthesized using niobium pentoxide and phosphoric acid as precursors. The existence of hydroxyl groups in the phosphates was confirmed and found to be preserved after heat treatment at 500 °C or higher, contributing to an anhydrous proton co...... are of high interest as potential proton conducting electrolytes for fuel cells operational in an intermediate temperature range....... conductivity of 1.6 × 10−2 S cm−1 at 250 °C. The conductivity increased with water content in the atmosphere and reached 5.8 × 10−2 S cm−1 under pure water vapour at the same temperature. The conductivity showed good stability in the low water partial pressure range of up to 0.05 atm. The metal phosphates...

Unraveling micro- and nanoscale degradation processes during operation of high-temperature polymer-electrolyte-membrane fuel cells

Science.gov (United States)

Hengge, K.; Heinzl, C.; Perchthaler, M.; Varley, D.; Lochner, T.; Scheu, C.

2017-10-01

The work in hand presents an electron microscopy based in-depth study of micro- and nanoscale degradation processes that take place during the operation of high-temperature polymer-electrolyte-membrane fuel cells (HT-PEMFCs). Carbon supported Pt particles were used as cathodic catalyst material and the bimetallic, carbon supported Pt/Ru system was applied as anode. As membrane, cross-linked polybenzimidazole was used. Scanning electron microscopy analysis of cross-sections of as-prepared and long-term operated membrane-electrode-assemblies revealed insight into micrometer scale degradation processes: operation-caused catalyst redistribution and thinning of the membrane and electrodes. Transmission electron microscopy investigations were performed to unravel the nanometer scale phenomena: a band of Pt and Pt/Ru nanoparticles was detected in the membrane adjacent to the cathode catalyst layer. Quantification of the elemental composition of several individual nanoparticles and the overall band area revealed that they stem from both anode and cathode catalyst layers. The results presented do not demonstrate any catastrophic failure but rather intermediate states during fuel cell operation and indications to proceed with targeted HT-PEMFC optimization.

Electrochemical investigation of LiMn2O4 cathodes in gel electrolyte at various temperatures

International Nuclear Information System (INIS)

Hjelm, Anna-Karin; Eriksson, Tom; Lindbergh, Goeran

2002-01-01

A composite lithium battery electrode of LiMn 2 O 4 in combination with a gel electrolyte (1 M LiBF 4 /24 wt% PMMA/1:1 EC:DEC) has been investigated by galvanostatic cycling experiments and electrochemical impedance spectroscopy (EIS) at various temperatures, i.e. -3 -1 ), the solid phase transfer (∼45 kJ mol -1 ) and of the ionic bulk and effective conductance in the gel phase (∼34 kJ mol -1 ), respectively, were also determined. The kinetic results related to ambient temperature were compared to those obtained in the corresponding liquid electrolyte. The incorporated PMMA was found to reduce the ionic conductivity of the free electrolyte, and it was concluded that the presence of 24 wt% PMMA does not have a significant influence on the kinetic properties of LiMn 2 O 4

Solid composite electrolytes for lithium batteries

Science.gov (United States)

Kumar, Binod; Scanlon, Jr., Lawrence G.

2000-01-01

Solid composite electrolytes are provided for use in lithium batteries which exhibit moderate to high ionic conductivity at ambient temperatures and low activation energies. In one embodiment, a ceramic-ceramic composite electrolyte is provided containing lithium nitride and lithium phosphate. The ceramic-ceramic composite is also preferably annealed and exhibits an activation energy of about 0.1 eV.

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.

Investigation of a nanoconfined, ceramic composite, solid polymer electrolyte

International Nuclear Information System (INIS)

Jayasekara, Indumini; Poyner, Mark; Teeters, Dale

2017-01-01

The challenges for further development of lithium rechargeable batteries are finding electrolyte materials that are safe, have mechanical and thermal stability and have sufficiently high ionic conduction. Polymer electrolytes have many of these advantages, but suffer with low ionic conduction. This study involves the use of anodic aluminum oxide (AAO) membranes having nanochannels filled with polymer electrolyte to make composite solid electrolytes having ionic conductivity several orders of magnitude higher (10 −4 Ω ‐1 cm −1 ) than non-confined polymer. SEM, ac impedance spectroscopy, temperature dependence studies, XRD, ATR- FTIR and DSC studies were done in order to characterize and understand the behavior of nanoconfined polymer electrolytes. The composite polymer electrolyte was found to be more amorphous with polymer chains aligned in the direction of the nanochannels, which is felt to promote ion conduction. The electrolyte systems, confined in nanoporous membranes, can be used as electrolytes for the fabrication of a room temperature all solid state battery.

Initial stages of high temperature metal oxidation

International Nuclear Information System (INIS)

Yang, C.Y.; O'Grady, W.E.

1981-01-01

The application of XPS and UPS to the study of the initial stages of high temperature (> 350 0 C) electrochemical oxidation of iron and nickel is discussed. In the high temperature experiments, iron and nickel electrodes were electrochemically oxidized in contact with a solid oxide electrolyte in the uhv system. The great advantages of this technique are that the oxygen activity at the interface may be precisely controlled and the ability to run the reactions in uhv allows the simultaneous observation of the reactions by XPS

A highly conductive, non-flammable polymer–nanoparticle hybrid electrolyte

KAUST Repository

Agrawal, Akanksha; Choudhury, Snehashis; Archer, Lynden A.

2015-01-01

liquid media as the electrolyte solvent. Remarkably, we also find that even in highly flammable liquid media, the bidisperse nanoparticle hybrid electrolytes can be formulated to exhibit low or no flammability without compromising their favorable room

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.)

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...

Novel Stable Gel Polymer Electrolyte: Toward a High Safety and Long Life Li-Air Battery.

Science.gov (United States)

Yi, Jin; Liu, Xizheng; Guo, Shaohua; Zhu, Kai; Xue, Hailong; Zhou, Haoshen

2015-10-28

Nonaqueous Li-air battery, as a promising electrochemical energy storage device, has attracted substantial interest, while the safety issues derived from the intrinsic instability of organic liquid electrolytes may become a possible bottleneck for the future application of Li-air battery. Herein, through elaborate design, a novel stable composite gel polymer electrolyte is first proposed and explored for Li-air battery. By use of the composite gel polymer electrolyte, the Li-air polymer batteries composed of a lithium foil anode and Super P cathode are assembled and operated in ambient air and their cycling performance is evaluated. The batteries exhibit enhanced cycling stability and safety, where 100 cycles are achieved in ambient air at room temperature. The feasibility study demonstrates that the gel polymer electrolyte-based polymer Li-air battery is highly advantageous and could be used as a useful alternative strategy for the development of Li-air battery upon further application.

Composition of highly concentrated silicate electrolytes and ultrasound influencing the plasma electrolytic oxidation of magnesium

Science.gov (United States)

Simchen, F.; Rymer, L.-M.; Sieber, M.; Lampke, T.

2017-03-01

Magnesium and its alloys are increasingly in use as lightweight construction materials. However, their inappropriate corrosion and wear resistance often prevent their direct practical use. The plasma electrolytic oxidation (PEO) is a promising, environmentally friendly method to improve the surface characteristics of magnesium materials by the formation of oxide coatings. These PEO layers contain components of the applied electrolyte and can be shifted in their composition by increasing the concentration of the electrolyte constituents. Therefore, in contrast to the use of conventional low concentrated electrolytes, the process results in more stable protective coatings, in which electrolyte species are the dominating constitutes. In the present work, the influence of the composition of highly concentrated alkaline silicate electrolytes with additives of phosphate and glycerol on the quality of PEO layers on the magnesium alloy AZ31 was examined. The effect of ultrasound coupled into the electrolyte bath was also considered. The process was monitored by recording the electrical process variables with a transient recorder and by observation of the discharge phenomena on the sample surface with a camera. The study was conducted on the basis of a design of experiments. The effects of the process parameter variation are considered with regard to the coatings thickness, hardness and corrosion resistance. Information about the statistical significance of the effects of the parameters on the considered properties is obtained by an analysis of variance (ANOVA).

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.

Electrolytic conductivity and molar heat capacity of two aqueous solutions of ionic liquids at room-temperature: Measurements and correlations

International Nuclear Information System (INIS)

Lin Peiyin; Soriano, Allan N.; Leron, Rhoda B.; Li Menghui

2010-01-01

As part of our systematic study on physicochemical characterization of ionic liquids, in this work, we report new measurements of electrolytic conductivity and molar heat capacity for aqueous solutions of two 1-ethyl-3-methylimidazolium-based ionic liquids, namely: 1-ethyl-3-methylimidazolium dicyanamide and 1-ethyl-3-methylimidazolium 2-(2-methoxyethoxy) ethylsulfate, at normal atmospheric condition and for temperatures up to 353.2 K. The electrolytic conductivity and molar heat capacity were measured by a commercial conductivity meter and a differential scanning calorimeter (DSC), respectively. The estimated experimental uncertainties for the electrolytic conductivity and molar heat capacity measurements were ±1% and ±2%, respectively. The property data are reported as functions of temperature and composition. A modified empirical equation from another researcher was used to correlate the temperature and composition dependence of the our electrolytic conductivity results. An excess molar heat capacity expression derived using a Redlich-Kister type equation was used to represent the temperature and composition dependence of the measured molar heat capacity and calculated excess molar heat capacity of the solvent systems considered. The correlations applied represent the our measurements satisfactorily as shown by an acceptable overall average deviation of 6.4% and 0.1%, respectively, for electrolytic conductivity and molar heat capacity.

Microstructure, thickness and sheet resistivity of Cu/Ni thin film produced by electroplating technique on the variation of electrolyte temperature

Science.gov (United States)

Toifur, M.; Yuningsih, Y.; Khusnani, A.

2018-03-01

In this research, it has been made Cu/Ni thin film produced with electroplating technique. The deposition process was done in the plating bath using Cu and Ni as cathode and anode respectively. The electrolyte solution was made from the mixture of HBrO3 (7.5g), NiSO4 (100g), NiCl2 (15g), and aquadest (250 ml). Electrolyte temperature was varied from 40°C up to 80°C, to make the Ni ions in the solution easy to move to Cu cathode. The deposition was done during 2 minutes on the potential of 1.5 volt. Many characterizations were done including the thickness of Ni film, microstructure, and sheet resistivity. The results showed that at all samples Ni had attacked on the Cu substrate to form Cu/Ni. The raising of electrolyte temperature affected the increasing of Ni thickness that is the Ni thickness increase with the increasing electrolyte temperature. From the EDS spectrum, it can be informed that samples already contain Ni and Cu elements and NiO and CuO compounds. Addition element and compound are found for sample Cu/Ni resulted from 70° electrolyte temperature of Ni deposition, that are Pt and PtO2. From XRD pattern, there are several phases which have crystal structure i.e. Cu, Ni, and NiO, while CuO and PtO2 have amorphous structure. The sheet resistivity linearly decreases with the increasing electrolyte temperature.

Concurrent aggregation and transport of graphene oxide in saturated porous media: Roles of temperature, cation type, and electrolyte concentration.

Science.gov (United States)

Wang, Mei; Gao, Bin; Tang, Deshan; Yu, Congrong

2018-04-01

Simultaneous aggregation and retention of nanoparticles can occur during their transport in porous media. In this work, the concurrent aggregation and transport of GO in saturated porous media were investigated under the conditions of different combinations of temperature, cation type (valence), and electrolyte concentration. Increasing temperature (6-24 °C) at a relatively high electrolyte concentration (i.e., 50 mM for Na + , 1 mM for Ca 2+ , 1.75 mM for Mg 2+ , and 0.03 and 0.05 mM for Al 3+ ) resulted in enhanced GO retention in the porous media. For instance, when the temperature increased from 6 to 24 °C, GO recovery rate decreased from 31.08% to 6.53% for 0.03 mM Al 3+ and from 27.11% to 0 for 0.05 mM Al 3+ . At the same temperature, increasing cation valence and electrolyte concentration also promoted GO retention. Although GO aggregation occurred in the electrolytes during the transport, the deposition mechanisms of GO retention in the media depended on cation type (valence). For 50 mM Na + , surface deposition via secondary minima was the dominant GO retention mechanism. For multivalent cation electrolytes, GO aggregation was rapid and thus other mechanisms such as physical straining and sedimentation also played important roles in controlling GO retention in the media. After passing through the columns, the GO particles in the effluents showed better stability with lower initial aggregation rates. This was probably because less stable GO particles with lower surface charge densities in the porewater were filtered by the porous media, resulting in more stable GO particle with higher surface charge densities in the effluents. An advection-dispersion-reaction model was applied to simulate GO breakthrough curves and the simulations matched all the experimental data well. Copyright © 2017 Elsevier Ltd. All rights reserved.

Internal shorting and fuel loss of a low temperature solid oxide fuel cell with SDC electrolyte

Energy Technology Data Exchange (ETDEWEB)

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

2007-02-10

A solid oxide fuel cell with Sm{sub 0.2}Ce{sub 0.8}O{sub 1.9} (SDC) electrolyte of 10 {mu}m in thickness and Ni-SDC anode of 15 {mu}m in thickness on a 0.8 mm thick Ni-YSZ cermet substrate was fabricated by tape casting, screen printing and co-firing. A composite cathode, 75 wt.% Sm{sub 0.5}Sr{sub 0.5}CoO{sub 3} (SSCo) + 25 wt.% SDC, approximately 50 {mu}m in thickness, was printed on the co-fired half-cell, and sintered at 950 C. The cell showed a high electrochemical performance at temperatures ranging from 500 to 650 C. Peak power density of 545 mW cm{sup -2} at 600 C was obtained. However, the cell exhibited severe internal shorting due to the mixed conductivity of the SDC electrolyte. Both the amount of water collected from the anode outlet and the open circuit voltage (OCV) indicated that the internal shorting current could reach 0.85 A cm{sup -2} or more at 600 C. Zr content inclusions were found at the surface and in the cross-section of the SDC electrolyte, which could be one of the reasons for reduced OCV and oxygen ionic conductivity. Fuel loss due to internal shorting of the thin SDC electrolyte cell becomes a significant concern when it is used in applications requiring high fuel utilization and electrical efficiency. (author)

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

A high-temperature high-pressure calorimeter for determining heats of solution up to 623 K.

Science.gov (United States)

Djamali, Essmaiil; Turner, Peter J; Murray, Richard C; Cobble, James W

2010-07-01

A high-temperature high-pressure isoperibol calorimeter for determining the heats of solution and reaction of very dilute substances in water (10(-4) m) at temperatures up to 623 K is described. The energies of vaporization of water at steam saturation pressure were measured as a function of temperature and the results agree with the corresponding values from steam tables to better than 0.08+/-0.18%. The novelties of the present instrument relative to flow type heat capacity calorimeters are that measurements can be made at orders of magnitude lower concentrations and that measurement of heat of reaction involving solids or gases or in the presence of high concentrations of supporting electrolytes, acids, and bases is possible. Furthermore, the advantage of using enthalpy data over heat capacity data for calculations of the standard state Gibbs free energies of electrolytes is that the experimental heat data of this research need only be integrated once to derive higher temperature free energy data from lower temperatures. The derived heat capacities can be used mathematically to obtain free energies by double integration. However, the resulting errors are much smaller than if experimental aqueous heat capacities were used for the integrations.

Ambipolar zinc-polyiodide electrolyte for a high-energy density aqueous redox flow battery.

Science.gov (United States)

Li, Bin; Nie, Zimin; Vijayakumar, M; Li, Guosheng; Liu, Jun; Sprenkle, Vincent; Wang, Wei

2015-02-24

Redox flow batteries are receiving wide attention for electrochemical energy storage due to their unique architecture and advantages, but progress has so far been limited by their low energy density (~25 Wh l(-1)). Here we report a high-energy density aqueous zinc-polyiodide flow battery. Using the highly soluble iodide/triiodide redox couple, a discharge energy density of 167 Wh l(-1) is demonstrated with a near-neutral 5.0 M ZnI2 electrolyte. Nuclear magnetic resonance study and density functional theory-based simulation along with flow test data indicate that the addition of an alcohol (ethanol) induces ligand formation between oxygen on the hydroxyl group and the zinc ions, which expands the stable electrolyte temperature window to from -20 to 50 °C, while ameliorating the zinc dendrite. With the high-energy density and its benign nature free from strong acids and corrosive components, zinc-polyiodide flow battery is a promising candidate for various energy storage applications.

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.

Polymer Electrolyte-Based Ambient Temperature Oxygen Microsensors for Environmental Monitoring

Science.gov (United States)

Hunter, Gary W.; Xu, Jennifer C.; Liu, Chung-Chiun

2011-01-01

An ambient temperature oxygen microsensor, based on a Nafion polymer electrolyte, has been developed and was microfabricated using thin-film technologies. A challenge in the operation of Nafion-based sensor systems is that the conductivity of Nafion film depends on the humidity in the film. Nafion film loses conductivity when the moisture content in the film is too low, which can affect sensor operation. The advancement here is the identification of a method to retain the operation of the Nafion films in lower humidity environments. Certain salts can hold water molecules in the Nafion film structure at room temperature. By mixing salts with the Nafion solution, water molecules can be homogeneously distributed in the Nafion film increasing the film s hydration to prevent Nafion film from being dried out in low-humidity environment. The presence of organics provides extra sites in the Nafion film to promote proton (H+) mobility and thus improving Nafion film conductivity and sensor performance. The fabrication of ambient temperature oxygen microsensors includes depositing basic electrodes using noble metals, and metal oxides layer on one of the electrode as a reference electrode. The use of noble metals for electrodes is due to their strong catalytic properties for oxygen reduction. A conducting polymer Nafion, doped with water-retaining components and extra sites facilitating proton movement, was used as the electrolyte material, making the design adequate for low humidity environment applications. The Nafion solution was coated on the electrodes and air-dried. The sensor operates at room temperature in potentiometric mode, which measures voltage differences between working and reference electrodes in different gases. Repeat able responses to 21-percent oxygen in nitrogen were achieved using nitrogen as a baseline gas. Detection of oxygen from 7 to 21 percent has also been demonstrated. The room-temperature oxygen micro sensor developed has extremely low power

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

High resolution neutron imaging of water in the polymer electrolyte fuel cell membrane

Energy Technology Data Exchange (ETDEWEB)

Mukherjee, Partha P [Los Alamos National Laboratory; Makundan, Rangachary [Los Alamos National Laboratory; Spendelow, Jacob S [Los Alamos National Laboratory; Borup, Rodney L [Los Alamos National Laboratory; Hussey, D S [NIST; Jacobson, D L [NIST; Arif, M [NIST

2009-01-01

Water transport in the ionomeric membrane, typically Nafion{reg_sign}, has profound influence on the performance of the polymer electrolyte fuel cell, in terms of internal resistance and overall water balance. In this work, high resolution neutron imaging of the Nafion{reg_sign} membrane is presented in order to measure water content and through-plane gradients in situ under disparate temperature and humidification conditions.

Systems and Methods for Implementing High-Temperature Tolerant Supercapacitors

Science.gov (United States)

Brandon, Erik J. (Inventor); West, William C. (Inventor); Bugga, Ratnakumar V. (Inventor)

2016-01-01

Systems and methods in accordance with embodiments of the invention implement high-temperature tolerant supercapacitors. In one embodiment, a high-temperature tolerant super capacitor includes a first electrode that is thermally stable between at least approximately 80C and approximately 300C; a second electrode that is thermally stable between at least approximately 80C and approximately 300C; an ionically conductive separator that is thermally stable between at least approximately 80C and 300C; an electrolyte that is thermally stable between approximately at least 80C and approximately 300C; where the first electrode and second electrode are separated by the separator such that the first electrode and second electrode are not in physical contact; and where each of the first electrode and second electrode is at least partially immersed in the electrolyte solution.

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

High Temperature Polymers for use in Fuel Cells

Science.gov (United States)

Peplowski, Katherine M.

2004-01-01

NASA Glenn Research Center (GRC) is currently working on polymers for fuel cell and lithium battery applications. The desire for more efficient, higher power density, and a lower environmental impact power sources has led to interest in proton exchanges membrane fuels cells (PEMFC) and lithium batteries. A PEMFC has many advantages as a power source. The fuel cell uses oxygen and hydrogen as reactants. The resulting products are electricity, heat, and water. The PEMFC consists of electrodes with a catalyst, and an electrolyte. The electrolyte is an ion-conducting polymer that transports protons from the anode to the cathode. Typically, a PEMFC is operated at a temperature of about 80 C. There is intense interest in developing a fuel cell membrane that can operate at higher temperatures in the range of 80 C- 120 C. Operating the he1 cell at higher temperatures increases the kinetics of the fuel cell reaction as well as decreasing the susceptibility of the catalyst to be poisoned by impurities. Currently, Nafion made by Dupont is the most widely used polymer membrane in PEMFC. Nafion does not function well above 80 C due to a significant decrease in the conductivity of the membrane from a loss of hydration. In addition to the loss of conductivity at high temperatures, the long term stability and relatively high cost of Nafion have stimulated many researches to find a substitute for Nafion. Lithium ion batteries are popular for use in portable electronic devices, such as laptop computers and mobile phones. The high power density of lithium batteries makes them ideal for the high power demand of today s advanced electronics. NASA is developing a solid polymer electrolyte that can be used for lithium batteries. Solid polymer electrolytes have many advantages over the current gel or liquid based systems that are used currently. Among these advantages are the potential for increased power density and design flexibility. Automobiles, computers, and cell phones require

High temperature electrical energy storage: advances, challenges, and frontiers.

Science.gov (United States)

Lin, Xinrong; Salari, Maryam; Arava, Leela Mohana Reddy; Ajayan, Pulickel M; Grinstaff, Mark W

2016-10-24

With the ongoing global effort to reduce greenhouse gas emission and dependence on oil, electrical energy storage (EES) devices such as Li-ion batteries and supercapacitors have become ubiquitous. Today, EES devices are entering the broader energy use arena and playing key roles in energy storage, transfer, and delivery within, for example, electric vehicles, large-scale grid storage, and sensors located in harsh environmental conditions, where performance at temperatures greater than 25 °C are required. The safety and high temperature durability are as critical or more so than other essential characteristics (e.g., capacity, energy and power density) for safe power output and long lifespan. Consequently, significant efforts are underway to design, fabricate, and evaluate EES devices along with characterization of device performance limitations such as thermal runaway and aging. Energy storage under extreme conditions is limited by the material properties of electrolytes, electrodes, and their synergetic interactions, and thus significant opportunities exist for chemical advancements and technological improvements. In this review, we present a comprehensive analysis of different applications associated with high temperature use (40-200 °C), recent advances in the development of reformulated or novel materials (including ionic liquids, solid polymer electrolytes, ceramics, and Si, LiFePO 4 , and LiMn 2 O 4 electrodes) with high thermal stability, and their demonstrative use in EES devices. Finally, we present a critical overview of the limitations of current high temperature systems and evaluate the future outlook of high temperature batteries with well-controlled safety, high energy/power density, and operation over a wide temperature range.

Hydrogen production through high-temperature electrolysis in a solid oxide cell

International Nuclear Information System (INIS)

Herring, J.St.; Lessing, P.; O'Brien, J.E.; Stoots, C.; Hartvigsen, J.; Elangovan, S.

2004-01-01

An experimental research programme is being conducted by the INEEL and Ceramatec, Inc., to test the high-temperature, electrolytic production of hydrogen from steam using a solid oxide cell. The research team is designing and testing solid oxide cells for operation in the electrolysis mode, producing hydrogen rising a high-temperature heat and electrical energy. The high-temperature heat and the electrical power would be supplied simultaneously by a high-temperature nuclear reactor. Operation at high temperature reduces the electrical energy requirement for electrolysis and also increases the thermal efficiency of the power-generating cycle. The high-temperature electrolysis process will utilize heat from a specialized secondary loop carrying a steam/hydrogen mixture. It is expected that, through the combination of a high-temperature reactor and high-temperature electrolysis, the process will achieve an overall thermal conversion efficiency of 40 to 50%o while avoiding the challenging chemistry and corrosion issues associated with the thermochemical processes. Planar solid oxide cell technology is being utilised because it has the best potential for high efficiency due to minimized voltage and current losses. These losses also decrease with increasing temperature. Initial testing has determined the performance of single 'button' cells. Subsequent testing will investigate the performance of multiple-cell stacks operating in the electrolysis mode. Testing is being performed both at Ceramatec and at INEEL. The first cells to be tested were single cells based on existing materials and fabrication technology developed at Ceramatec for production of solid oxide fuel cells. These cells use a relatively thick (∼ 175 μm) electrolyte of yttria- or scandia-stabilised zirconia, with nickel-zirconia cermet anodes and strontium-doped lanthanum manganite cathodes. Additional custom cells with lanthanum gallate electrolyte have been developed and tested. Results to date have

Solid electrolyte fuel cells

Science.gov (United States)

Isaacs, H. S.

Progress in the development of functioning solid electrolyte fuel cells is summarized. The solid electrolyte cells perform at 1000 C, a temperature elevated enough to indicate high efficiencies are available, especially if the cell is combined with a steam generator/turbine system. The system is noted to be sulfur tolerant, so coal containing significant amounts of sulfur is expected to yield satisfactory performances with low parasitic losses for gasification and purification. Solid oxide systems are electrically reversible, and are usable in both fuel cell and electrolysis modes. Employing zirconium and yttrium in the electrolyte provides component stability with time, a feature not present with other fuel cells. The chemical reactions producing the cell current are reviewed, along with materials choices for the cathodes, anodes, and interconnections.

Novel Organic-Inorganic Hybrid Electrolyte to Enable LiFePO4 Quasi-Solid-State Li-Ion Batteries Performed Highly around Room Temperature.

Science.gov (United States)

Tan, Rui; Gao, Rongtan; Zhao, Yan; Zhang, Mingjian; Xu, Junyi; Yang, Jinlong; Pan, Feng

2016-11-16

A novel type of organic-inorganic hybrid polymer electrolytes with high electrochemical performances around room temperature is formed by hybrid of nanofillers, Y-type oligomer, polyoxyethylene and Li-salt (PBA-Li), of which the T g and T m are significantly lowered by blended heterogeneous polyethers and embedded nanofillers with benefit of the dipole modification to achieve the high Li-ion migration due to more free-volume space. The quasi-solid-state Li-ion batteries based on the LiFePO 4 /15PBA-Li/Li-metal cells present remarkable reversible capacities (133 and 165 mAh g -1 @0.2 C at 30 and 45 °C, respectively), good rate ability and stable cycle performance (141.9 mAh g -1 @0.2 C at 30 °C after 150 cycles).

Achievement report for 1st phase (fiscal 1974-80) Sunshine Program research and development - Hydrogen energy. Research on fuel cell (Research on high-temperature solid electrolyte fuel cell); 1974-1980 nendo suiso energy seika hokokusho. Nenryo denchi no kenkyu (koon kotai denkaishitsu nenryo denchi no kenkyu)

Energy Technology Data Exchange (ETDEWEB)

NONE

1981-03-01

Relative to the research and development of technologies for fabricating, and assessing, materials for the constitution of high-temperature solid electrolyte fuel cells, stabilized zirconia solid electrolyte fuel cell manufacturing technologies are developed by use of thin film formation techniques such as high-frequency sputtering, plasma CVD (chemical vapor deposition), and the thermolysis of organic zirconia compound coating. As the result, it is found that high-frequency sputtering produces thin film which is satisfying in terms of cost efficiency. Furthermore, it is found that defects in solid electrolytic thin film formed by the high-frequency sputtering method, that is, pinholes and cracks, will be remedied when the coating thermolysis method is jointly applied. In the research on fuel cell power systems, column-type high-temperature solid electrolyte fuel cells are built, and a power generation test is conducted. The test is successfully completed when the output of a fuel cell of the 9-column module structure gradually increases until a maximum output of 110W is achieved. (NEDO)

Li-Ion Electrolytes with Improved Safety and Tolerance to High-Voltage Systems

Science.gov (United States)

Smart, Marshall C.; Bugga, Ratnakumar V.; Prakash, Surya; Krause, Frederick C.

2013-01-01

Given that lithium-ion (Li-ion) technology is the most viable rechargeable energy storage device for near-term applications, effort has been devoted to improving the safety characteristics of this system. Therefore, extensive effort has been devoted to developing nonflammable electrolytes to reduce the flammability of the cells/battery. A number of promising electrolytes have been developed incorporating flame-retardant additives, and have been shown to have good performance in a number of systems. However, these electrolyte formulations did not perform well when utilizing carbonaceous anodes with the high-voltage materials. Thus, further development was required to improve the compatibility. A number of Li-ion battery electrolyte formulations containing a flame-retardant additive [i.e., triphenyl phosphate (TPP)] were developed and demonstrated in high-voltage systems. These electrolytes include: (1) formulations that incorporate varying concentrations of the flame-retardant additive (from 5 to 15%), (2) the use of mono-fluoroethylene carbonate (FEC) as a co-solvent, and (3) the use of LiBOB as an electrolyte additive intended to improve the compatibility with high-voltage systems. Thus, improved safety has been provided without loss of performance in the high-voltage, high-energy system.

Intermediate Temperature Fuel Cell Using Gypsum Based Electrolyte And Electrodes

International Nuclear Information System (INIS)

Suzuki, Satoshi; Nagai, Masayuki; Katagiri, Yuji

2011-01-01

The proton conductive electrolyte membrane and the electrodes for intermediate temperature fuel cell were made from the phosphoric acid treated gypsum as a proton conductor. The membrane and the electrodes were built into single cell and tested at intermediate temperature region. The power density of the fuel cell was 0.56 mW/cm -2 at 150 deg. C without any humidification and 1.38 mW/cm -2 at 150 deg. C, 5% relative humidity. The open circuit voltage of the cell was increased higher than 0.7 V when the electrodes were annealed at 150 deg. C, 5%R.H., however the reasons for this are still to be further investigated. The results show that the potential of the phosphoric acid treated gypsum for the intermediate temperature proton conductor.

Synthesis of polymer gel electrolyte with high molecular weight poly(methyl methacrylate)-clay nanocomposite

International Nuclear Information System (INIS)

Meneghetti, Paulo; Qutubuddin, Syed; Webber, Andrew

2004-01-01

Polymer nanocomposite gel electrolytes consisting of high molecular weight poly(methyl methacrylate) PMMA-clay nanocomposite, ethylene carbonate (EC)/propylene carbonate (PC) as plasticizer, and LiClO 4 electrolyte are reported. Montmorillonite clay was ion exchanged with a zwitterionic surfactant (octadecyl dimethyl betaine) and dispersed in methyl methacrylate, which was then polymerized to synthesize PMMA-clay nanocomposites. The nanocomposite was dissolved in a mixture of EC/PC with LiClO 4 , heated and pressed to obtain polymer gel electrolyte. X-ray diffraction (XRD) of the gels indicated intercalated clay structure with d-spacings of 2.85 and 1.40 nm. In the gel containing plasticizer, the clay galleries shrink suggesting intercalation rather than partial exfoliation observed in the PMMA-clay nanocomposite. Ionic conductivity varied slightly and exhibited a maximum value of 8 x 10 -4 S/cm at clay content of 1.5 wt.%. The activation energy was determined by modeling the conductivity with a Vogel-Tamman-Fulcher expression. The clay layers are primarily trapped inside the polymer matrix. Consequently, the polymer does not interact significantly with LiClO 4 electrolyte as shown by FTIR. The presence of the clay increased the glass transition temperature (Tg) of the gel as determined by differential scanning calorimetry. The PMMA nanocomposite gel electrolyte shows a stable lithium interfacial resistance over time, which is a key factor for use in electrochemical applications

Temperature dependent dielectric properties and ion transportation in solid polymer electrolyte for lithium ion batteries

Energy Technology Data Exchange (ETDEWEB)

Sengwa, R. J., E-mail: rjsengwa@rediffmail.com; Dhatarwal, Priyanka, E-mail: dhatarwalpriyanka@gmail.com; Choudhary, Shobhna, E-mail: shobhnachoudhary@rediffmail.com [Dielectric Research Laboratory, Department of Physics, Jai Narain Vyas University, Jodhpur – 342 005 (India)

2016-05-06

Solid polymer electrolyte (SPE) film consisted of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blend matrix with lithium tetrafluroborate (LiBF{sub 4}) as dopant ionic salt and poly(ethylene glycol) (PEG) as plasticizer has been prepared by solution casting method followed by melt pressing. Dielectric properties and ionic conductivity of the SPE film at different temperatures have been determined by dielectric relaxation spectroscopy. It has been observed that the dc ionic conductivity of the SPE film increases with increase of temperature and also the decrease of relaxation time. The temperature dependent relaxation time and ionic conductivity values of the electrolyte are governed by the Arrhenius relation. Correlation observed between dc conductivity and relaxation time confirms that ion transportation occurs with polymer chain segmental dynamics through hopping mechanism. The room temperature ionic conductivity is found to be 4 × 10{sup −6} S cm{sup −1} which suggests the suitability of the SPE film for rechargeable lithium batteries.

Heat and fuel coupled operation of a high temperature polymer electrolyte fuel cell with a heat exchanger methanol steam reformer

Science.gov (United States)

Schuller, G.; Vázquez, F. Vidal; Waiblinger, W.; Auvinen, S.; Ribeirinha, P.

2017-04-01

In this work a methanol steam reforming (MSR) reactor has been operated thermally coupled to a high temperature polymer electrolyte fuel cell stack (HT-PEMFC) utilizing its waste heat. The operating temperature of the coupled system was 180 °C which is significantly lower than the conventional operating temperature of the MSR process which is around 250 °C. A newly designed heat exchanger reformer has been developed by VTT (Technical Research Center of Finland LTD) and was equipped with commercially available CuO/ZnO/Al2O3 (BASF RP-60) catalyst. The liquid cooled, 165 cm2, 12-cell stack used for the measurements was supplied by Serenergy A/S. The off-heat from the electrochemical fuel cell reaction was transferred to the reforming reactor using triethylene glycol (TEG) as heat transfer fluid. The system was operated up to 0.4 A cm-2 generating an electrical power output of 427 Wel. A total stack waste heat utilization of 86.4% was achieved. It has been shown that it is possible to transfer sufficient heat from the fuel cell stack to the liquid circuit in order to provide the needed amount for vaporizing and reforming of the methanol-water-mixture. Furthermore a set of recommendations is given for future system design considerations.

Solid-state graft copolymer electrolytes for lithium battery applications.

Science.gov (United States)

Hu, Qichao; Caputo, Antonio; Sadoway, Donald R

2013-08-12

Battery safety has been a very important research area over the past decade. Commercially available lithium ion batteries employ low flash point (battery costs and can malfunction which can lead to battery malfunction and explosions, thus endangering human life. Increases in petroleum prices lead to a huge demand for safe, electric hybrid vehicles that are more economically viable to operate as oil prices continue to rise. Existing organic based electrolytes used in lithium ion batteries are not applicable to high temperature automotive applications. A safer alternative to organic electrolytes is solid polymer electrolytes. This work will highlight the synthesis for a graft copolymer electrolyte (GCE) poly(oxyethylene) methacrylate (POEM) to a block with a lower glass transition temperature (Tg) poly(oxyethylene) acrylate (POEA). The conduction mechanism has been discussed and it has been demonstrated the relationship between polymer segmental motion and ionic conductivity indeed has a Vogel-Tammann-Fulcher (VTF) dependence. Batteries containing commercially available LP30 organic (LiPF6 in ethylene carbonate (EC):dimethyl carbonate (DMC) at a 1:1 ratio) and GCE were cycled at ambient temperature. It was found that at ambient temperature, the batteries containing GCE showed a greater overpotential when compared to LP30 electrolyte. However at temperatures greater than 60 °C, the GCE cell exhibited much lower overpotential due to fast polymer electrolyte conductivity and nearly the full theoretical specific capacity of 170 mAh/g was accessed.

Promising Ni-Fe-LSGMC anode compatible with lanthanum gallate electrolyte

Energy Technology Data Exchange (ETDEWEB)

Wang Shizhong [Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005 (China); School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, GA 30332-0245 (United States)], E-mail: shizwang@sohu.com; He, Qiong [Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005 (China); Liu Meilin [School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, GA 30332-0245 (United States)], E-mail: meilin.liu@mse.gatech.edu

2009-06-01

A number of composite materials in the Ni-Fe-LSGMC family have been studied as potential anodes for solid oxide fuel cells (SOFCs) based on strontium, magnesium, and cobalt doped lanthanum gallate electrolyte (LSGMC). The results show that Ni reacts with LSGMC especially under reducing conditions at high temperatures, resulting in high contact resistance, large electrode polarization, and poor performance. The reaction between Ni and LSGMC depends strongly on the composition and pre-sintering temperature of LSGMC, the concentration of iron in the electrode, and the processing and operating temperatures. Under proper conditions, Ni-Fe-LSGMC5 could be a promising high-performance anode with good compatibility with LSGMC5 electrolyte.

Promising Ni-Fe-LSGMC anode compatible with lanthanum gallate electrolyte

International Nuclear Information System (INIS)

Wang Shizhong; He, Qiong; Liu Meilin

2009-01-01

A number of composite materials in the Ni-Fe-LSGMC family have been studied as potential anodes for solid oxide fuel cells (SOFCs) based on strontium, magnesium, and cobalt doped lanthanum gallate electrolyte (LSGMC). The results show that Ni reacts with LSGMC especially under reducing conditions at high temperatures, resulting in high contact resistance, large electrode polarization, and poor performance. The reaction between Ni and LSGMC depends strongly on the composition and pre-sintering temperature of LSGMC, the concentration of iron in the electrode, and the processing and operating temperatures. Under proper conditions, Ni-Fe-LSGMC5 could be a promising high-performance anode with good compatibility with LSGMC5 electrolyte.

Sparingly Solvating Electrolytes for High Energy Density Lithium-Sulfur Batteries

Energy Technology Data Exchange (ETDEWEB)

Cheng, Lei; Curtiss, Larry A.; Zavadil, Kevin R.; Gewirth, Andrew A.; Shao, Yuyan; Gallagher, Kevin

2016-07-11

Moving to lighter and less expensive battery chemistries compared to lithium-ion requires the control of energy storage mechanisms based on chemical transformations rather than intercalation. Lithium sulfur (Li/S) has tremendous theoretical specific energy, but contemporary approaches to control this solution-mediated, precipitation-dissolution chemistry requires using large excesses of electrolyte to fully solubilize the polysulfide intermediate. Achieving reversible electrochemistry under lean electrolyte operation is the only path for Li/S to move beyond niche applications to potentially transformational performance. An emerging topic for Li/S research is the use of sparingly solvating electrolytes and the creation of design rules for discovering new electrolyte systems that fundamentally decouple electrolyte volume from reaction mechanism. This perspective presents an outlook for sparingly solvating electrolytes as the key path forward for longer-lived, high-energy density Li/S batteries including an overview of this promising new concept and some strategies for accomplishing it.

Materials system for intermediate temperature solid oxide fuel cells based on doped lanthanum-gallate electrolyte

Science.gov (United States)

Gong, Wenquan

2005-07-01

The objective of this work was to identify a materials system for intermediate temperature solid oxide fuel cells (IT-SOFCs). Towards this goal, alternating current complex impedance spectroscopy was employed as a tool to study electrode polarization effects in symmetrical cells employing strontium and magnesium doped lanthanum gallate (LSGM) electrolyte. Several cathode materials were investigated including strontium doped lanthanum manganite (LSM), Strontium and iron doped lanthanum cobaltate (LSCF), LSM-LSGM, and LSCF-LSGM composites. Investigated Anode materials included nickel-gadolinium or lanthanum doped cerium oxide (Ni-GDC, or Ni-LDC) composites. The ohmic and the polarization resistances of the symmetrical cells were obtained as a function of temperature, time, thickness, and the composition of the electrodes. Based on these studies, the single phase LSM electrode had the highest polarization resistance among the cathode materials. The mixed-conducting LSCF electrode had polarization resistance orders of magnitude lower than that of the LSM-LSGM composite electrodes. Although incorporating LSGM in the LSCF electrode did not reduce the cell polarization resistance significantly, it could reduce the thermal expansion coefficient mismatch between the LSCF electrodes and LSGM electrolyte. Moreover, the polarization resistance of the LSCF electrode decreased asymptotically as the electrode thickness was increased thus suggesting that the electrode thickness needed not be thicker than this asymptotic limit. On the anode side of the IT-SOFC, Ni reacted with LSGM electrolyte, and lanthanum diffusion occurred from the LSGM electrolyte to the GDC barrier layer, which was between the LSGM electrolyte and the Ni-composite anode. However, LDC served as an effective barrier layer. Ni-LDC (70 v% Ni) anode had the largest polarization resistance, while all other anode materials, i.e. Ni-LDC (50 v% Ni), Ni-GDC (70 v% NO, and Ni-GDC (50 v% Ni), had similar polarization

Electrochemical Study of Hydrocarbon-Derived Electrolytes for Supercapacitors

Science.gov (United States)

Noorden, Zulkarnain A.; Matsumoto, Satoshi

2013-10-01

In this paper, we evaluate the essential electrochemical properties - capacitive and resistive behaviors - of hydrocarbon-derived electrolytes for supercapacitor application using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The electrolytes were systematically prepared from three hydrocarbon-derived compounds, which have different molecular structures and functional groups, by treatment with high-concentration sulfuric acid (H2SO4) at room temperature. Two-electrode cells were assembled by sandwiching an electrolyte-containing glass wool separator with two active electrodes of activated carbon sheets. The dc electrical properties of the tested cells in terms of their capacitive behavior were investigated by CV, and in order to observe the frequency characteristics of the constructed cells, EIS was carried out. Compared with the tested cell with only high-concentration H2SO4 as the electrolyte, the cell with the derived electrolytes exhibit a capacitance as high as 135 F/g with an improved overall internal resistance of 2.5 Ω. Through the use of a simple preparation method and low-cost precursors, hydrocarbon-derived electrolytes could potentially find large-scale and higher-rating supercapacitor applications.

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.

"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.

Highly conducting leakage-free electrolyte for SrCoOx-based non-volatile memory device

Science.gov (United States)

Katase, Takayoshi; Suzuki, Yuki; Ohta, Hiromichi

2017-10-01

The electrochemical switching of SrCoOx-based non-volatile memory with a thin-film-transistor structure was examined by using liquid-leakage-free electrolytes with different conductivities (σ) as the gate insulator. We first examined leakage-free water, which is incorporated in the amorphous (a-) 12CaO.7Al2O3 film with a nanoporous structure (Calcium Aluminate with Nanopore), but the electrochemical oxidation/reduction of the SrCoOx layer required the application of a high gate voltage (Vg) up to 20 V for a very long current-flowing-time (t) ˜40 min, primarily due to the low σ [2.0 × 10-8 S cm-1 at room temperature (RT)] of leakage-free water. We then controlled the σ of the leakage-free electrolyte, infiltrated in the a-NaxTaO3 film with a nanopillar array structure, from 8.0 × 10-8 S cm-1 to 2.5 × 10-6 S cm-1 at RT by changing the x = 0.01-1.0. As the result, the t, required for the metallization of the SrCoOx layer under small Vg = -3 V, becomes two orders of magnitude shorter with increase of the σ of the a-NaxTaO3 leakage-free electrolyte. These results indicate that the ion migration in the leakage-free electrolyte is the rate-determining step for the electrochemical switching, compared to the other electrochemical process, and the high σ of the leakage-free electrolyte is the key factor for the development of the non-volatile SrCoOx-based electro-magnetic phase switching device.

Molecular motion in polymer electrolytes. An investigation of methods for improving the conductivity of solid polymer electrolytes

International Nuclear Information System (INIS)

Webster, Mark Ian

2002-01-01

Three methods were explored with a view to enhancing the ionic conductivity of polymer electrolytes; namely the addition of an inert, inorganic filler, the addition of a plasticizer and the incorporation of the electrolyte in the pores of silica matrices. There have been a number of reports, which suggest the addition of nanocrystalline oxides to polymer electrolytes increases the ionic conductivities by about a factor of two. In this thesis studies of the polymer electrolyte NaSCN.P(EO) 8 with added nanocrystalline alumina powder are reported which show no evidence of enhanced conductivity. The addition of a plasticizer to polymer electrolytes will increase the ionic conductivity. A detailed study was made of the polymer electrolytes LiT.P(EO) 10 and LiClO 4 .P(EO) 10 with added ethylene carbonate plasticizer. The conductivities showed an enhancement, however this disappeared on heating under vacuum. The present work suggests that the plasticised system is not thermodynamically stable and will limit the applications of the material. A series of samples were prepared from the polymer electrolyte LiT.P(EO) 8 and a range of porous silicas. The silicas were selected to give a wide range of pore size and included Zeolite Y, ZSM5, mesoporous silica and a range of porous glasses. This gave pore sizes from less than one nm to 50 nm. A variety of experiments, including X-ray diffraction, DSC and NMR, showed that the polymer electrolyte entered to pores of the silica. As a result the polymer was amorphous and the room temperature conductivity was enhanced. The high temperature conductivity was not increased above that for the pure electrolyte. The results suggest that this could be employed in applications, however would require higher conducting electrolytes to be of practical benefit. (author)

A novel and high-effective redox-mediated gel polymer electrolyte for supercapacitor

International Nuclear Information System (INIS)

Ma, Guofu; Feng, Enke; Sun, Kanjun; Peng, Hui; Li, Jiajia; Lei, Ziqiang

2014-01-01

Graphical abstract: - Highlights: • Alkali and P-phenylenediamine doped polyvinyl alcohol gel electrolyte is prepared. • The PVA-KOH-PPD gel electrolyte can also be used as separator. • The introduction of PPD increases the ionic conductivity of electrolyte. • The supercapacitor exhibits flexible and high energy density. - Abstract: A supercapacitor utilize a novel redox-mediated gel polymer (PVA-KOH-PPD) as electrolyte and separator, and activated carbon as electrodes is assembled. The PVA-KOH-PPD gel polymer as potential electrolyte for supercapacitor is investigated by cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy techniques. It is found that the supercapacitor exhibits high ionic conductivity (25 mS cm −1 ), large electrode specific capacitance (611 F g −1 ) and high energy density (82.56 Wh kg −1 ). The high performance is attributed to the addition of quick redox reactions at the electrolyte|electrode interface as PPD undergoes a two-proton/two-electron reduction and oxidation during cycling. Furthermore, the supercapacitor with PVA-KOH-PPD gel polymer shows excellent charge-discharge stability, after 1000 charge-discharge cycles, the supercapacitor still retains a high electrode specific capacitance of 470 F g −1 . It is believed that the idea using redox mediator has a good prospect for improving the performances of supercapacitors

Solid state electrolyte systems

Energy Technology Data Exchange (ETDEWEB)

Pederson, L.R.; Armstrong, B.L.; Armstrong, T.R. [Pacific Northwest Lab., Richland, WA (United States)] [and others

1997-12-01

Lanthanum gallates are a new family of solid electrolytes that exhibit high ionic conductivity and are stable to high temperatures. Compositions have been developed that are as much as a factor of two more conductive than yttria-stabilized zirconia at a given temperature, through partial replacement of lanthanum by calcium, strontium, and/or barium and through partial replacement of gallium by magnesium. Oxide powders were prepared using combustion synthesis techniques developed in this laboratory; these were sintered to >95% of theoretical density and consisted of a single crystalline phase. Electrical conductivities, electron and ion transference numbers, thermal expansion, and phase behavior were evaluated as a function of temperature and oxygen partial pressure. A key advantage of the use of lanthanum gallate electrolytes in solid oxide fuel cells is that the temperature of operation may be lowered to perhaps 800 C, yet provide approximately the same power density as zirconia-based cells operating at 1000 C. Ceramic electrolytes that conduct both oxygen ions and electrons are potentially useful to passively separate pure oxygen from an air source at low cost. In such materials, an oxygen ion flux in one direction is charge-compensated by an opposing electron flux. The authors have examined a wide range of mixed ion and electron conducting perovskite ceramics in the system La{sub 1{minus}x}M{sub x}Co{sub 1{minus}y{minus}z}Fe{sub y}N{sub z}O{sub 3{minus}{delta}}, where M = Sr, Ca, and Ba, and N = Pr, Mn, Ni, Cu, Ti, and Al, as well as mixed conducting brownmillerite ceramics, and have characterized oxygen permeation behavior, defect chemistry, structural and phase stability, and performance as cathodes.

Li-Ion Cells Employing Electrolytes With Methyl Propionate and Ethyl Butyrate Co-Solvents

Science.gov (United States)

Smart, Marshall C.; Bugga, Ratnakumar V.

2011-01-01

Future NASA missions aimed at exploring Mars and the outer planets require rechargeable batteries that can operate at low temperatures to satisfy the requirements of such applications as landers, rovers, and penetrators. A number of terrestrial applications, such as hybrid electric vehicles (HEVs) and electric vehicles (EVs) also require energy storage devices that can operate over a wide temperature range (i.e., -40 to +70 C), while still providing high power capability and long life. Currently, the state-of-the-art lithium-ion system has been demonstrated to operate over a wide range of temperatures (-30 to +40 C); however, the rate capability at the lower temperatures is very poor. These limitations at very low temperatures are due to poor electrolyte conductivity, poor lithium intercalation kinetics over the electrode surface layers, and poor ionic diffusion in the electrode bulk. Two wide-operating-temperature-range electrolytes have been developed based on advances involving lithium hexafluorophosphate-based solutions in carbonate and carbonate + ester solvent blends, which have been further optimized in the context of the technology and targeted applications. The approaches employed include further optimization of electrolytes containing methyl propionate (MP) and ethyl butyrate (EB), which are effective co-solvents, to widen the operating temperature range beyond the baseline systems. Attention was focused on further optimizing ester-based electrolyte formulations that have exhibited the best performance at temperatures ranging from -60 to +60 C, with an emphasis upon improving the rate capability at -20 to -40 C. This was accomplished by increasing electrolyte salt concentration to 1.20M and increasing the ester content to 60 percent by volume to increase the ionic conductivity at low temperatures. Two JPL-developed electrolytes 1.20M LiPF6 in EC+EMC+MP (20:20:60 v/v %) and 1.20M LiPF6 in EC+EMC+EB (20:20:60 v/v %) operate effectively over a wide

Low temperature electrochemistry at normal conductor/frozen electrolyte interface

International Nuclear Information System (INIS)

Borkowska, Z.; Stimming, U.

1991-01-01

The frozen electrolyte technique (FREECE = FRozen Electrolyte ElectroChEmistry) is based on the experimental result that frozen electrolytes are suitable for electrochemical studies. This technique has been used in our laboratory and also by others to investigate interfacial electrochemical behavior. An argument will be given as to why the FREECE technique is advantageous in a number of respects and what kind of electrolyte systems can be used. Reference is made to electrochemical results such as interfacial reactions and double layer properties. 26 refs

Electrocatalysis of fuel cell reactions: Investigation of alternate electrolytes

Science.gov (United States)

Chin, D. T.; Hsueh, K. L.; Chang, H. H.

1984-01-01

Oxygen reduction and transport properties of the electrolyte in the phosphoric acid fuel cell are studied. The areas covered were: (1) development of a theoretical expression for the rotating ring disk electrode technique; (2) determination of the intermediate reaction rate constants for oxygen reduction on platinum in phosphoric acid electrolyte; (3) determination of oxygen reduction mechanism in trifluoreomethanesulfonic acid (TFMSA) which was considered as an alternate electrolyte for the acid fuel cells; and (4) the measurement of transport properties of the phosphoric acid electrolyte at high concentrations and temperatures.

Electrospun polymer membrane activated with room temperature ionic liquid: Novel polymer electrolytes for lithium batteries

Science.gov (United States)

Cheruvally, Gouri; Kim, Jae-Kwang; Choi, Jae-Won; Ahn, Jou-Hyeon; Shin, Yong-Jo; Manuel, James; Raghavan, Prasanth; Kim, Ki-Won; Ahn, Hyo-Jun; Choi, Doo Seong; Song, Choong Eui

A new class of polymer electrolytes (PEs) based on an electrospun polymer membrane incorporating a room-temperature ionic liquid (RTIL) has been prepared and evaluated for suitability in lithium cells. The electrospun poly(vinylidene fluoride- co-hexafluoropropylene) P(VdF-HFP) membrane is activated with a 0.5 M solution of LiTFSI in 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMITFSI) or a 0.5 M solution of LiBF 4 in 1-butyl-3-methylimidazolium tetrafluoroborate (BMIBF 4). The resulting PEs have an ionic conductivity of 2.3 × 10 -3 S cm -1 at 25 °C and anodic stability at >4.5 V versus Li +/Li, making them suitable for practical applications in lithium cells. A Li/LiFePO 4 cell with a PE based on BMITFSI delivers high discharge capacities when evaluated at 25 °C at the 0.1 C rate (149 mAh g -1) and the 0.5 C rate (132 mAh g -1). A very stable cycle performance is also exhibited at these low current densities. The properties decrease at the higher, 1 C rate, when operated at 25 °C. Nevertheless, improved properties are obtained at a moderately elevated temperature of operation, i.e. 40 °C. This is attributed to enhanced conductivity of the electrolyte and faster reaction kinetics at higher temperatures. At 40 °C, a reversible capacity of 140 mAh g -1 is obtained at the 1 C rate.

NiF2/NaF:CaF2/Ca Solid-State High-Temperature Battery Cells

Science.gov (United States)

West, William; Whitacre, Jay; DelCastillo, Linda

2009-01-01

Experiments and theoretical study have demonstrated the promise of all-solid-state, high-temperature electrochemical battery cells based on NiF2 as the active cathode material, CaF2 doped with NaF as the electrolyte material, and Ca as the active anode material. These and other all-solid-state cells have been investigated in a continuing effort to develop batteries for instruments that must operate in environments much hotter than can be withstood by ordinary commercially available batteries. Batteries of this type are needed for exploration of Venus (where the mean surface temperature is about 450 C), and could be used on Earth for such applications as measuring physical and chemical conditions in geothermal wells and oil wells. All-solid-state high-temperature power cells are sought as alternatives to other high-temperature power cells based, variously, on molten anodes and cathodes or molten eutectic salt electrolytes. Among the all-solid-state predecessors of the present NiF2/NaF:CaF2/Ca cells are those described in "Solid-State High-Temperature Power Cells" (NPO-44396), NASA Tech Briefs, Vol. 32, No. 5 (May 2008), page 40. In those cells, the active cathode material is FeS2, the electrolyte material is a crystalline solid solution of equimolar amounts of Li3PO4 and LiSiO4, and the active anode material is Li contained within an alloy that remains solid in the intended high operational temperature range.

Facilely solving cathode/electrolyte interfacial issue for high-voltage lithium ion batteries by constructing an effective solid electrolyte interface film

International Nuclear Information System (INIS)

Xu, Jingjing; Xia, Qingbo; Chen, Fangyuan; Liu, Tao; Li, Li; Cheng, Xueyuan; Lu, Wei; Wu, Xiaodong

2016-01-01

The cathode/electrolyte interface stability is the key factor for the cyclic performance and the safety performance of lithium ion batteries. Suppression of consuming key elements in the electrode materials is essential in this concern. In this purpose, we investigate a facile strategy to solve interfacial issue for high-voltage lithium ion batteries by adding an oxidable fluorinated phosphate, Bis(2,2,2-trifluoroethyl) Phosphite (BTFEP), as a sacrificial additive in electrolyte. We demonstrate that BTFEP additive could be oxidized at slightly above 4.28 V which is a relatively lower voltage than that of solvents, and the oxidative products facilitate in-situ forming a stable solid electrolyte interphase (SEI) film on the cathode surface. The results manifest the SEI film validly restrains the generation of HF and the interfacial side reaction between high-voltage charged LiNi 0.5 Mn 1.5 O 4 (LNMO) and electrolyte, hence, the dissolution of Mn and Ni is effectively suppressed. Finally, the cyclic performance of LNMO after 200 cycles was remarkably improved from 68.4% in blank electrolyte to 95% in 1 wt% BTFEP-adding electrolyte.

Modeling and simulation of high-temperature polymer electrolyte fuel cells; Modellierung und Simulation von Hochtemperatur-Polymerelektrolyt-Brennstoffzellen

Energy Technology Data Exchange (ETDEWEB)

Kvesic, Mirko

2012-07-01

Fuel cells are electrochemical energy converters that convert chemical energy of constantly fed reactants directly into electricity. The most commonly used fuel gas in this respect is hydrogen, which is either produced in pure form by electrolysis, for example, or as a hydrogen-rich gas mixture (reformate gas), produced by reforming diesel or kerosene e.g. However, a disadvantage of reformate gas is that it contains additional carbon monoxide (CO), which leads to catalyst poisoning in the fuel cell. Since higher operating temperatures also lead to a higher CO tolerance, the use of high-temperature Polymer-Electrolyte-Fuel-Cells (HT-PEFCs) is particularly suitable for reformate operation. The aim of the presented work is the modeling and CFD-simulation of HT-PEFC stacks with the intention of gaining a better understanding of multi-physical processes in the stack operation as well as the optimization and analysis of existing stack designs. The geometric modeling used is based on the Porous Volume Model, which significantly reduces the required number of computing elements. Furthermore, the electrochemical models for hydrogen / air and reformate / air operation, which were taking the CO poisoning effects into account, are developed in this work and implemented in the software ANSYS / Fluent. The resulting simulations indicated the optimal flow configuration for the stack operation in terms of the homogeneous current density distribution, which has a positive effect on the stack aging. Thus, the current densities showed a strong homogeneity regarding the stack configuration anode / cathode in counter-flow and anode / cooling in co-flow. The influence of cooling strategies was examined for the stack performance in a similar way. In the following, the local temperature distribution as well as temperature peaks within the stack could be predicted and validated with experimental measurements. Further on, the model scalability and thus the general validity of the developed

Thermally responsive polymer electrolytes for inherently safe electrochemical energy storage

Science.gov (United States)

Kelly, Jesse C.

Electrochemical double layer capacitors (EDLCs), supercapacitors and Li-ion batteries have emerged as premier candidates to meet the rising demands in energy storage; however, such systems are limited by thermal hazards, thermal runaway, fires and explosions, all of which become increasingly more dangerous in large-format devices. To prevent such scenarios, thermally-responsive polymer electrolytes (RPEs) that alter properties in electrochemical energy storage devices were designed and tested. These RPEs will be used to limit or halt device operation when temperatures increase beyond a predetermined threshold, therefore limiting further heating. The development of these responsive systems will offer an inherent safety mechanism in electrochemical energy storage devices, while preserving the performance, lifetimes, and versatility that large-format systems require. Initial work focused on the development of a model system that demonstrated the concept of RPEs in an electrochemical device. Aqueous electrolyte solutions of polymers exhibiting properties that change in response to temperature were developed for applications in EDLCs and supercapacitors. These "smart materials" provide a means to control electrochemical systems where polymer phase separation at high temperatures affects electrolyte properties and inhibits device performance. Aqueous RPEs were synthesized using N-isopropylacrylamide, which governs the thermal properties, and fractions of acrylic acid or vinyl sulfonic acids, which provide ions to the solution. The molecular properties of these aqueous RPEs, specifically the ionic composition, were shown to influence the temperature-dependent electrolyte properties and the extent to which these electrolytes control the energy storage characteristics of a supercapacitor device. Materials with high ionic content provided the highest room temperature conductivity and electrochemical activity; however, RPEs with low ionic content provided the highest "on

Role of perfluoropolyether-based electrolytes in lithium metal batteries: Implication for suppressed Al current collector corrosion and the stability of Li metal/electrolytes interfaces

Science.gov (United States)

Cong, Lina; Liu, Jia; Armand, Michel; Mauger, Alain; Julien, Christian M.; Xie, Haiming; Sun, Liqun

2018-03-01

The development of safe and high performance lithium metal batteries represents a major technological challenge for this new century. Historically, intrinsic instabilities of conventional liquid organic electrolytes induced battery failures and safety issues that hinder the practical utilization of advanced rechargeable lithium metal batteries. Herein, we report a multifunctional perfluoropolyether-based liquid polymer electrolyte (PFPE-MC/LiTFSI), presenting a unique "anion-solvent" interaction. This interaction optimizes the interfacial chemistry of lithium metal batteries, which effectively inhibits the corrosion of aluminum current collectors, suppresses lithium dendrite growth, and also facilitates the formation of a thin and stable SEI layer on Li anode. Even at a high current density of 0.7 mA cm-2, the lithium dendrites do not form after 1360 h of continuous operation. The LiFePO4|PFPE-MC/LiTFSI|Li cell delivers a stable cycling performance with over 99.9% columbic efficiency either at ambient temperature or high temperature, which is significantly superior to those using traditional carbonate electrolytes. In addition, PFPE-MC/LiTFSI electrolyte also possesses eye-catching properties, such as being non-flammable, non-volatile, non-hygroscopic, and existing in the liquid state between -90 °C and 200 °C, which further ensures the high safety of the lithium metal batteries, making this electrolyte promising for the development of high energy lithium metal batteries.

A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles.

KAUST Repository

Choudhury, Snehashis; Mangal, Rahul; Agrawal, Akanksha; Archer, Lynden A

2015-01-01

Rough electrodeposition, uncontrolled parasitic side-reactions with electrolytes and dendrite-induced short-circuits have hindered development of advanced energy storage technologies based on metallic lithium, sodium and aluminium electrodes. Solid polymer electrolytes and nanoparticle-polymer composites have shown promise as candidates to suppress lithium dendrite growth, but the challenge of simultaneously maintaining high mechanical strength and high ionic conductivity at room temperature has so far been unmet in these materials. Here we report a facile and scalable method of fabricating tough, freestanding membranes that combine the best attributes of solid polymers, nanocomposites and gel-polymer electrolytes. Hairy nanoparticles are employed as multifunctional nodes for polymer crosslinking, which produces mechanically robust membranes that are exceptionally effective in inhibiting dendrite growth in a lithium metal battery. The membranes are also reported to enable stable cycling of lithium batteries paired with conventional intercalating cathodes. Our findings appear to provide an important step towards room-temperature dendrite-free batteries.

A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles.

KAUST Repository

Choudhury, Snehashis

2015-12-04

Rough electrodeposition, uncontrolled parasitic side-reactions with electrolytes and dendrite-induced short-circuits have hindered development of advanced energy storage technologies based on metallic lithium, sodium and aluminium electrodes. Solid polymer electrolytes and nanoparticle-polymer composites have shown promise as candidates to suppress lithium dendrite growth, but the challenge of simultaneously maintaining high mechanical strength and high ionic conductivity at room temperature has so far been unmet in these materials. Here we report a facile and scalable method of fabricating tough, freestanding membranes that combine the best attributes of solid polymers, nanocomposites and gel-polymer electrolytes. Hairy nanoparticles are employed as multifunctional nodes for polymer crosslinking, which produces mechanically robust membranes that are exceptionally effective in inhibiting dendrite growth in a lithium metal battery. The membranes are also reported to enable stable cycling of lithium batteries paired with conventional intercalating cathodes. Our findings appear to provide an important step towards room-temperature dendrite-free batteries.

Charge carrier dynamics in PMMA-LiClO4 based polymer electrolytes plasticized with different plasticizers

Science.gov (United States)

Pal, P.; Ghosh, A.

2017-07-01

We have studied the charge carrier dynamics in poly(methylmethacrylate)-LiClO4 polymer electrolytes plasticized with different plasticizers such as ethylene carbonate (EC), propylene carbonate (PC), polyethylene glycol (PEG), and dimethyl carbonate (DMC). We have measured the broadband complex conductivity spectra of these electrolytes in the frequency range of 0.01 Hz-3 GHz and in the temperature range of 203 K-363 K and analyzed the conductivity spectra in the framework of the random barrier model by taking into account the contribution of the electrode polarization observed at low frequencies and/or at high temperatures. It is observed that the temperature dependences of the ionic conductivity and relaxation time follow the Vogel-Tammann-Fulcher relation for all plasticized electrolytes. We have also performed the scaling of the conductivity spectra, which indicates that the charge carrier dynamics is almost independent of temperature and plasticizers in a limited frequency range. The existence of nearly constant loss in these electrolytes has been observed at low temperatures and/or high frequencies. We have studied the dielectric relaxation in these electrolytes using electric modulus formalism and obtained the stretched exponent and the decay function. We have observed less cooperative ion dynamics in electrolytes plasticized with DMC compared to electrolytes plasticized with EC, PC, and PEG.

Epoxy-silica hybrid organic–inorganic electrolytes with a high Li-ion conductivity

International Nuclear Information System (INIS)

Vélez, J.F.; Procaccini, R.A.; Aparicio, M.; Mosa, J.

2013-01-01

Organic–inorganic hybrid electrolytes were prepared by co-hydrolysis and co-condensation of 3-glycidoxipropyltrimethoxysilane (GPTMS) and tetraethyl orthosilicate (TEOS) doped with lithium acetate as self-supported materials and thin-films. The effects of the relative molar content of LiAc on the physicochemical properties of electrolytes, such as morphology, thermal, chemical and electrochemical properties were investigated. Two and four probes test cells were designed for comparative studies of ionic conductivity of hybrid electrolytes using electrochemical impedance spectroscopy (EIS). Similar ionic conductivities were obtained using both measurement methods, reaching a maximum ionic conductivity value of around 10 −6 S/cm at 25 °C. The conductivity mechanism presents Arrehenius behavior with the increase of the temperature from 25 °C to 120 °C. The electrochemical stability window is found to be in the range of 0–5 V, which ensures that hybrid organic–inorganic materials are potential electrolytes for solid-state rechargeable lithium ion batteries

Conductivity, dielectric behavior and FTIR studies of high molecular weight poly(vinylchloride)-lithium triflate polymer electrolytes

International Nuclear Information System (INIS)

Ramesh, S.; Chai, M.F.

2007-01-01

Thin films of high molecular weight polyvinyl chloride (PVC) with lithium triflate (LiCF 3 SO 3 ) salt were prepared by solution casting method. The ionic conductivity and dielectric measurements were carried out on these films over a wide frequency regime at various temperatures. The conductivity-temperature plots were found to obey classical Arrhenius relationship. The dielectric behavior was analysed using dielectric permittivity and dielectric modulus of the samples. FTIR studies show some simple overlapping and shift in peaks between high molecular weight polyvinyl chloride (PVC) with lithium triflate (LiCF 3 SO 3 ) salt in the polymer electrolyte complexes

Metal Phosphates as Intermediate Temperature Proton Conducting Electrolytes

DEFF Research Database (Denmark)

Huang, Yunjie; Li, Q.F.; Pan, Chao

2012-01-01

A series of metal phosphates were synthesized and screened as potential proton conductor electrolytes for fuel cells and electrolysers operational at intermediate temperatures. Among the selected, niobium and bismuth phosphates exhibited a proton conductivity of 10-2 and 10-7 S cm-1, respectively......, under the anhydrous atmosphere at 250 °C, showing close correlation with the presence of hydroxyl groups in the phosphate phases. At the water partial pressure of above 0.6 atm, both phosphates possessed a proton conductivity to a level of above 3 x 10-2 S cm-1. Reasonable stability of the proton...... conductivity was observed under either a constant low water partial pressure or under a humidity cycling test within a period of more than 80 hours....

Chapter 6. Operation of electrolytic cell in standard operating practices

International Nuclear Information System (INIS)

Yanko, E.A.; Kabirov, Sh.O.; Safiev, Kh.; Azizov, B.S.; Mirpochaev, Kh.A.

2011-01-01

This chapter is devoted to operation of electrolytic cell in standard operating practices. Therefore, the electrolyte temperature, the composition of electrolyte, including the level of metals was considered. The regulation of electrolyte composition by liquidus temperature and electrolyte overheating was studied. Damping of anode effects was studied as well. Maintenance of electrolytic cells was described. Heat and energy balances of aluminium electrolytic cells were considered.

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 CPA equation of state for very high temperature and pressure reservoir and basin applications

Science.gov (United States)

Courtial, Xavier; Ferrando, Nicolas; de Hemptinne, Jean-Charles; Mougin, Pascal

2014-10-01

In this work, an electrolyte version of the Cubic Plus Association (eCPA) equation of state has been adapted to systems containing CH4, CO2, H2O and NaCl (up to 5 molal) at pressures up to 200 MPa and temperatures up to 773 K for salt-free systems and 573 K for salt-containing systems. Its purpose is to represent the phase behavior (including salting-out effect and critical point) and the phase densities in a range of temperature and pressure encountered in deep reservoirs and basins. The goal of the parameterization proposed is not to reach a very high accuracy for phase equilibrium and volumetric properties, but rather to develop a semi-predictive approach to model the phase and volumetric behavior of this system while allowing an easy extension to other compounds. Without salt, predictions for pure component vapor pressures and liquid molar volumes present an average absolute deviation (AAD) lower than 3% compared to experimental reference values. The pure component molar volumes out of saturation show an AAD lower than 4%. The highest deviations in densities are observed as expected in the vicinity of the critical coordinates of pure water and this effect increases when gases or salts are added to the system. For each binary system, CH4 + CO2, CH4 + H2O and CO2 + H2O, binary interaction parameters have been fitted to correctly represent the shape of the fluid phase envelopes (including all critical points) in the entire temperature and pressure range considered (219 K to 633 K and up to 250 MPa). The methane concentration in both phases of the CH4 + CO2 binary system is represented with an AAD lower than 9%. The methane solubility in water is represented within 16% and 8% for the methane content of the vapor. The CO2 solubility in water is within 26%, while the CO2 in the vapor phase shows an average deviation of 12%. All molar volumes are represented with an AAD lower than 3%. The few VLE experimental data for the CH4 + CO2 + H2O ternary system are fairly well

Electrolytic treatment of liquid waste containing ammonium nitrate

International Nuclear Information System (INIS)

Komori, R.; Ogawa, N.; Ohtsuka, K.; Ohuchi, J.

1981-01-01

A study was made on the safe decomposition of ammonium nitrate, which is the main component of α-liquid waste from plutonium fuel facilities, by means of electrolytic reduction and thermal decomposition. In the first stage, ammonium nitrate is reduced to ammonium nitrite by electrolytic reduction using an electrolyser with a cation exchange membrane as a diaphragm. In the second stage, ammonium nitrite is decomposed to N 2 and H 2 O. The alkaline region and a low temperature are preferable for electrolytic reduction and the acidic region and high temperature for thermal decomposition. A basis was established for an ammonium nitrate treatment system in aqueous solution through the operation of a bench-scale unit, and the operating data obtained was applied to the basic design of a 10-m 3 /a facility. (author)

Enabling electrolyte compositions for columnar silicon anodes in high energy secondary batteries

Science.gov (United States)

Piwko, Markus; Thieme, Sören; Weller, Christine; Althues, Holger; Kaskel, Stefan

2017-09-01

Columnar silicon structures are proven as high performance anodes for high energy batteries paired with low (sulfur) or high (nickel-cobalt-aluminum oxide, NCA) voltage cathodes. The introduction of a fluorinated ether/sulfolane solvent mixture drastically improves the capacity retention for both battery types due to an improved solid electrolyte interface (SEI) on the surface of the silicon electrode which reduces irreversible reactions normally causing lithium loss and rapid capacity fading. For the lithium silicide/sulfur battery cycling stability is significantly improved as compared to a frequently used reference electrolyte (DME/DOL) reaching a constant coulombic efficiency (CE) as high as 98%. For the silicon/NCA battery with higher voltage, the addition of only small amounts of fluoroethylene carbonate (FEC) to the novel electrolyte leads to a stable capacity over at least 50 cycles and a CE as high as 99.9%. A high volumetric energy density close to 1000 Wh l-1 was achieved with the new electrolyte taking all inactive components of the stack into account for the estimation.

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.

Ni-SDC cermet anode for medium-temperature solid oxide fuel cell with lanthanum gallate electrolyte

Energy Technology Data Exchange (ETDEWEB)

Zhang, Xinge; Ohara, Satoshi; Maric, R.; Mukai, Kazuo; Fukui, Takehisa [Japan Fine Ceramics Center, Nagoya (Japan); Yoshida, Hiroyuki; Nishimura, Masayoshi; Inagaki, Toru [Kansai Electr. Power Co. Inc., Hyogo (Japan); Miura, Kazuhiro [Kanden Kakou, Amagasaki (Japan)

1999-10-01

The polarization properties and microstructure of Ni-SDC (samaria-doped ceria) cermet anodes prepared from spray pyrolysis (SP) composite powder, and element interface diffusion between the anode and a La{sub 0.9}Sr{sub 0.1}Ga{sub 0.8}Mg{sub 0.2}O{sub 3-{delta}} (LSGM) electrolyte are investigated as a function of anode sintering temperature. The anode sintered at 1250 C displays minimum anode polarization (with anode ohmic loss), while the anode prepared at 1300 C has the best electrochemical overpotential, viz., 27 mV at 300 mA cm{sup -2} operating at 800 C. The anode ohmic loss gradually increases with increase in the sintering temperature at levels below 1300 C, and sharply increases at 1350 C. Electron micrographs show a clear grain growth at sintering temperatures higher than 1300 C. The anode microstructure appears to be optimized at 1300 C, in which nickel particles form a network with well-connected SDC particles finely distributed over the surfaces of the nickel particles. The anode sintered at 1350 C has severe grain growth and an apparent interface diffusion of nickel from the anode to the electrolyte. The nickel interface diffusion is assumed to be the main reason for the increment in ohmic loss, and the resulting loss in anode performance. The findings suggest that sintering Ni-SDC composite powder near 1250 C is the best method to prepare the anode on a LSGM electrolyte. (orig.)

Ni-SDC cermet anode for medium-temperature solid oxide fuel cell with lanthanum gallate electrolyte

Science.gov (United States)

Zhang, Xinge; Ohara, Satoshi; Maric, Radenka; Mukai, Kazuo; Fukui, Takehisa; Yoshida, Hiroyuki; Nishimura, Masayoshi; Inagaki, Toru; Miura, Kazuhiro

The polarization properties and microstructure of Ni-SDC (samaria-doped ceria) cermet anodes prepared from spray pyrolysis (SP) composite powder, and element interface diffusion between the anode and a La 0.9Sr 0.1Ga 0.8Mg 0.2O 3- δ (LSGM) electrolyte are investigated as a function of anode sintering temperature. The anode sintered at 1250°C displays minimum anode polarization (with anode ohmic loss), while the anode prepared at 1300°C has the best electrochemical overpotential, viz., 27 mV at 300 mA cm -2 operating at 800°C. The anode ohmic loss gradually increases with increase in the sintering temperature at levels below 1300°C, and sharply increases at 1350°C. Electron micrographs show a clear grain growth at sintering temperatures higher than 1300°C. The anode microstructure appears to be optimized at 1300°C, in which nickel particles form a network with well-connected SDC particles finely distributed over the surfaces of the nickel particles. The anode sintered at 1350°C has severe grain growth and an apparent interface diffusion of nickel from the anode to the electrolyte. The nickel interface diffusion is assumed to be the main reason for the increment in ohmic loss, and the resulting loss in anode performance. The findings suggest that sintering Ni-SDC composite powder near 1250°C is the best method to prepare the anode on a LSGM electrolyte.

Ultramicroelectrode voltammetry and scanning electrochemical microscopy in room-temperature ionic liquid electrolytes.

Science.gov (United States)

Walsh, Darren A; Lovelock, Kevin R J; Licence, Peter

2010-11-01

The high viscosity and unusual properties of room temperature ionic liquids (RTILs) present a number of challenges when performing steady-state voltammetry and scanning electrochemical microscopy in RTILs. These include difficulties in recording steady-state currents at ultramicroelectrode surfaces due to low diffusion coefficients of redox species and problems associated with unequal diffusion coefficients of oxidised and reduced species in RTILs. In this tutorial review, we highlight the recent progress in the use of RTILs as electrolytes for ultramicroelectrode voltammetry and SECM. We describe the basic principles of ultramicroelectrode voltammetry and SECM and, using examples from the recent literature, we discuss the conditions that must be met to perform steady-state voltammetry and SECM measurements in RTILs. Finally, we briefly discuss the electrochemical insights that can be obtained from such measurements.

Electrolyte Additives for Phosphoric Acid Fuel Cells

DEFF Research Database (Denmark)

Gang, Xiao; Hjuler, H.A.; Olsen, C.A.

1993-01-01

, as a fuel-cell performance with the modified electrolytes. Specific conductivity measurements of some of the modified phosphoric acid electrolytes are reported. At a given temperature, the conductivity of the C4F9SO3K-modified electrolyte decreases with an increasing amount of the additive; the conductivity...... of the remains at the same value as the conductivity of the pure phosphoric acid. At a given composition, the conductivity of any modified electrolyte increases with temperature. We conclude that the improved cell performance for modified electrolytes is not due to any increase in conductivity.......Electrochemical characteristics of a series of modified phosphoric acid electrolytes containing fluorinated car on compounds and silicone fluids as additives are presented. When used in phosphoric acid fuel cells, the modified electrolytes improve the performance due to the enhanced oxygen...

The temperature influence against conductivity of solid state electrolyte of (CuI)0,5(β-Al2O3)0,5

International Nuclear Information System (INIS)

Purwanto, -P; Kartini, -E; Purnama, Safei

2004-01-01

The solid electrolyte (CuI) 0,5 (β-Al 2 O 3 ) 0,5 has been prepared by a solid state reaction, by mixing of CuI with β-Al 2 O 3 powders. The mixture was compacted and heated at the temperature 300 o C for 3 hours. The conductivity values of (CuI) 0,5 (β-Al 2 O 3 ) 0,5 increased with the temperature and frequency. The x ray diffraction peaks of the solid electrolyte (CuI) 0,5 (β-Al 2 O 3 ) 0,5 are dominated by the peaks of CuI than the peaks of β-Al 2 O 3 . The activation energy of the solid electrolyte is relatively stable, with the range from 0.09 eV to 0.13 eV. The conductivities solid electrolyte (CuI) 0,5 (β-Al 2 O 3 ) 0,5 at room temperature and at 300 o C are 1.48 x 10 -5 S/cm and 8.33 x 10 -4 S/cm, respectively

Preparation and performance of intermediate-temperature fuel cells based on Gd-doped ceria electrolytes with different compositions

International Nuclear Information System (INIS)

Li, Zhimin; Mori, Toshiyuki; Yan, Pengfei; Wu, Yuanyuan; Li, ZhiPeng

2012-01-01

Highlights: ► Gd 0.1 Ce 0.9 O 1.95 electrolyte had less density of oxygen vacancies ordering. ► Gd 0.2 Ce 0.8 O 1.9 fuel cell showed better performance than Gd 0.1 Ce 0.9 O 1.95 . ► The relationship between microstructures and performance for cells were discussed. ► Gd 0.2 Ce 0.8 O 1.9 electrolyte with higher grain boundary conductivity was concluded. - Abstract: In this work, the effect of two frequently used Gd x Ce 1−x O 2−x/2 electrolytes (x = 0.1 and x = 0.2) on the performance of fuel cells operated at intermediate temperature was studied. The microstructures of ceria electrolytes responsible for the performance were discussed. Electrochemical measurements of as-prepared cells showed that the cell with Gd 0.2 Ce 0.8 O 1.9 electrolyte had a better performance than that of Gd 0.1 Ce 0.9 O 1.95 . It can be concluded that the increase of grain boundary conductivity of Gd 0.2 Ce 0.8 O 1.9 electrolyte contributes to its better cell performance.

Facile and scalable fabrication of polymer-ceramic composite electrolyte with high ceramic loadings

Science.gov (United States)

Pandian, Amaresh Samuthira; Chen, X. Chelsea; Chen, Jihua; Lokitz, Bradley S.; Ruther, Rose E.; Yang, Guang; Lou, Kun; Nanda, Jagjit; Delnick, Frank M.; Dudney, Nancy J.

2018-06-01

Solid state electrolytes are a promising alternative to flammable liquid electrolytes for high-energy lithium battery applications. In this work polymer-ceramic composite electrolyte membrane with high ceramic loading (greater than 60 vol%) is fabricated using a model polymer electrolyte poly(ethylene oxide) + lithium trifluoromethane sulfonate and a lithium-conducting ceramic powder. The effects of processing methods, choice of plasticizer and varying composition on ionic conductivity of the composite electrolyte are thoroughly investigated. The physical, structural and thermal properties of the composites are exhaustively characterized. We demonstrate that aqueous spray coating followed by hot pressing is a scalable and inexpensive technique to obtain composite membranes that are amazingly dense and uniform. The ionic conductivity of composites fabricated using this protocol is at least one order of magnitude higher than those made by dry milling and solution casting. The introduction of tetraethylene glycol dimethyl ether further increases the ionic conductivity. The composite electrolyte's interfacial compatibility with metallic lithium and good cyclability is verified by constructing lithium symmetrical cells. A remarkable Li+ transference number of 0.79 is discovered for the composite electrolyte.

Nafion titania nanotubes nanocomposite electrolytes for high-temperature direct methanol fuel cells

CSIR Research Space (South Africa)

Cele, NP

2012-01-01

Full Text Available electrolytes membranes. This promotes to study the Nafion/TNTs nanocomposite membranes behaviour with the aim to improve Nafion properties such as fuel permeability and thermal and mechanical stability. Nafion, whose primary structure consists of acid... membrane properties, further investigations were carried out. In this study, the effects of TiO2 nanotubes on Nafion properties such as water uptake, thermal stability, methanol (MeOH) permeability, and ion conductivity were investigated...

Conductivity, dielectric behavior and FTIR studies of high molecular weight poly(vinylchloride)-lithium triflate polymer electrolytes

Energy Technology Data Exchange (ETDEWEB)

Ramesh, S. [Faculty of Engineering and Science, Universiti Tunku Abdul Rahman, Setapak, 53300 Kuala Lumpur (Malaysia)]. E-mail: ramesh@mail.utar.edu.my; Chai, M.F. [Faculty of Engineering and Science, Universiti Tunku Abdul Rahman, Setapak, 53300 Kuala Lumpur (Malaysia)

2007-05-15

Thin films of high molecular weight polyvinyl chloride (PVC) with lithium triflate (LiCF{sub 3}SO{sub 3}) salt were prepared by solution casting method. The ionic conductivity and dielectric measurements were carried out on these films over a wide frequency regime at various temperatures. The conductivity-temperature plots were found to obey classical Arrhenius relationship. The dielectric behavior was analysed using dielectric permittivity and dielectric modulus of the samples. FTIR studies show some simple overlapping and shift in peaks between high molecular weight polyvinyl chloride (PVC) with lithium triflate (LiCF{sub 3}SO{sub 3}) salt in the polymer electrolyte complexes.

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.

Direct dimethyl ether high temperature polymer electrolyte membrane fuel cells

DEFF Research Database (Denmark)

Vassiliev, Anton; Jensen, Jens Oluf; Li, Qingfeng

and suffers from low DME solubility in water. When the DME - water mixture is fed as vapour miscibility is no longer a problem. The increased temperature is more beneficial for the kinetics of the direct oxidation of DME than of methanol. The Open Circuit Voltage (OCV) with DME operation was 50 to 100 m......A high temperature polybenzimidazole (PBI) polymer fuel cell was fed with dimethyl ether (DME) and water vapour mixture on the anode at ambient pressure with air as oxidant. A peak power density of 79 mW/cm2 was achieved at 200°C. A conventional polymer based direct DME fuel cell is liquid fed......V higher than that of methanol, indicating less fuel crossover....

Ionic liquids as electrolytes for non-aqueous solutions electrochemical supercapacitors in a temperature range of 20 °C-80 °C

Science.gov (United States)

Zhang, Lei; Tsay, Ken; Bock, Christina; Zhang, Jiujun

2016-08-01

To increase the operating temperature of the supercapacitors (SCs) without compromising their high cycle-life, several typical fluoro- and non-fluoro containing ionic liquids (EMI-mesylate, EMI-hydrogen sulfate, PP13-triflate, PP13-TFSI, and EMI-TFSI, as shown in Fig. 1) are studied as the electrolytes to prepare organic solutions for SC performance measurements using a two-electrode cell. Both cyclic voltammograms and charge/discharge curves at various temperatures such as 20, 40, 60 and 80 °C are collected. At 60 °C, the increased performance order in both rating and cyclability measurements are found to be as follows: 1) EMI-hydrogen sulfate < PP13-TFSI < EMI-mesylate < PP13-triflate < EMI-TFSI for rating; and 2) EMI-hydrogen sulfate < EMI-mesylate < PP13-Triflate < PP13-TFSI < EMI-TFSI for life-time. The fluoro-containing group of ILs, i.e., PP13-Triflate, PP13-TFSI and EMI-TFSI can give a specific capacitance between 100 and 170 F/g for various scan rates for a conventional carbon electrode, and an extended lifetime test of 10, 000 cycles with a capacitance degradation of less than 10%, indicating that these two ion liquids can be used for SC electrolytes operated at high temperature.

Polyampholyte hydrogel electrolytes for flexible and self-healing aqueous supercapacitor for low temperature applications

Science.gov (United States)

Chung, Hyun-Joong; Li, Xinda

Quenched polyampholytes provide a novel class of tough hydrogel that has self-healing ability, strong adhesion, and mechanical flexibility. In this study, we show that the polyampholyte hydrogels can be utilized as an aqueous gel electrolyte material that is especially useful for low temperature operations; at -30 °C, energy density of 10.5 Wh/kg at a power density of 500 W/kg was achieved. The high performance at the low temperature is associated to the concept of non-freezable water near the hydrophilic polymer chains. A comparison between differential scanning calorimetry (DSC) measurements for polyampholytes that contained KOH and neat KOH solution revealed that increased amount of water molecules become non-freezable when the solution is contained in the hydrogel networks. In addition, the crosslinked network structure of the polyampholyte chains disrupts the crystalline growth of ice, resulting in `slush-like' ice formation. The interplay between the increased amount of unfrozen water and the limited growth of ice crystals leads to the enhanced supercapacitor performance at low temperatures.

THERMODYNAMICS OF ELECTROLYTES. XI. PROPERTIES OF 3-2, 4-2, AND OTHER HIGH-VALENCE TYPES

Energy Technology Data Exchange (ETDEWEB)

Pitzer, Kenneth S.; Silvester, Leonard F.

1977-12-01

Various thermodynamic properties are considered for very high-valence 3-2 and 4-2 electrolytes in water at room temperature. These solutions show the behavior described by Davies in which ion pairing arises as the concentration increases follow by re-dissociation at still higher concentrations. Heat of dilution data, which extend below 10{sup -4} M, are interpreted with the same form of equation used earlier for 2-2 electrolytes. Activity and osmotic coefficient data do not extend to low enough concentration for independent, interpretation, but they are treated with the aid of conductance data in the more dilute range. Parameters are reported for A{ell}{sub 2}(SO{sub 4}){sub 3}, La{sub 2}(SO{sub 4}){sub 3}, In{sub 2}(SO{sub 4}){sub 3}, and several cyanoferrates. High-valence electrolytes show a special behavior at very low concentrations which was recognized by Bjerrum who showed in 1926 that purely electrostatic forces would yield an ion association. Davies showed that this association commonly reached a maximum at an intermediate concentration above which there was a re-dissociation. From one viewpoint, this ion association is an artifact of the linearization approximation in the Debye-Hueckel theory since a more exact statistical treatment yields agreement with experiment without assuming a separate associated species. If an association equilibrium is assumed for these electrolytes, it is found that the value of the association constant depends on the assumptions about the activity coefficients of the ions. To the extent that these effects are important for 2-2 electrolytes, they are discussed in paper III{sup 6} of this series. While in 3-2 and 4-2 electrolytes the effects are of the same nature as those in the 2-2 solutes, they occur at much lower concentration in the higher-valence solutes; consequently new problems arise in treating experimental data. Indeed, it is only the conductance and heat-of-dilution measurements, which extend down to 10{sup -5} M

Nanoporous Polymer-Ceramic Composite Electrolytes for Lithium Metal Batteries

KAUST Repository

Tu, Zhengyuan; Kambe, Yu; Lu, Yingying; Archer, Lynden A.

2013-01-01

A nanoporous composite material that offers the unique combination of high room-temperature ionic conductivity and high mechanical modulus is reported. When used as the separator/electrolyte in lithium batteries employing metallic lithium as anode

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.

High-performance electrolyte in the presence of dextrose and its derivatives for aluminum electrolytic capacitors

Science.gov (United States)

Tsai, Ming-Liao; Lu, Yi-Fang; Do, Jing-Shan

Dextrose and its derivatives (e.g. glucose, gluconic acid and gluconic lactone) are added to modify the characteristics of electrolytes used in aluminum electrolytic capacitors. The results show that the conductivity and sparking voltage of the electrolytes are severely affected by the concentration of dextrose gluconic acid and gluconic lactone. In addition, the pH of the electrolyte is only slightly affected by the quantity of gluconic acid and gluconic lactone. The capacitance, dissipation factor, and leakage current of capacitors impregnated with the electrolytes prepared in this work are periodically measured under storage conditions and loading at 105 °C.

Analysis of influence of heat exchange conditions on the outer surface of the lithium-ion battery to electrolyte temperature under the conditions of high current loads

Directory of Open Access Journals (Sweden)

Krasnoshlykov Alexander

2017-01-01

Full Text Available Numerical analysis of thermal conditions of a lithium-ion battery using the software package ANSYS Electric and ANSYS Fluent has been carried out. Time dependence of the electrolyte temperature on the various heat exchange conditions on the outer surface has been obtained.

High temperature corrosion of separator materials for MCFC

Energy Technology Data Exchange (ETDEWEB)

Yanagida, Masahiro; Tanimoto, Kazumi; Kojima, Toshikatsu [Osaka National Research Institute (Japan)] [and others

1996-12-31

The Molten Carbonate Fuel Cell (MCFC) is one of promising high efficiency power generation devices with low emission. Molten carbonate used for its electrolyte plays an important role in MCFC. It separates between anode and cathode gas environment and provides ionic conductivity on MCFC operation. Stainless steel is conventionally used as separator/current collector materials in MCFC cathode environment. As corrosion of the components of MCFC caused by the electrolyte proceeds with the electrolyte consumption, the corrosion in the MCFC is related to its performance and life. To understand and inhibit the corrosion in the MCFC is important to realize MCFC power generation system. We have studied the effect of alkaline earth carbonate addition into carbonate on corrosion of type 316L stainless steel. In this paper, we describe the effect of the temperature on corrosion behavior of type 316L stainless steel with carbonate mixture, (Li{sub 0.62}K{sub 0.38}){sub 2}CO{sub 3}, under the cathode environment in out-of-cell test.

Evaluation of MHD materials for use in high-temperature fuel cells

Energy Technology Data Exchange (ETDEWEB)

Guidotti, R.

1978-06-15

The MHD and high-temperature fuel cell literature was surveyed for data pertaining to materials properties in order to identify materials used in MHD power generation which also might be suitable for component use in high-temperature fuel cells. Classes of MHD-electrode materials evaluated include carbides, nitrides, silicides, borides, composites, and oxides. Y/sub 2/O/sub 3/-stabilized ZrO/sub 2/ used as a reference point to evaluate materials for use in the solid-oxide fuel cell. Physical and chemical properties such as electrical resistivity, coefficient of thermal expansion, and thermodynamic stability toward oxidation were used to screen candidate materials. A number of the non-oxide ceramic MHD-electrode materials appear promising for use in the solid-electrolyte and molten-carbonate fuel cell as anodes or anode constituents. The MHD-insulator materials appear suitable candidates for electrolyte-support tiles in the molten-carbonate fuel cells. The merits and possible problem areas for these applications are discussed and additional needed areas of research are delineated.

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

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 quasi-direct methanol fuel cell system based on blend polymer membrane electrolytes

DEFF Research Database (Denmark)

Li, Qingfeng; Hjuler, Hans Aage; Hasiotis, C.

2002-01-01

, compared to less than 100 ppm CO for the Nafion-based technology at 80degrees C. The high CO tolerance makes it possible to use the reformed hydrogen directly from a simple methanol reformer without further CO removal. That both the fuel cell and the methanol reformer operate at temperatures around 200......On the basis of blend polymer electrolytes of polybenzimidazole and sulfonated polysulfone, a polymer electrolyte membrane fuel cell was developed with an operational temperature up to 200degrees C. Due to the high operational temperature, the fuel cell can tolerate 1.0-3.0 vol % CO in the fuel...

Des-acyl ghrelin prevents heatstroke-like symptoms in rats exposed to high temperature and high humidity.

Science.gov (United States)

Inoue, Yoshiyuki; Hayashi, Yujiro; Kangawa, Kenji; Suzuki, Yoshihiro; Murakami, Noboru; Nakahara, Keiko

2016-02-26

We have shown previously that des-acyl ghrelin decreases body temperature in rats through activation of the parasympathetic nervous system. Here we investigated whether des-acyl ghrelin ameliorates heatstroke in rats exposed to high temperature. Peripheral administration of des-acyl ghrelin significantly attenuated hyperthermia induced by exposure to high-temperature (35°C) together with high humidity (70-80%). Although biochemical analysis revealed that exposure to high temperature significantly increased hematocrit and the serum levels of aspartate amino transferase (AST), alanine transaminase (ALT), blood urea nitrogen (BUN), creatinine and electrolytes (Na(+), K(+), Cl(-)), most of these heatstroke-associated reactions were significantly reduced by treatment with des-acyl ghrelin. The level of des-acyl ghrelin in plasma was also found to be significantly increased under high-temperature conditions. These results suggest that des-acyl ghrelin could be useful for preventing heatstroke under high temperature condition. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

High Temperature PEM Fuel Cell Stacks with Advent TPS Meas

Directory of Open Access Journals (Sweden)

Neophytides Stylianos

2017-01-01

Full Text Available High power/high energy applications are expected to greatly benefit from high temperature Polymer Electrolyte Membrane Fuel Cells (PEMFCs. In this work, a combinatorial approach is presented, in which separately developed and evaluated MEAs, design and engineering are employed to result in reliable and effective stacks operating above 180°C and having the characteristics well matched to applications including auxiliary power, micro combined heat and power, and telecommunication satellites.

Improved ionic conductivity of lithium-zinc-tellurite glass-ceramic electrolytes

Science.gov (United States)

Widanarto, W.; Ramdhan, A. M.; Ghoshal, S. K.; Effendi, M.; Cahyanto, W. T.; Warsito

An enhancement in the secondary battery safety demands the optimum synthesis of glass-ceramics electrolytes with modified ionic conductivity. To achieve improved ionic conductivity and safer operation of the battery, we synthesized Li2O included zinc-tellurite glass-ceramics based electrolytes of chemical composition (85-x)TeO2·xLi2O·15ZnO, where x = 0, 5, 10, 15 mol%. Samples were prepared using the melt quenching method at 800 °C followed by thermal annealing at 320 °C for 3 h and characterized. The effects of varying temperature, alternating current (AC) frequency and Li2O concentration on the structure and ionic conductivity of such glass-ceramics were determined. The SEM images of the annealed glass-ceramic electrolytes displayed rough surface with a uniform distribution of nucleated crystal flakes with sizes less than 1 μm. X-ray diffraction analysis confirmed the well crystalline nature of achieved electrolytes. Incorporation of Li2O in the electrolytes was found to generate some new crystalline phases including hexagonal Li6(TeO6), monoclinic Zn2Te3O8 and monoclinic Li2Te2O5. The estimated crystallite size of the electrolyte was ranged from ≈40 to 80 nm. AC impedance measurement revealed that the variation in the temperatures, Li2O contents, and high AC frequencies have a significant influence on the ionic conductivity of the electrolytes. Furthermore, electrolyte doped with 15 mol% of Li2O exhibited the optimum performance with an ionic conductivity ≈2.4 × 10-7 S cm-1 at the frequency of 54 Hz and in the temperature range of 323-473 K. This enhancement in the conductivity was attributed to the sizable alteration in the ions vibration and ruptures of covalent bonds in the electrolytes network structures.

Rotating disk electrode study of borohydride oxidation in a molten eutectic electrolyte and advancements in the intermediate temperature borohydride battery

Science.gov (United States)

Wang, Andrew; Gyenge, Előd L.

2017-08-01

The electrode kinetics of the NaBH4 oxidation reaction (BOR) in a molten NaOH-KOH eutectic mixture is investigated by rotating disk electrode (RDE) voltammetry on electrochemically oxidized Ni at temperatures between 458 K and 503 K. The BH4- diffusion coefficient in the molten alkali eutectic together with the BOR activation energy, exchange current density, transfer coefficient and number of electrons exchanged, are determined. Electrochemically oxidized Ni shows excellent BOR electrocatalytic activity with a maximum of seven electrons exchanged and a transfer coefficient up to one. X-ray photoelectron spectroscopy (XPS) reveals the formation of NiO as the catalytically active species. The high faradaic efficiency and BOR rate on oxidized Ni anode in the molten electrolyte compared to aqueous alkaline electrolytes is advantageous for power sources. A novel molten electrolyte battery design is investigated using dissolved NaBH4 at the anode and immobilized KIO4 at the cathode. This battery produces a stable open-circuit cell potential of 1.04 V, and a peak power density of 130 mW cm-2 corresponding to a superficial current density of 160 mA cm-2 at 458 K. With further improvements and scale-up borohydride molten electrolyte batteries and fuel cells could be integrated with thermal energy storage systems.

Application of PtSn/C catalysts and Nafion SiO2 membranes in direct ethanol fuel cell at high temperatures

International Nuclear Information System (INIS)

Dresch, Mauro Andre

2014-01-01

This work has as objective to evaluate anodes and electrolytes in direct ethanol fuel cells (DEFC) operating at high temperature (130 deg C). As anode materials, electrocatalysts based on Pt Sn/C were prepared by Modified Polyol Method with various Pt:Sn atomic ratios. Such methodology promotes self organized electrocatalysts production with narrow particle size distribution and high alloying degree. The electrocatalysts were characterized by XRD, and CO stripping. The results showed that these materials presented high alloying degree and Eonset CO oxidation at lower potential as commercial materials. As electrolyte, Nafion-SiO 2 hybrids were synthesized by sol-gel reaction, by the incorporation of oxide directly into the ionic aggregates of various kinds of Nafion membranes. The synthesis parameter, such sol-gel solvent, membrane thickness and silicon precursor concentration were studied in terms of silica incorporation degree and hybrid mechanical stability. Finally, the optimized anodes and electrolytes were evaluated in DEFC operating at 80 - 130 deg C temperature range. The results showed a significant improvement of the DEFC performance (122 mW cm -2 ), resulted from the acceleration of ethanol oxidation reaction rate due to anode material optimization and high temperature operation once the use of hybrids possibilities the increase of temperature without a significant conductivity loses. In this sense, the combination of optimized electrodes and electrolytes are a promising alternative for the development of these devices. (author)

Ultrasonic hydrometer. [Specific gravity of electrolyte

Science.gov (United States)

Swoboda, C.A.

1982-03-09

The disclosed ultrasonic hydrometer determines the specific gravity (density) of the electrolyte of a wet battery, such as a lead-acid battery. The hydrometer utilizes a transducer that when excited emits an ultrasonic impulse that traverses through the electrolyte back and forth between spaced sonic surfaces. The transducer detects the returning impulse, and means measures the time t between the initial and returning impulses. Considering the distance d between the spaced sonic surfaces and the measured time t, the sonic velocity V is calculated with the equation V = 2d/t. The hydrometer also utilizes a thermocouple to measure the electrolyte temperature. A hydrometer database correlates three variable parameters including sonic velocity in and temperature and specific gravity of the electrolyte, for temperature values between 0 and 40/sup 0/C and for specific gravity values between 1.05 and 1.30. Upon knowing two parameters (the calculated sonic velocity and the measured temperature), the third parameter (specific gravity) can be uniquely found in the database. The hydrometer utilizes a microprocessor for data storage and manipulation.

In Situ formation of pentafluorophosphate benzimidazole anion stabilizes high-temperature performance of lithium-ion batteries

International Nuclear Information System (INIS)

Pradanawati, Sylvia Ayu; Wang, Fu-Ming; Rick, John

2014-01-01

Highlights: • A new pentafluorophosphate benzimidazole anion was formed by Lewis acid-base reaction. • This pentafluorophosphate benzimidazole anion is fabricated with the benzimidazole anion and PF 5 . • This pentafluorophosphate benzimidazole anion avoids the ominous side reactions that PF 5 reacts SEI to form LiF and HF at high temperature. • The additional pentafluorophosphate benzimidazole anion formation well maintains the battery performance at 60 °C measurement compares to the electrolyte only with contains the salt, LiPF 6 . - Abstract: Lithium salts play a critical role in initiating electrochemical reactions in Li-ion batteries. Single Li ions dissociate from bulk-salt and associate with carbonates to form a solid electrolyte interface (SEI) during the first charge-discharge of the battery. SEI formation and the chemical stability of salt must both be controlled and optimized to minimize irreversible reactions in SEI formation and to suppress the decomposition of the salt at high temperatures. This study synthesizes a new benzimidazole-based anion in the electrolyte. This anion, pentafluorophosphate benzimidazole, results from a Lewis acid-base reaction between the benzimidazole anion and PF 5 . The new pentafluorophosphate benzimidazole anion inhibits the decomposition of LiPF 6 by inhibiting PF 5 side reactions, which degrade the SEI, and lead to the formation of LiF and HF at high temperatures. In addition, the use of the pentafluorophosphate benzimidazole anion results in the formation of a modified SEI that is able to modify the battery's performance. Cyclic voltammetry, scanning electron microscopy, differential scanning calorimetry, electrochemical impedance spectroscopy, as well as charge-discharge and X-ray photoelectron spectroscopy measurements have been used to characterize the materials in this study. The formation of the pentafluorophosphate benzimidazole anion in the electrolyte caused a 14% decrease in the activation energy

Double electrolyte sensor for monitoring hydrogen permeation rate in steels

International Nuclear Information System (INIS)

Ouyang, Y.J.; Yu, G.; Ou, A.L.; Hu, L.; Xu, W.J.

2011-01-01

Highlights: → Designed an amperometric hydrogen sensor with double electrolytes. → Explained the principle of determining hydrogen permeation rate. → Verified good stability, reproducibility and correctness of the developed sensor. → Field on-line monitoring the susceptivity of hydrogen induced cracks. - Abstract: An amperometric hydrogen sensor with double electrolytes composed of a gelatiniform electrolyte and KOH solution has been developed to determine the permeation rate of hydrogen atoms in steel equipment owing to hydrogen corrosion. The gelatiniform electrolyte was made of sodium polyacrylate (PAAS), carboxyl methyl cellulose (CMC) and 0.2 mol dm -3 KOH solution. The results show that the gelatiniform electrolyte containing 50 wt.% polymers has suitable viscosity and high electrical conductivity. The consistent permeation curves were detected by the sensor of the double electrolyte and single liquid KOH electrolyte, respectively. The developed sensor has good stability and reproducibility at room temperature.

Double electrolyte sensor for monitoring hydrogen permeation rate in steels

Energy Technology Data Exchange (ETDEWEB)

Ouyang, Y.J. [State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082 (China); Department of Chemistry and Chemical Engineering, Huaihua College, Huaihua 418008 (China); Yu, G., E-mail: yuganghnu@163.co [State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082 (China); Ou, A.L.; Hu, L.; Xu, W.J. [State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082 (China)

2011-06-15

Highlights: {yields} Designed an amperometric hydrogen sensor with double electrolytes. {yields} Explained the principle of determining hydrogen permeation rate. {yields} Verified good stability, reproducibility and correctness of the developed sensor. {yields} Field on-line monitoring the susceptivity of hydrogen induced cracks. - Abstract: An amperometric hydrogen sensor with double electrolytes composed of a gelatiniform electrolyte and KOH solution has been developed to determine the permeation rate of hydrogen atoms in steel equipment owing to hydrogen corrosion. The gelatiniform electrolyte was made of sodium polyacrylate (PAAS), carboxyl methyl cellulose (CMC) and 0.2 mol dm{sup -3} KOH solution. The results show that the gelatiniform electrolyte containing 50 wt.% polymers has suitable viscosity and high electrical conductivity. The consistent permeation curves were detected by the sensor of the double electrolyte and single liquid KOH electrolyte, respectively. The developed sensor has good stability and reproducibility at room temperature.

Modelling the effect of temperature and free acid, silver, copper and lead concentrations on silver electrorefining electrolyte conductivity

OpenAIRE

Aji, Arif T.; Kalliomäki, Taina; Wilson, Benjamin P.; Aromaa, Jari; Lundström, Mari

2016-01-01

Conductivity is one of the key physico-chemical properties of electrolyte in silver electrorefining since it affects the energy consumption of the process. As electrorefining process development trends towards high current density operation, having electrolytes with high conductivities will greatly reduce the energy consumption of the process. This study outlines investigations into silver electrorefining electrolyte conductivity as a function of silver, free acid, copper and lead concentrati...

Daikin Advanced Lithium Ion Battery Technology – High Voltage Electrolyte - REVISED

Energy Technology Data Exchange (ETDEWEB)

Sunstrom, Joseph [Daikin America, Inc., Orangeburg, NY (United States); Hendershot, Ron E. [Daikin America, Inc., Orangeburg, NY (United States)

2017-03-06

An evaluation of high voltage electrolytes which contain fluorochemicals as solvents/additive has been completed with the objective of formulating a safe, stable electrolyte capable of operation to 4.6 V. Stable cycle performance has been demonstrated in LiNi1/3Mn1/3Co1/3O2 (NMC111)/graphite cells to 4.5 V. The ability to operate at high voltage results in significant energy density gain (>30%) which would manifest as longer battery life resulting in higher range for electric vehicles. Alternatively, a higher energy density battery can be made smaller without sacrificing existing energy. In addition, the fluorinated electrolytes examined showed better safety performance when tested in abuse conditions. The results are promising for future advanced battery development for vehicles as well as other applications.

Thermally-responsive, nonflammable phosphonium ionic liquid electrolytes for lithium metal batteries: operating at 100 degrees celsius.

Science.gov (United States)

Lin, X; Kavian, R; Lu, Y; Hu, Q; Shao-Horn, Y; Grinstaff, M W

2015-11-13

Rechargeable batteries such as Li ion/Li metal batteries are widely used in the electronics market but the chemical instability of the electrolyte limits their use in more demanding environmental conditions such as in automotive, oil exploration, or mining applications. In this study, a series of alkyl phosphonium ionic liquid electrolyte are described with high thermal stability and solubility for LiTFSI. A lithium metal battery (LMB) containing a tailored phosphonium ionic liquid/LiTFSI electrolyte operates at 100 °C with good specific capacities and cycling stability. Substantial capacity is maintained during 70 cycles or 30 days. Instant on-off battery operation is realized via the significant temperature dependence of the electrolyte material, demonstrating the robustness and potential for use at high temperature.

A self-standing hydrogel neutral electrolyte for high voltage and safe flexible supercapacitors

Science.gov (United States)

Batisse, N.; Raymundo-Piñero, E.

2017-04-01

The development of safe flexible supercapacitors implies the use of new non-liquid electrolytes for avoiding device leakage which combine mechanical properties and electrochemical performance. In this sense, hydrogel electrolytes composed of a solid non-conductive matrix holding an aqueous electrolytic phase are a reliable solution. In this work, we propose a green physical route for producing self-standing hydrogel films from a PVA polymer based on the freezing/thawing method without using chemical cross-linking agents. Moreover, a neutral electrolytic phase as Na2SO4 is used for reaching higher cell voltages than in an acidic or basic electrolyte. Such new PVA-Na2SO4 hydrogel electrolyte, which also acts as separator, allows reaching voltages windows as high as 1.8 V in a symmetric carbon/carbon supercapacitor with optimal capacitance retention through thousands of cycles. Additionally, in reason of the fast mobility of the ions inside of the polymeric matrix, the hydrogel electrolyte based supercapacitor keeps the power density of the liquid electrolyte device.

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

THERMODYNAMICS OF ELECTROLYTES. X. ENTHALPY AND THE EFFECT OF TEMPERATURE ON THE ACTIVITY COEFFICIENTS.

Energy Technology Data Exchange (ETDEWEB)

Silvester, Leonard F.; Pitzer, Kenneth S.

1977-11-01

Heat of dilution and of solution data are fitted to the form of equation corresponding to that used successfully for activity and osmotic coefficients over a wide range of concentration. The resulting parameters give the change with temperature of the activity and osmotic coefficients. Results are reported for 84 electrolytes of 1-1, 2-1, 3-1, and 2-2 valence types.

Development of solid electrolytes for water electrolysis at higher temperature

Energy Technology Data Exchange (ETDEWEB)

Linkous, C.A. [Florida Solar Energy Center, Cocoa, FL (United States)

1996-10-01

This report describes efforts in developing new solid polymer electrolytes that will enable operation of proton exchange membrane electrolyzers at higher temperatures than are currently possible. Several ionomers have been prepared from polyetheretherketone (PEEK), polyethersulfone (PES), and polyphenylquinoxaline (PPQ) by employing various sulfonation procedures. By controlling the extent of sulfonation, a range of proton conductivities could be achieved, whose upper limit actually exceeded that of commercially available perfluoralkyl sulfonates. Thermoconductimetric analysis of samples at various degrees of sulfonation showed an inverse relationship between conductivity and maximum operating temperature. This was attributed to the dual effect of adding sulfonate groups to the polymer: more acid groups produce more protons for increased conductivity, but they also increase water uptake, which mechanically weakens the membrane. This situation was exacerbated by the limited acidity of the aromatic sulfonic acids (pK{sub A} {approx} 2-3). The possibility of using partial fluorination to raise the acid dissociation constant is discussed.

Anthraquinone derivative as high-performance anode material for sodium-ion batteries using ether-based electrolytes

Directory of Open Access Journals (Sweden)

Linqin Mu

2018-01-01

Full Text Available Organic materials, especially the carbonyl compounds, are promising anode materials for room temperature sodium-ion batteries owing to their high reversible capacity, structural diversity as well as eco-friendly synthesis from bio-mass. Herein, we report a novel anthraquinone derivative, C14H6O4Na2 composited with carbon nanotube (C14H6O4Na2-CNT, used as an anode material for sodium-ion batteries in ether-based electrolyte. The C14H6O4Na2-CNT electrode delivers a reversible capacity of 173 mAh g−1 and an ultra-high initial Coulombic efficiency of 98% at the rate of 0.1 C. The capacity retention is 82% after 50 cycles at 0.2 C and a good rate capability is displayed at 2 C. Furthermore, the average Na insertion voltage of 1.27 V vs. Na+/Na makes it a unique and safety battery material, which would avoid Na plating and formation of solid electrolyte interface. Our contribution provides new insights for designing developed organic anode materials with high initial Coulombic efficiency and improved safety capability for sodium-ion batteries.

Stable solid state reference electrodes for high temperature water chemistry

International Nuclear Information System (INIS)

Jayaweera, P.; Millett, P.J.

1995-01-01

A solid state electrode capable of providing a stable reference potential under a wide range of temperatures and chemical conditions has been demonstrated. The electrode consists of a zirconia or yttria-stabilized zirconia tube packed with an inorganic polymer electrolyte and a silver/silver chloride sensing element. The sensing element is maintained near room temperature by a passive cooling heat sink. The electrode stability was demonstrated by testing it in high temperature (280 C) aqueous solutions over extended periods of time. This reference electrode is useful in many applications, particularly for monitoring the chemistry in nuclear and fossil power plants

A porous ceramic membrane tailored high-temperature supercapacitor

Science.gov (United States)

Zhang, Xin; He, Benlin; Zhao, Yuanyuan; Tang, Qunwei

2018-03-01

The supercapacitor that can operate at high-temperature are promising for markedly increase in capacitance because of accelerated charge movement. However, the state-of-the-art polymer-based membranes will decompose at high temperature. Inspired by solid oxide fuel cells, we present here the experimental realization of high-temperature supercapacitors (HTSCs) tailored with porous ceramic separator fabricated by yttria-stabilized zirconia (YSZ) and nickel oxide (NiO). Using activated carbon electrode and supporting electrolyte from potassium hydroxide (KOH) aqueous solution, a category of symmetrical HTSCs are built in comparison with a conventional polymer membrane based device. The dependence of capacitance performance on temperature is carefully studied, yielding a maximized specific capacitance of 272 F g-1 at 90 °C for the optimized HTSC tailored by NiO/YSZ membrane. Moreover, the resultant HTSC has relatively high durability when suffer repeated measurement over 1000 cycles at 90 °C, while the polymer membrane based supercapacitor shows significant reduction in capacitance at 60 °C. The high capacitance along with durability demonstrates NiO/YSZ membrane tailored HTSCs are promising in future advanced energy storage devices.

In situ spectroscopy and spectroelectrochemistry of uranium in high-temperature alkali chloride molten salts.

Science.gov (United States)

Polovov, Ilya B; Volkovich, Vladimir A; Charnock, John M; Kralj, Brett; Lewin, Robert G; Kinoshita, Hajime; May, Iain; Sharrad, Clint A

2008-09-01

Soluble uranium chloride species, in the oxidation states of III+, IV+, V+, and VI+, have been chemically generated in high-temperature alkali chloride melts. These reactions were monitored by in situ electronic absorption spectroscopy. In situ X-ray absorption spectroscopy of uranium(VI) in a molten LiCl-KCl eutectic was used to determine the immediate coordination environment about the uranium. The dominant species in the melt was [UO 2Cl 4] (2-). Further analysis of the extended X-ray absorption fine structure data and Raman spectroscopy of the melts quenched back to room temperature indicated the possibility of ordering beyond the first coordination sphere of [UO 2Cl 4] (2-). The electrolytic generation of uranium(III) in a molten LiCl-KCl eutectic was also investigated. Anodic dissolution of uranium metal was found to be more efficient at producing uranium(III) in high-temperature melts than the cathodic reduction of uranium(IV). These high-temperature electrolytic processes were studied by in situ electronic absorption spectroelectrochemistry, and we have also developed in situ X-ray absorption spectroelectrochemistry techniques to probe both the uranium oxidation state and the uranium coordination environment in these melts.

A Highly Flexible Supercapacitor Based on MnO2/RGO Nanosheets and Bacterial Cellulose-Filled Gel Electrolyte

Directory of Open Access Journals (Sweden)

Haojie Fei

2017-10-01

Full Text Available The flexible supercapacitors (SCs of the conventional sandwich-type structure have poor flexibility due to the large thickness of the final entire device. Herein, we have fabricated a highly flexible asymmetric SC using manganese dioxide (MnO2 and reduced graphene oxide (RGO nanosheet-piled hydrogel films and a novel bacterial cellulose (BC-filled polyacrylic acid sodium salt-Na2SO4 (BC/PAAS-Na2SO4 neutral gel electrolyte. Apart from being environmentally friendly, this BC/PAAS-Na2SO4 gel electrolyte has high viscosity and a sticky property, which enables it to combine two electrodes together. Meanwhile, the intertangling of the filled BC in the gel electrolyte hinders the decrease of the viscosity with temperature, and forms a separator to prevent the two electrodes from short-circuiting. Using these materials, the total thickness of the fabricated device does not exceed 120 μm. This SC device demonstrates high flexibility, where bending and even rolling have no obvious effect on the electrochemical performance. In addition, owing to the asymmetric configuration, the cell voltage of this flexible SC has been extended to 1.8 V, and the energy density can reach up to 11.7 Wh kg−1 at the power density of 441 W kg−1. This SC also exhibits a good cycling stability, with a capacitance retention of 85.5% over 5000 cycles.

Electrolytic exfoliation of graphite in water with multifunctional electrolytes: en route towards high quality, oxide-free graphene flakes.

Science.gov (United States)

Munuera, J M; Paredes, J I; Villar-Rodil, S; Ayán-Varela, M; Martínez-Alonso, A; Tascón, J M D

2016-02-07

Electrolytic--usually referred to as electrochemical--exfoliation of graphite in water under anodic potential holds enormous promise as a simple, green and high-yield method for the mass production of graphene, but currently suffers from several drawbacks that hinder its widespread adoption, one of the most critical being the oxidation and subsequent structural degradation of the carbon lattice that is usually associated with such a production process. To overcome this and other limitations, we introduce and implement the concept of multifunctional electrolytes. The latter are amphiphilic anions (mostly polyaromatic hydrocarbons appended with sulfonate groups) that play different relevant roles as (1) an intercalating electrolyte to trigger exfoliation of graphite into graphene flakes, (2) a dispersant to afford stable aqueous colloidal suspensions of the flakes suitable for further use, (3) a sacrificial agent to prevent graphene oxidation during exfoliation and (4) a linker to promote nanoparticle anchoring on the graphene flakes, yielding functional hybrids. The implementation of this strategy with some selected amphiphiles even furnishes anodically exfoliated graphenes of a quality similar to that of flakes produced by direct, ultrasound- or shear-induced exfoliation of graphite in the liquid phase (i.e., almost oxide- and defect-free). These high quality materials were used for the preparation of catalytically efficient graphene-Pt nanoparticle hybrids, as demonstrated by model reactions (reduction of nitroarenes). The multifunctional performance of these electrolytes is also discussed and rationalized, and a mechanistic picture of their oxidation-preventing ability is proposed. Overall, the present results open the prospect of anodic exfoliation as a competitive method for the production of very high quality graphene flakes.

Study of Plasma Electrolytic Oxidation Coatings on Aluminum Composites

Directory of Open Access Journals (Sweden)

Leonid Agureev

2018-06-01

Full Text Available Coatings, with a thickness of up to 75 µm, were formed by plasma electrolytic oxidation (PEO under the alternating current electrical mode in a silicate-alkaline electrolyte on aluminum composites without additives and alloyed with copper (1–4.5%. The coatings’ structure was analyzed by scanning electron microscopy, X-ray microanalysis, X-ray photoelectron spectroscopy, nuclear backscattering spectrometry, and XRD analysis. The coatings formed for 60 min were characterized by excessive aluminum content and the presence of low-temperature modifications of alumina γ-Al2O3 and η-Al2O3. The coatings formed for 180 min additionally contained high-temperature corundum α-Al2O3, and aluminum inclusions were absent. The electrochemical behavior of coated composites and uncoated ones in 3% NaCl was studied. Alloyage of aluminum composites with copper increased the corrosion current density. Plasma electrolytic oxidation reduced it several times.

Recent progress in sulfide-based solid electrolytes for Li-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Liu, D., E-mail: liu.dongqiang@ireq.ca; Zhu, W.; Feng, Z.; Guerfi, A.; Vijh, A.; Zaghib, K.

2016-11-15

Graphical abstract: Li{sub 2}S-GeS{sub 2}-P{sub 2}S{sub 5} ternary diagram showing various sulphide compounds as solid electrolytes for Li-ion batteries. - Highlights: • Recent progress of sulfide-based solid electrolytes is described from point of view of structure. • Thio-LISICON type electrolytes exhibited high ionic conductivity due to their bcc sublattice and unique Li{sup +} diffusion pathway. • “Mixed-anion effect” is also an effective way to modify the energy landscape as well as the ionic conductivity. - Abstract: Sulfide-based ionic conductors are one of most attractive solid electrolyte candidates for all-solid-state batteries. In this review, recent progress of sulfide-based solid electrolytes is described from point of view of structure. In particular, lithium thio-phosphates such as Li{sub 7}P{sub 3}S{sub 11}, Li{sub 10}GeP{sub 2}S{sub 12} and Li{sub 11}Si{sub 2}PS{sub 12} etc. exhibit extremely high ionic conductivity of over 10{sup −2} S cm{sup −1} at room temperature, even higher than those of commercial organic carbonate electrolytes. The relationship between structure and unprecedented high ionic conductivity is delineated; some potential drawbacks of these electrolytes are also outlined.

High-performance supercapacitors based on vertically aligned carbon nanotubes and nonaqueous electrolytes

International Nuclear Information System (INIS)

Kim, Byungwoo; Kim, Woong; Chung, Haegeun

2012-01-01

We demonstrate the high performance of supercapacitors fabricated with vertically aligned carbon nanotubes and nonaqueous electrolytes such as ionic liquids and conventional organic electrolytes. Specific capacitance, maximum power and energy density of the supercapacitor measured in ionic liquid were ∼75 F g −1 , ∼987 kW kg −1 and ∼27 W h kg −1 , respectively. The high power performance was consistently indicated by a fast relaxation time constant of 0.2 s. In addition, electrochemical oxidation of the carbon nanotubes improved the specific capacitance (∼158 F g −1 ) and energy density (∼53 W h kg −1 ). Both high power and energy density could be attributed to the fast ion transport realized by the alignment of carbon nanotubes and the wide operational voltage defined by the ionic liquid. The demonstrated carbon-nanotube- and nonaqueous-electrolyte-based supercapacitors show great potential for the development of high-performance energy storage devices. (paper)

High-performance supercapacitors based on vertically aligned carbon nanotubes and nonaqueous electrolytes.

Science.gov (United States)

Kim, Byungwoo; Chung, Haegeun; Kim, Woong

2012-04-20

We demonstrate the high performance of supercapacitors fabricated with vertically aligned carbon nanotubes and nonaqueous electrolytes such as ionic liquids and conventional organic electrolytes. Specific capacitance, maximum power and energy density of the supercapacitor measured in ionic liquid were ~75 F g(-1), ~987 kW kg(-1) and ~27 W h kg(-1), respectively. The high power performance was consistently indicated by a fast relaxation time constant of 0.2 s. In addition, electrochemical oxidation of the carbon nanotubes improved the specific capacitance (~158 F g(-1)) and energy density (~53 W h kg(-1)). Both high power and energy density could be attributed to the fast ion transport realized by the alignment of carbon nanotubes and the wide operational voltage defined by the ionic liquid. The demonstrated carbon-nanotube- and nonaqueous-electrolyte-based supercapacitors show great potential for the development of high-performance energy storage devices. © 2012 IOP Publishing Ltd

High-performance supercapacitors based on vertically aligned carbon nanotubes and nonaqueous electrolytes

Science.gov (United States)

Kim, Byungwoo; Chung, Haegeun; Kim, Woong

2012-04-01

We demonstrate the high performance of supercapacitors fabricated with vertically aligned carbon nanotubes and nonaqueous electrolytes such as ionic liquids and conventional organic electrolytes. Specific capacitance, maximum power and energy density of the supercapacitor measured in ionic liquid were ˜75 F g-1, ˜987 kW kg-1 and ˜27 W h kg-1, respectively. The high power performance was consistently indicated by a fast relaxation time constant of 0.2 s. In addition, electrochemical oxidation of the carbon nanotubes improved the specific capacitance (˜158 F g-1) and energy density (˜53 W h kg-1). Both high power and energy density could be attributed to the fast ion transport realized by the alignment of carbon nanotubes and the wide operational voltage defined by the ionic liquid. The demonstrated carbon-nanotube- and nonaqueous-electrolyte-based supercapacitors show great potential for the development of high-performance energy storage devices.

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

Improved ionic conductivity of lithium-zinc-tellurite glass-ceramic electrolytes

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W. Widanarto

Full Text Available An enhancement in the secondary battery safety demands the optimum synthesis of glass-ceramics electrolytes with modified ionic conductivity. To achieve improved ionic conductivity and safer operation of the battery, we synthesized Li2O included zinc-tellurite glass-ceramics based electrolytes of chemical composition (85-xTeO2·xLi2O·15ZnO, where x = 0, 5, 10, 15 mol%. Samples were prepared using the melt quenching method at 800 °C followed by thermal annealing at 320 °C for 3 h and characterized. The effects of varying temperature, alternating current (AC frequency and Li2O concentration on the structure and ionic conductivity of such glass-ceramics were determined. The SEM images of the annealed glass-ceramic electrolytes displayed rough surface with a uniform distribution of nucleated crystal flakes with sizes less than 1 μm. X-ray diffraction analysis confirmed the well crystalline nature of achieved electrolytes. Incorporation of Li2O in the electrolytes was found to generate some new crystalline phases including hexagonal Li6(TeO6, monoclinic Zn2Te3O8 and monoclinic Li2Te2O5. The estimated crystallite size of the electrolyte was ranged from ≈40 to 80 nm. AC impedance measurement revealed that the variation in the temperatures, Li2O contents, and high AC frequencies have a significant influence on the ionic conductivity of the electrolytes. Furthermore, electrolyte doped with 15 mol% of Li2O exhibited the optimum performance with an ionic conductivity ≈2.4 × 10−7 S cm−1 at the frequency of 54 Hz and in the temperature range of 323–473 K. This enhancement in the conductivity was attributed to the sizable alteration in the ions vibration and ruptures of covalent bonds in the electrolytes network structures. Keywords: Zinc-tellurite, Glass-ceramics, X-ray diffraction, Ionic conductivity, Lithium oxide

Alkaline polymer electrolyte fuel cells stably working at 80 °C

Science.gov (United States)

Peng, Hanqing; Li, Qihao; Hu, Meixue; Xiao, Li; Lu, Juntao; Zhuang, Lin

2018-06-01

Alkaline polymer electrolyte fuel cells are a new class of polymer electrolyte fuel cells that fundamentally enables the use of nonprecious metal catalysts. The cell performance mostly relies on the quality of alkaline polymer electrolytes, including the ionic conductivity and the chemical/mechanical stability. For a long time, alkaline polymer electrolytes are thought to be too weak in stability to allow the fuel cell to be operated at elevated temperatures, e.g., above 60 °C. In the present work, we report a progress in the state-of-the-art alkaline polymer electrolyte fuel cell technology. By using a newly developed alkaline polymer electrolyte, quaternary ammonia poly (N-methyl-piperidine-co-p-terphenyl), which simultaneously possesses high ionic conductivity and excellent chemical/mechanical stability, the fuel cell can now be stably operated at 80 °C with high power density. The peak power density reaches ca. 1.5 W/cm2 at 80 °C with Pt/C catalysts used in both the anode and the cathode. The cell works stably in a period of study over 100 h.

Optimization of the transport and mechanical properties of polysiloxane/polyether hybrid polymer electrolytes

International Nuclear Information System (INIS)

Boaretto, Nicola; Horn, Theresa; Popall, Michael; Sextl, Gerhard

2017-01-01

In this study, the thermo-mechanical properties of networked, polysiloxane/polyether-based, hybrid polymer electrolytes are optimized with the aim of enabling room-temperature operation in lithium metal-polymer batteries. The structural parameters of the electrolytes (polyether chain length, cross-linking and salt concentration) are varied in order to get the best tradeoff between conductivity and mechanical stability. The optimized material has a conductivity close to 1.5·10 −4 S cm −1 at room temperature and a shear storage modulus of 50 kPa up to 100 °C. The effect of TiO 2 nano-particles is also studied with the results showing an overall ambiguous effect on the materials properties. Finally, one of the materials with the highest conductivity is used as electrolyte in a Li/LiFePO 4 cell. This cell has good rate capability and cyclability due to the high conductivity of the electrolyte. However, the high conductivity is reached at expense of the mechanical stability and the resulting electrolyte proves to be too weak to work as an efficient barrier against lithium dendrite growth.

Nanoporous Hybrid Electrolytes for High-Energy Batteries Based on Reactive Metal Anodes

Energy Technology Data Exchange (ETDEWEB)

Tu, Zhengyuan [Department of Materials Science and Engineering, Cornell University, Ithaca NY 14850 USA; Zachman, Michael J. [School of Applied and Engineering Physics, Cornell University, Ithaca NY 14850 USA; Choudhury, Snehashis [School of Chemical Engineering and Biomolecular Engineering, Cornell University, Ithaca NY 14850 USA; Wei, Shuya [School of Chemical Engineering and Biomolecular Engineering, Cornell University, Ithaca NY 14850 USA; Ma, Lin [Department of Materials Science and Engineering, Cornell University, Ithaca NY 14850 USA; Yang, Yuan [Department of Chemistry and Geochemistry, Colorado School of Mines, Golden CO 80401 USA; Kourkoutis, Lena F. [School of Applied and Engineering Physics, Cornell University, Ithaca NY 14850 USA; Kavli Institute at Cornell for Nanoscale Science, Cornell University, Ithaca NY 14853 USA; Archer, Lynden A. [Department of Materials Science and Engineering, Cornell University, Ithaca NY 14850 USA; School of Chemical Engineering and Biomolecular Engineering, Cornell University, Ithaca NY 14850 USA

2017-01-06

Successful strategies for stabilizing electrodeposition of reactive metals, including lithium, sodium, and aluminum are a requirement for safe, high-energy electrochemical storage technologies that utilize these metals as anodes. Unstable deposition produces high-surface area dendritic structures at the anode/electrolyte interface, which causes premature cell failure by complex physical and chemical processes that have presented formidable barriers to progress. Here, it is reported that hybrid electrolytes created by infusing conventional liquid electrolytes into nanoporous membranes provide exceptional ability to stabilize Li. Electrochemical cells based on γ-Al2O3 ceramics with pore diameters below a cut-off value above 200 nm exhibit long-term stability even at a current density of 3 mA cm-2. The effect is not limited to ceramics; similar large enhancements in stability are observed for polypropylene membranes with less monodisperse pores below 450 nm. These findings are critically assessed using theories for ion rectification and electrodeposition reactions in porous solids and show that the source of stable electrodeposition in nanoporous electrolytes is fundamental.

Nanoporous Hybrid Electrolytes for High-Energy Batteries Based on Reactive Metal Anodes

KAUST Repository

Tu, Zhengyuan

2017-01-06

Successful strategies for stabilizing electrodeposition of reactive metals, including lithium, sodium, and aluminum are a requirement for safe, high-energy electrochemical storage technologies that utilize these metals as anodes. Unstable deposition produces high-surface area dendritic structures at the anode/electrolyte interface, which causes premature cell failure by complex physical and chemical processes that have presented formidable barriers to progress. Here, it is reported that hybrid electrolytes created by infusing conventional liquid electrolytes into nanoporous membranes provide exceptional ability to stabilize Li. Electrochemical cells based on γ-Al2O3 ceramics with pore diameters below a cut-off value above 200 nm exhibit long-term stability even at a current density of 3 mA cm−2. The effect is not limited to ceramics; similar large enhancements in stability are observed for polypropylene membranes with less monodisperse pores below 450 nm. These findings are critically assessed using theories for ion rectification and electrodeposition reactions in porous solids and show that the source of stable electrodeposition in nanoporous electrolytes is fundamental.

High Power Electric Double-Layer Capacitors based on Room-Temperature Ionic Liquids and Nanostructured Carbons

Science.gov (United States)

Perez, Carlos R.

The efficient storage of electrical energy constitutes both a fundamental challenge for 21st century science and an urgent requirement for the sustainability of our technological civilization. The push for cleaner renewable forms of energy production, such as solar and wind power, strongly depends on a concomitant development of suitable storage methods to pair with these intermittent sources, as well as for mobile applications, such as vehicles and personal electronics. In this regard, Electrochemical Double-Layer Capacitors (supercapacitors) represent a vibrant area of research due to their environmental friendliness, long lifetimes, high power capability, and relative underdevelopment when compared to electrochemical batteries. Currently supercapacitors have gravimetric energies one order of magnitude lower than similarly advanced batteries, while conversly enjoying a similar advantage over them in terms of power. The challenge is to increase the gravimentric energies and conserve the high power. On the material side, research focuses on highly porous supports and electrolytes, the critical components of supercapacitors. Through the use of electrolyte systems with a wider electrochemical stability window, as well as properly tailored carbon nanomaterials as electrodes, significant improvements in performance are possible. Room Temperature Ionic Liquids and Carbide-Derived Carbons are promising electrolytes and electrodes, respectively. RTILs have been shown to be stable at up to twice the voltage of organic solvent-salt systems currently employed in supercapacitors, and CDCs are tunable in pore structure, show good electrical conductivity, and superior demonstrated capability as electrode material. This work aims to better understand the interplay of electrode and electrolyte parameters, such as pore structure and ion size, in the ultimate performance of RTIL-based supercapacitors in terms of power, energy, and temperature of operation. For this purpose, carbon

Poisson-Fermi modeling of ion activities in aqueous single and mixed electrolyte solutions at variable temperature

Science.gov (United States)

Liu, Jinn-Liang; Eisenberg, Bob

2018-02-01

The combinatorial explosion of empirical parameters in tens of thousands presents a tremendous challenge for extended Debye-Hückel models to calculate activity coefficients of aqueous mixtures of the most important salts in chemistry. The explosion of parameters originates from the phenomenological extension of the Debye-Hückel theory that does not take steric and correlation effects of ions and water into account. By contrast, the Poisson-Fermi theory developed in recent years treats ions and water molecules as nonuniform hard spheres of any size with interstitial voids and includes ion-water and ion-ion correlations. We present a Poisson-Fermi model and numerical methods for calculating the individual or mean activity coefficient of electrolyte solutions with any arbitrary number of ionic species in a large range of salt concentrations and temperatures. For each activity-concentration curve, we show that the Poisson-Fermi model requires only three unchanging parameters at most to well fit the corresponding experimental data. The three parameters are associated with the Born radius of the solvation energy of an ion in electrolyte solution that changes with salt concentrations in a highly nonlinear manner.

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.

Two Players Make a Formidable Combination: In Situ Generated Poly(acrylic anhydride-2-methyl-acrylic acid-2-oxirane-ethyl ester-methyl methacrylate) Cross-Linking Gel Polymer Electrolyte toward 5 V High-Voltage Batteries.

Science.gov (United States)

Ma, Yue; Ma, Jun; Chai, Jingchao; Liu, Zhihong; Ding, Guoliang; Xu, Gaojie; Liu, Haisheng; Chen, Bingbing; Zhou, Xinhong; Cui, Guanglei; Chen, Liquan

2017-11-29

Electrochemical performance of high-voltage lithium batteries with high energy density is limited because of the electrolyte instability and the electrode/electrolyte interfacial reactivity. Hence, a cross-linking polymer network of poly(acrylic anhydride-2-methyl-acrylic acid-2-oxirane-ethyl ester-methyl methacrylate) (PAMM)-based electrolyte was introduced via in situ polymerization inspired by "shuangjian hebi", which is a statement in a traditional Chinese Kungfu story similar to the synergetic effect of 1 + 1 > 2. A poly(acrylic anhydride) and poly(methyl methacrylate)-based system is very promising as electrolyte materials for lithium-ion batteries, in which the anhydride and acrylate groups can provide high voltage resistance and fast ionic conductivity, respectively. As a result, the cross-linking PAMM-based electrolyte possesses a significant comprehensive enhancement, including electrochemical stability window exceeding 5 V vs Li + /Li, an ionic conductivity of 6.79 × 10 -4 S cm -1 at room temperature, high mechanical strength (27.5 MPa), good flame resistance, and excellent interface compatibility with Li metal. It is also demonstrated that this gel polymer electrolyte suppresses the negative effect resulting from dissolution of Mn 2+ ions at 25 and 55 °C. Thus, the LiNi 0.5 Mn 1.5 O 4 /Li and LiNi 0.5 Mn 1.5 O 4 /Li 4 Ti 5 O 12 cells using the optimized in situ polymerized cross-linking PAMM-based gel polymer electrolyte deliver stable charging/discharging profiles and excellent rate performance at room temperature and even at 55 °C. These findings suggest that the cross-linking PAMM is an intriguing candidate for 5 V class high-voltage gel polymer electrolyte toward high-energy lithium-on batteries.

High-energy green supercapacitor driven by ionic liquid electrolytes as an ultra-high stable next-generation energy storage device

Science.gov (United States)

Thangavel, Ranjith; Kannan, Aravindaraj G.; Ponraj, Rubha; Thangavel, Vigneysh; Kim, Dong-Won; Lee, Yun-Sung

2018-04-01

Development of supercapacitors with high energy density and long cycle life using sustainable materials for next-generation applications is of paramount importance. The ongoing challenge is to elevate the energy density of supercapacitors on par with batteries, while upholding the power and cyclability. In addition, attaining such superior performance with green and sustainable bio-mass derived compounds is very crucial to address the rising environmental concerns. Herein, we demonstrate the use of watermelon rind, a bio-waste from watermelons, towards high energy, and ultra-stable high temperature green supercapacitors with a high-voltage ionic liquid electrolyte. Supercapacitors assembled with ultra-high surface area, hierarchically porous carbon exhibits a remarkable performance both at room temperature and at high temperature (60 °C) with maximum energy densities of ∼174 Wh kg-1 (25 °C), and 177 Wh kg-1 (60 °C) - based on active mass of both electrodes. Furthermore, an ultra-high specific power of ∼20 kW kg-1 along with an ultra-stable cycling performance with 90% retention over 150,000 cycles has been achieved even at 60 °C, outperforming supercapacitors assembled with other carbon based materials. These results demonstrate the potential to develop high-performing, green energy storage devices using eco-friendly materials for next generation electric vehicles and other advanced energy storage systems.

Electrospun PVdF-based fibrous polymer electrolytes for lithium ion polymer batteries

International Nuclear Information System (INIS)

Kim, Jeong Rae; Choi, Sung Won; Jo, Seong Mu; Lee, Wha Seop; Kim, Byung Chul

2004-01-01

This paper discusses the preparation of microporous fibrous membranes from PVdF solutions with different polymer contents, using the electrospinning technique. Electrospun PVdF-based fibrous membranes with average fiber diameters (AFD's) of 0.45-1.38 μm have an apparent porosity and a mean pore size (MPS) of 80-89% and 1.1-4.3 μm, respectively. They exhibited a high uptake of the electrolyte solution (320-350%) and a high ionic conductivity of above 1 x 10 -3 s/cm at room temperature. Their ionic conductivity increased with the decrease in the AFD of the fibrous membrane due to its high electrolyte uptake. The interaction between the electrolyte molecules and the PVdF with a high crystalline content may have had a minor effect on the lithium ion transfer in the fibrous polymer electrolyte, unlike in a nanoporous gel polymer electrolyte. The fibrous polymer electrolyte that contained a 1 M LiPF 6 -EC/DMC/DEC (1/1/1 by weight) solution showed a high electrochemical stability of above 5.0 V, which increased with the decrease in the AFD The interfacial resistance (R i ) between the polymer electrolyte and the lithium electrode slightly increased with the storage time, compared with the higher increase in the interfacial resistance of other gel polymer electrolytes. The prototype cell (MCMB/PVdF-based fibrous electrolyte/LiCoO 2 ) showed a very stable charge-discharge behavior with a slight capacity loss under constant current and voltage conditions at the C/2-rate of 20 and 60 deg. C

Borate electrolyte additives for high voltage lithium nickel manganese oxide electrode: A comparative study

International Nuclear Information System (INIS)

Chen, Zhiting; Wang, Cun; Xing, Lidan; Wang, Xianshu; Tu, Wenqiang; Zhu, Yunmin; Li, Weishan

2017-01-01

Highlights: •TMB and TEB effective improve the cyclic stability of LNMO at high voltage. •The performance of LNMO with TMB-containing electrolyte is superior to that of TEB. •LNMO shows catalytic effect on the oxidation reaction of TEB. •The film generated in TMB shows better ability on suppressing LNMO shedding than TEB. -- Abstract: Trimethyl borate (TMB) and triethyl borate (TEB) are used as film-forming electrolyte additives for high voltage Lithium nickel manganese oxide (LNMO) cathode. DFT calculation and initial charge curve of LNMO reveal that the oxidation activity of TEB is higher than that of TMB. Addition of 2% TMB and 2% TEB effectively improve the capacity retention of high voltage LNMO from 23.4% to 85.3% and 72.6% after 600 cycles, respectively. The film generated in TMB-containing electrolyte shows better ability on suppressing the LNMO shedding in comparison with that of TEB, resulting in higher capacity retention of LNMO in TMB-containing electrolyte at high voltage. The superior performance of LNMO with TMB-containing electrolyte should be ascribed to its less intense film-forming reaction which generates a denser protective surface film on LNMO surface. However, why LNMO shows catalyzation effect on TEB oxidation but not on TMB is unclear, which needs further intensive investigation.

Synthesis and characterization of ionomers as polymer electrolytes for energy conversion devices

Science.gov (United States)

Oh, Hyukkeun

group and a poly(ether ether ketone) backbone showed the highest proton conductivity and proton diffusion coefficient among the three ionomers, demonstrating the effect of the perfluorinated side chains. The proton conductivity of the novel ionomer was comparable to that of Nafion over a wide humidity range and temperature. A lithium perfluorosulfonate ionomer based on aromatic poly(arylene ether)s with pendant lithium perfluoroethyl sulfonates was prepared by ion exchange of the perlfuorosulfonic acid ionomer, and subsequently incoroporated into a lithium-ion battery cell as a single-ion conducting electrolyte. The microporous polymer film saturated with organic carbonates exhibited a nearly unity Li + transfer number, high ionic conductivity (e.g. > 10-3 S m-1 at room temperature) over a wide range of temperatures, high electrochemical stability, and excellent mechanical properties. Excellent cyclability with almost identical charge and discharge capacities have been demonstrated at ambient temperature in the batteries assembled from the prepared single-ion conductors. The mechanical stability of the polymer film was attributed to the rigid polymer backbone which was largely unaffected by the presence of plasticizing organic solvents, while the porous channels with high concentration of the perfluorinated side chains resulted in high ionic conductivity. The expected high charge-rate performance was not achieved, however, due to the high interfacial impedance present between the polymer electrolyte and the electrodes. Several procedural modifications were employed in order to decrease the interfacial impedance of the battery cell. The poly(arylene ether) based ionomer was saturated with an ionic liquid mixture, in order to explore the possibility of its application as a safe, inflammable electrolyte. A low-viscosity ionic liquid with high ionic conductivity, 1-butyl-3-methylimidazolium thiocyanate which has never been successfully utilized as an electrolyte for lithium

Electrode for improving electrochemical measurements in high temperature water

International Nuclear Information System (INIS)

Sengarsai, T.

2005-01-01

A silver/silver-chloride (Ag/AgCl) reference electrode was specially designed and constructed in a body of oxidized titanium for potentiometric measurements under high-temperature and high-pressure conditions. To avoid the thermal decomposition of silver-chloride, the electrode is designed to maintain the reference element at low temperature while it is still connected to high-temperature process zone via a non-isothermal electrolyte bridge. This configuration leads to the development of a thermal gradient along the length of the electrode. At room temperature, the stability of the Ag/AgCl reference electrode versus a standard calomel electrode (SCE) is maintained with an accuracy of 5 mV. The electrode's performance at high temperature and pressure (up to 300 o C and 1500 psi) was examined by measuring the potential difference against platinum, which acted as a reversible hydrogen electrode (RHE). Comparison of the experimental and theoretical values verifies the reliability and reproducibility of the electrode. Deviation from the Nernst equation is considered and related to the thermal liquid junction potential (TLJP). An empirical correction factor is used to maintain the Ag/AgCl potential within an acceptable accuracy limit of ±20 mV at high temperature. (author)

Hydrogen Production System with High Temperature Electrolysis for Nuclear Power Plant

International Nuclear Information System (INIS)

Kentaro, Matsunaga; Eiji, Hoashi; Seiji, Fujiwara; Masato, Yoshino; Taka, Ogawa; Shigeo, Kasai

2006-01-01

Steam electrolysis with solid oxide cells is one of the most promising methods for hydrogen production, which has the potential to be high efficiency. Its most parts consist of environmentally sound and common materials. Recent development of ceramics with high ionic conductivity suggests the possibility of widening the range of operating temperature with maintaining the high efficiency. Toshiba is constructing a hydrogen production system with solid oxide electrolysis cells for nuclear power plants. Tubular-type cells using YSZ (Yttria-Stabilized- Zirconia) as electrolyte showed good performance of steam electrolysis at 800 to 900 deg C. Larger electrolysis cells with present configuration are to be combined with High Temperature Reactors. The hydrogen production efficiency on the present designed system is expected around 50% at 800 to 900 deg C of operating temperature. For the Fast Reactors, 'advanced cell' with higher efficiency at lower temperature are to be introduced. (authors)

Halogen effect for improving high temperature oxidation resistance of Ti-50Al by anodization

Science.gov (United States)

Mo, Min-Hua; Wu, Lian-Kui; Cao, Hua-Zhen; Lin, Jun-Pin; Zheng, Guo-Qu

2017-06-01

The high temperature oxidation resistance of Ti-50Al was significantly improved via halogen effect which was achieved by anodizing in an ethylene glycol solution containing with fluorine ion. The anodized Ti-50Al with holes and micro-cracks could be self-repaired during oxidation at 1000 °C. The thickness of the oxide scale increases with the prolonging of oxidation time. On the basis of halogen effect for improving the high temperature oxidation resistance of Ti-50Al by anodization, only fluorine addition into the electrolyte can effectively improve the high temperature oxidation resistance of Ti-50Al.

Physiological and biochemical response to high temperature stress in Okra (Abelmoschus esculentus L. Moench)

Science.gov (United States)

Hayamanesh, Shahnoosh; Keitel, Claudia; Ahmad, Nabil; Trethowan, Richard

2016-04-01

High temperature has been shown to lower the growth and yield of Okra, an important summer vegetable crop grown in Asia, Africa, the Middle East and Australia. We aimed to characterise the physiological and biochemical response of Okra to heat stress. 150 genotypes from Pakistan and the AVRDC (The World Vegetable Centre) were screened for their physiological response (fluorescence, electrolyte leakage and yield) to heat in a greenhouse. Four genotypes (including heat tolerant and sensitive) were selected and subsequently grown in control and hot greenhouses. Daytime temperatures were on average 10°C warmer in the hot greenhouse, whereas nighttime temperatures were similar between the two temperature treatments. During a 12 week period, the physiological (assimilation rate, transpiration rate, stomatal conductance, fluorescence, electrolyte leakage, water potential) and biochemical (carbohydrates, sugar alcohols, C content) response of the four genotypes to heat stress was assessed. The effect of heat stress on the C allocation patterns and yield in Okra will be discussed.

Primary and Secondary Lithium Batteries Capable of Operating at Low Temperatures for Planetary Exploration

Science.gov (United States)

Smart, M. C.; Ratnakumar, B. V.; West, W. C.; Brandon, E. J.

2011-01-01

Objectives and Approach: (1) Develop advanced Li ]ion electrolytes that enable cell operation over a wide temperature range (i.e., -60 to +60 C). Improve the high temperature stability and lifetime characteristics of wide operating temperature electrolytes. (2) Define the performance limitations at low and high temperature extremes, as well as, life limiting processes. (3) Demonstrate the performance of advanced electrolytes in large capacity prototype cells.

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.)

Multi-layer thin-film electrolytes for metal supported solid oxide fuel cells

Science.gov (United States)

Haydn, Markus; Ortner, Kai; Franco, Thomas; Uhlenbruck, Sven; Menzler, Norbert H.; Stöver, Detlev; Bräuer, Günter; Venskutonis, Andreas; Sigl, Lorenz S.; Buchkremer, Hans-Peter; Vaßen, Robert

2014-06-01

A key to the development of metal-supported solid oxide fuel cells (MSCs) is the manufacturing of gas-tight thin-film electrolytes, which separate the cathode from the anode. This paper focuses the electrolyte manufacturing on the basis of 8YSZ (8 mol.-% Y2O3 stabilized ZrO2). The electrolyte layers are applied by a physical vapor deposition (PVD) gas flow sputtering (GFS) process. The gas-tightness of the electrolyte is significantly improved when sequential oxidic and metallic thin-film multi-layers are deposited, which interrupt the columnar grain structure of single-layer electrolytes. Such electrolytes with two or eight oxide/metal layers and a total thickness of about 4 μm obtain leakage rates of less than 3 × 10-4 hPa dm3 s-1 cm-2 (Δp: 100 hPa) at room temperature and therefore fulfill the gas tightness requirements. They are also highly tolerant with respect to surface flaws and particulate impurities which can be present on the graded anode underground. MSC cell tests with double-layer and multilayer electrolytes feature high power densities more than 1.4 W cm-2 at 850 °C and underline the high potential of MSC cells.

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.

Cross-linked Composite Gel Polymer Electrolyte using Mesoporous Methacrylate-Functionalized SiO2 Nanoparticles for Lithium-Ion Polymer Batteries

Science.gov (United States)

Shin, Won-Kyung; Cho, Jinhyun; Kannan, Aravindaraj G.; Lee, Yoon-Sung; Kim, Dong-Won

2016-01-01

Liquid electrolytes composed of lithium salt in a mixture of organic solvents have been widely used for lithium-ion batteries. However, the high flammability of the organic solvents can lead to thermal runaway and explosions if the system is accidentally subjected to a short circuit or experiences local overheating. In this work, a cross-linked composite gel polymer electrolyte was prepared and applied to lithium-ion polymer cells as a safer and more reliable electrolyte. Mesoporous SiO2 nanoparticles containing reactive methacrylate groups as cross-linking sites were synthesized and dispersed into the fibrous polyacrylonitrile membrane. They directly reacted with gel electrolyte precursors containing tri(ethylene glycol) diacrylate, resulting in the formation of a cross-linked composite gel polymer electrolyte with high ionic conductivity and favorable interfacial characteristics. The mesoporous SiO2 particles also served as HF scavengers to reduce the HF content in the electrolyte at high temperature. As a result, the cycling performance of the lithium-ion polymer cells with cross-linked composite gel polymer electrolytes employing methacrylate-functionalized mesoporous SiO2 nanoparticles was remarkably improved at elevated temperatures. PMID:27189842

Electrolytic coloration of O22--doped NaCl crystals

International Nuclear Information System (INIS)

Qin Fang; Gu Hongen; Song Cuiying; Wang Na; Guo Meili; Wang Fen; Liu Jia

2007-01-01

O 2 2- -doped NaCl crystals are colored electrolytically by using a pointed cathode and a flat anode at various temperatures and voltages, which mainly benefit from appropriate coloration temperatures and voltages as well as anode structure of used electrolysis apparatus. Characteristic OH - , U, V 2 m , U A , V 2 , V 3 , O 2- -V a + complex, F, R 1 , R 2 and M absorption bands are observed in absorption spectra of the colored crystals. Production and conversion of color centers in electrolytic coloration is explained. Current-time curves for electrolytic colorations and their relationships with electrolytic colorations were given

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

Secondary batteries based on lithium are the most important energy storage technology for contemporary portable devices. The lithium ion battery (LIB) in widespread commercial use today is a compromise technology. It compromises high energy, high power, and design flexibility for long cell operating lifetimes and safety. Materials science, transport phenomena, and electrochemistry in the electrodes and electrolyte that constitute such batteries are areas of active study worldwide because significant improvements in storage capacity and cell lifetime are required to meet new demands, including the electrification of transportation and for powering emerging autonomous aircraft and robotics technologies. By replacing the carbonaceous host material used as the anode in an LIB with metallic lithium, rechargeable lithium metal batteries (LMBs) with higher storage capacity and compatibility with low-cost, high-energy, unlithiated cathodes such as sulfur, manganese dioxide, carbon dioxide, and oxygen become possible. Large-scale, commercial deployment of LMBs are today limited by safety concerns associated with unstable electrodeposition and lithium dendrite formation during cell recharge. LMBs are also limited by low cell operating lifetimes due to parasitic chemical reactions between the electrode and electrolyte. These concerns are greater in rechargeable batteries that utilize other, more earth abundant metals such as sodium and to some extent even aluminum. Inspired by early theoretical works, various strategies have been proposed for alleviating dendrite proliferation in LMBs. A commonly held view among these early studies is that a high modulus, solid-state electrolyte that facilitates fast ion transport, is nonflammable, and presents a strong-enough physical barrier to dendrite growth is a requirement for any commercial LMB. Unfortunately, poor room-temperature ionic conductivity, challenging processing, and the high cost of ceramic electrolytes that meet the

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.

Effect of ionic conductivity of zirconia electrolytes on polarization properties of various electrodes in SOFC

Energy Technology Data Exchange (ETDEWEB)

Watanabe, Masahiro; Uchida, Hiroyuki; Yoshida, Manabu [Yamanashi Univ., Kofu (Japan)

1996-12-31

Solid oxide fuel cells (SOFCs) have been intensively investigated because, in principle, their energy conversion efficiency is fairly high. Lowering the operating temperature of SOFCs from 1000{degrees}C to around 800{degrees}C is desirable for reducing serious problems such as physical and chemical degradation of the constructing materials. The object of a series of the studies is to find a clue for achieving higher electrode performances at a low operating temperature than those of the present level. Although the polarization loss at electrodes can be reduced by using mixed-conducting ceria electrolytes, or introducing the mixed-conducting (reduced zirconia or ceria) laver on the conventional zirconia electrolyte surface, no reports are available on the effect of such an ionic conductivity of electrolytes on electrode polarizations. High ionic conductivity of the electrolyte, of course, reduces the ohmic loss. However, we have found that the IR-free polarization of a platinum anode attached to zirconia electrolytes is greatly influenced by the ionic conductivity, {sigma}{sub ion}, of the electrolytes used. The higher the {sigma}{sub ion}, the higher the exchange current density, j{sub 0}, for the Pt anode in H{sub 2} at 800 {approximately} 1000{degrees}C. It was indicated that the H{sub 2} oxidation reaction rate was controlled by the supply rate of oxide ions through the Pt/zirconia interface which is proportional to the {sigma}{sub ion}. Recently, we have proposed a new concept of the catalyzed-reaction layers which realizes both high-performances of anodes and cathodes for medium-temperature operating SOFCs. We present the interesting dependence of the polarization properties of various electrodes (the SDC anodes with and without Ru microcatalysts, Pt cathode, La(Sr)MnO{sub 3} cathodes with and without Pt microcatalysts) on the {sigma}{sub ion} of various zirconia electrolytes at 800 {approximately} 1000{degrees}C.

Synthesis and Characterization of Nafion-SiO2 Composite Membranes as an Electrolyte for Medium Temperature and Low Relative Humidity

Directory of Open Access Journals (Sweden)

Mahreni Mahreni

2011-12-01

Full Text Available The weakness of the Nafion membrane as electrolyte of PEMFC associated with physical properties that is easy to shrink at temperatures above 80°C due to dehydration. Shrinkage will decrease the conductivity and membrane damage. Nafion-SiO2 composite membranes can improve membrane stability. The role of SiO2 in the Nafion clusters is as water absorbent cause the membrane remains wet at high temperatures and low humidity and conductivity remains high. The results showed the content of 2.8 wt% of SiO2 in the Nafion membrane, the conductivity of composite membrane is higher than the pure Nafion membrane that are 0.127 S cm-1 in dry conditions and 0.778 S cm-1 in wet conditions at room temperature. Compared with the pure Nafion membrane conductivity are 0.0661 S cm-1 and 0.448 S cm-1 respectively in dry and wet conditions.

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.

Piperidinium tethered nanoparticle-hybrid electrolyte for lithium metal batteries

KAUST Repository

Korf, Kevin S.

2014-06-23

We report on the synthesis of novel piperidinium-based ionic liquid tethered nanoparticle hybrid electrolytes and investigate their physical and electrochemical properties. Hybrid electrolytes based on the ionic liquid 1-methyl-1-propylpiperidinium bis(trifluoromethanesulfone) imide covalently tethered to silica nanoparticles (SiO2-PP-TFSI) were blended with propylene carbonate-1 M lithium bis(trifluoromethanesulfone) imide (LiTFSI). We employed NMR analysis to confirm the successful creation of the hybrid material. Dielectric and rheological measurements show that these electrolytes exhibit exceptional room-temperature DC ionic conductivity (10-2 to 10 -3 S cm-1) as well as high shear mechanical moduli (105 to 106 Pa). Lithium transference numbers were found to increase with particle loading and to reach values as high as 0.22 at high particle loadings where the particle jam to form a soft glassy elastic medium. Analysis of lithium electrodeposits obtained in the hybrid electrolytes using SEM and EDX spectra show that the SiO2-PP-TFSI nanoparticles are able to smooth lithium deposition and inhibit lithium dendrite proliferation in Li metal batteries. LTOSiO2-PP-TFSI/PC in 1 M LiTFSILi half-cells based on the SiO2-PP-TFSI hybrid electrolytes exhibit attractive voltage profiles and trouble-free extended cycling behavior over more than 1000 cycles of charge and discharge. This journal is © the Partner Organisations 2014.

High-Efficiency Glass and Printable Flexible Dye-Sensitized Solar Cells with Water-Based Electrolytes

Directory of Open Access Journals (Sweden)

Omar Moudam

2014-01-01

Full Text Available The performance of a flexible and glass dye-sensitized solar cell (DSSC with water-based electrolyte solutions is described. High concentrations of alkylamidazoliums were used to overcome the deleterious effect of water and, based on this variable, pure water-based electrolyte DSSCs were tested displaying the highest recorded efficiency so far of 3.45% and 6% for flexible and glass cells, respectively, under a simulated air mass 1.5 solar spectrum illumination at 100 mWcm−2. An improvement in the Jsc with high water content and the positive impact of GuSCN on the enhancement of the performance of pure water-based electrolytes were also observed.

Boronic ionogel electrolytes to improve lithium transport for Li-ion batteries

International Nuclear Information System (INIS)

Lee, Albert S.; Lee, Jin Hong; Hong, Soon Man; Lee, Jong-Chan; Hwang, Seung Sang; Koo, Chong Min

2016-01-01

Boron containing ionogels were fabricated through chemical crosslinking of boron allyloxide with polyethylene glycol dimethacrylate in an ionic liquid electrolyte solution to obtain mechanically robust gels. Because of the relatively small concentration of crosslinking agent required to fully solidify the ionic liquid electrolyte, good characters of high ionic conductivity, high thermal stability, and good electrochemical stability were observed. A spectroscopic investigation of the boronic ionogels revealed that the lithium mobility was noticeably enhanced compared with ionogels fabricated without the boronic crosslinker, leading to promising Li-ion battery performance at elevated temperatures.

Fabrication of titanium dioxide nanotube arrays using organic electrolytes

Science.gov (United States)

Yoriya, Sorachon

anodization rates are relatively slower in DEG electrolyte; as a result, the nanotube length is typically less than 10 microm. Pore size of nanotubes grown in DEG has been extended from 150 nm up to approximately 400 nm. The approach to pore widening could be achieved by using a specific condition of low HF concentration and prolonged anodization time. The study of evolution of nanotubes grown in DEG electrolytes showed that a fibrous layer was formed in the early growth stages and then was chemically and gradually removed after a long duration, leaving behind the nanotubes with large pore size. In DEG electrolyte, the closer spacing between Ti and Pt electrodes resulted in the larger nanotube morphological parameters due to the enhanced electrode kinetics facilitating the electrode reactions. Furthermore, this dissertation showed possibilities to crystallize the titania nanotube array films at room temperature via anodization in either DMSO or DEG electrolytes. The partially crystallized films could be achieved specifically in the optimum slow growth process conditions. Due to partial crystallization of the as-anodized samples, the high temperature annealing study revealed that the temperatures of phase transformation are 260 ºC and 430°C for respectively amorphous to anatase and anatase to rutile, which are accounted as the lowest phase transformation temperatures reported to date (2010). Finally, the photoelectrochemical properties of the DMSO fabricated nanotubes were investigated. The maximum photocurrent density of ~ 11 mA cm--2 was achieved by using the 46-microm long nanotube array sample with completely open pores, and photoconversion efficiencies of 5.425 % (+/- 0.087) (under UV light) and 0.197 % (+/- 0.001) (under solar spectrum AM 1.5) have been demonstrated. Biomedical applications of the DEG fabricated nanotube arrays films such as blood clotting, hemocompatibility, and drug delivery were investigated. The titania nanotube arrays showed a significant platelet

Preparation of poly(acrylonitrile-butyl acrylate) gel electrolyte for lithium-ion batteries

International Nuclear Information System (INIS)

Tian Zheng; He Xiangming; Pu Weihua; Wan Chunrong; Jiang Changyin

2006-01-01

Poly(acrylonitrile-butyl acrylate) gel polymer electrolyte was prepared for lithium ion batteries. The preparation started with synthesis of poly(acrylonitrile-butyl acrylate) by radical emulsion polymerization, followed by phase inversion to produce microporous membrane. Then, the microporous gel polymer electrolytes (MGPEs) was prepared with the microporous membrane and LiPF 6 in ethylene carbonate/diethyl carbonate. The dry microporous membrane showed a fracture strength as high as 18.98 MPa. As-prepared gel polymer electrolytes presented ionic conductivity in excess of 3.0 x 10 -3 S cm -1 at ambient temperature and a decomposition voltage over 6.6 V. The results showed that the as-prepared gel polymer electrolytes were promising materials for Li-ion batteries

Designing Artificial Solid-Electrolyte Interphases for Single-Ion and High-Efficiency Transport in Batteries

KAUST Repository

Tu, Zhengyuan

2017-09-21

Substrates able to rectify transport of ions based on charge and/or size are ubiquitous in biological systems. Electrolytes and interphases that selectively transport electrochemically active ions are likewise of broad interest in all electrical energy storage technologies. In lithium-ion batteries, electrolytes with single- or near-single-ion conductivity reduce losses caused by ion polarization. In emergent lithium or sodium metal batteries, they maintain high conductivity at the anode and stabilize metal deposition by fundamental mechanisms. We report that 20- to 300-nm-thick, single-ion-conducting membranes deposited at the anode enable electrolytes with the highest combination of cation transference number, ionic conductivity, and electrochemical stability reported. By means of direct visualization we find that single-ion membranes also reduce dendritic deposition of Li in liquids. Galvanostatic measurements further show that the electrolytes facilitate long (3 mAh) recharge of full Li/LiNi0.8Co0.15Al0.05O2 (NCA) cells with high cathode loadings (3 mAh cm−2/19.9 mg cm−2) and at high current densities (3 mA cm−2).

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.

Intrinsically stretchable supercapacitors composed of polypyrrole electrodes and highly stretchable gel electrolyte.

Science.gov (United States)

Zhao, Chen; Wang, Caiyun; Yue, Zhilian; Shu, Kewei; Wallace, Gordon G

2013-09-25

There has been an emerging interest in stretchable power sources compatible with flexible/wearable electronics. Such power sources must be able to withstand large mechanical strains and still maintain function. Here we report a highly stretchable H3PO4-poly(vinyl alcohol) (PVA) polymer electrolyte obtained by optimizing the polymer molecular weight and its weight ratio to H3PO4 in terms of conductivity and mechanical properties. The electrolyte demonstrates a high conductivity of 3.4 × 10(-3) S cm(-1), and a high fracture strain at 410% elongation. It is mechanically robust with a tensile strength of 2 MPa and a Young's modulus of 1 MPa, and displays a small plastic deformation (5%) after 1000 stretching cycles at 100% strain. A stretchable supercapacitor device has been developed based on buckled polypyrrole electrodes and the polymer electrolyte. The device shows only a small capacitance loss of 5.6% at 30% strain, and can retain 81% of the initial capacitance after 1000 cycles of such stretching.

Polymer electrolytes: an investigation of some poly (N-propylaziridine)/lithium salt compositions

Energy Technology Data Exchange (ETDEWEB)

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

1984-04-01

Poly (N-propylaziridine)/lithium salt compositions were synthesized and their electrical conductivities were measured 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 were studied. The salts markedly improve conductivity of the compositions over that of the undoped polymer but they are insufficiently conducting to be considered as battery electrolytes, due possibly to ion pairing. Their creep resistance is also low. Less fluid compositions containing higher molecular weight polymers better able to promote ion separation are more suitable. (ESA)

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.)

Determination of hydration numbers of electrolytes from temperature dependence of PMR chemical shifts

International Nuclear Information System (INIS)

Subramanian, N.

1979-01-01

The method proposed by Malinowski et al. for the determination of effective hydration numbers (h) of electrolytes leads to a consistent incrrease in the observed values of 'h' with increase in solution concentration. An attempt is made to rationalize the experimental results by cosidering the simultaneous effects of temperature and concentration on the proton chemical shift. It is suggested that Malinowski's technique might yeld 'h' values very close to the true value for those ions for which there is a fortuitous cancellation of structure-making and structure-breaking properties. (Author) [pt

Molybdenum cell for x-ray diffraction measurements of fluid alkali metals at high temperatures and high pressures

Science.gov (United States)

Matsuda, Kazuhiro; Tamura, Kozaburo; Katoh, Masahiro; Inui, Masanori

2004-03-01

We have developed a sample cell for x-ray diffraction measurements of fluid alkali metals at high temperatures and high pressures. All parts of the cell are made of molybdenum which is resistant to the chemical corrosion of alkali metals. Single crystalline molybdenum disks electrolytically thinned down to 40 μm were used as the walls of the cell through which x rays pass. The crystal orientation of the disks was controlled in order to reduce the background from the cell. All parts of the cell were assembled and brazed together using a high-temperature Ru-Mo alloy. Energy dispersive x-ray diffraction measurements have been successfully carried out for fluid rubidium up to 1973 K and 16.2 MPa. The obtained S(Q) demonstrates the applicability of the molybdenum cell to x-ray diffraction measurements of fluid alkali metals at high temperatures and high pressures.

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.

Ethoxy (pentafluoro) cyclotriphosphazene (PFPN) as a multi-functional flame retardant electrolyte additive for lithium-ion batteries

Science.gov (United States)

Li, Xi; Li, Weikang; Chen, Lai; Lu, Yun; Su, Yuefeng; Bao, Liying; Wang, Jing; Chen, Renjie; Chen, Shi; Wu, Feng

2018-02-01

With the wide application of lithium-ion batteries (LiBs), safety performance is an important constraint on the commercialization of large-scale, high-capacity LIBs. The main reason for the safety problem is that the electrolyte of LiBs is highly flammable, especially under high temperature and high voltage. It is an effective method to improve the safety of cells by mixing flame retardant with conventional electrolyte comprising of LiPF6 and carbonates. Herein, ethoxy (pentafluoro) cyclotriphosphazene (PFPN) is studied as a high efficiency flame retardant. Adding 5 vol% of PFPN results in a non-flammable electrolyte with self-extinguishing time (SET) of 12.38 s g-1 and critical oxygen index (COI) of 22.9, without compromising the capacity of cathode material. The initial discharge capacity of the LiCoO2 electrode with 5% PFPN is 150.7 mAh g-1, with a capacity retention of 99.14% after 30 cycles at 0.1 C. The results show that 5 vol% is the best adding amount of PFPN for electrolyte, which can modify the solid electrolyte interface (SEI). Moreover, PFPN reduces charge transfer resistance of the cells, resulting decreased electrode polarization and enhanced electrochemistry performances at low temperature. These results have confirmed that PFPN has the potential to be a multi-function additive for commercial LIBs production.

Interactions of alkali metals and electrolyte with cathode carbons

Energy Technology Data Exchange (ETDEWEB)

Naas, Tyke

1997-12-31

The Hall-Heroult process for electrolytic reduction of alumina has been the only commercial process for production of primary aluminium. The process runs at high temperature and it is important to minimize the energy consumption. To save energy it is desirable to reduce the operating temperature. This can be achieved by adding suitable additives such as LiF or KF to the cryolitic electrolyte. This may conflict with the objective of extending the lifetime of the cathode linings of the cell as much as possible. The thesis investigates this possibility and the nature of the interactions involved. It supports the hypothesis that LiF-additions to the Hall-Heroult cell electrolyte is beneficial to the carbon cathode performance because the diminished sodium activity reduces the sodium induced stresses during the initial period of electrolysis. The use of KF as an additive is more dangerous, but the results indicate that additions up to 5% KF may be tolerated in acidic melts with semigraphitic or graphitic cathodes with little risk of cathode problems. 153 refs., 94 figs., 30 tabs.

Application of the nanocomposite membrane as electrolyte of proton exchange membrane fuel cell

International Nuclear Information System (INIS)

Mahreni

2010-01-01

Hydrogen fuel cells proton exchange membrane fuel cell (PEMFC) is currently still in development and commercialization. Several barriers to the commercialization of these Nafion membrane as electrolyte is its very sensitive to humidity fluctuation. Nafion must be modified by making a composite Nafion-SiO 2 -HPA to increase electrolyte resistance against humidity fluctuations during the cell used. Research carried out by mixing Nafion solution with Tetra Ethoxy Ortho Silicate (TEOS) and conductive materials is phosphotungstic acid (PWA) by varying the ratio of Nafion, TEOS and PWA. The membrane is produced by heating a mixture of Nafion, TEOS and PWA by varying the evaporation temperature, time and annealing temperature to obtain the transparent membrane. The resulting membrane was analyzed its physical, chemical and electrochemical properties by applying the membrane as electrolyte of PEMFC at various humidity and temperature of operation. The results showed that at low temperatures (30-90 °C) and high humidity at 100 % RH, pure Nafion membrane is better than composite membrane (Nafion-SiO 2 -PWA), but at low humidity condition composite membrane is better than the pure Nafion membrane. It can be concluded that the composite membranes of (Nafion-SiO 2 -PWA) can be used as electrolyte of PEMFC operated at low humidity (40 % RH) and temperature between (30-90 °C). (author)

Disintegration of graphite matrix from the simulative high temperature gas-cooled reactor fuel element by electrochemical method

International Nuclear Information System (INIS)

Tian Lifang; Wen Mingfen; Li Linyan; Chen Jing

2009-01-01

Electrochemical method with salt as electrolyte has been studied to disintegrate the graphite matrix from the simulative high temperature gas-cooled reactor fuel elements. Ammonium nitrate was experimentally chosen as the appropriate electrolyte. The volume average diameter of disintegrated graphite fragments is about 100 μm and the maximal value is less than 900 μm. After disintegration, the weight of graphite is found to increase by about 20% without the release of a large amount of CO 2 probably owing to the partial oxidation to graphite in electrochemical process. The present work indicates that the improved electrochemical method has the potential to reduce the secondary nuclear waste and is a promising option to disintegrate graphite matrix from high temperature gas-cooled reactor spent fuel elements in the head-end of reprocessing.

Development of semiindustrial technology for electrolytic powder production

International Nuclear Information System (INIS)

Suchkov, A.B.; Kovalev, B.F.; Zhbanov, A.M.; Rabinovich, E.M.; Sozina, A.L.

1978-01-01

The technology of the production of Fe, Mn, Cr, W pure metal powders by electrolysis of industrial waste in molten chloride-fluoride media with the addition of lower chlorides of refining metal was tested in laboratory and then in industrial electrolysers (2kA). The cathode deposit was subjected to hydrometallurgical treatment. Approximate technological parameters of electrorefining are presented. A high-temperature (700-1000 deg C) hydrogen annealing was applied to increase the quality and to change physicochemical and technological characteristics of electrolytic powders. The data on the chemical composition of Mowders are presented, testifying to their high purity. It is shown that electrolytic powders are not uniform in granulometric composition (from 1 to 100 μm), their particles being characterized mainly by the dendrite structure

Facile preparation of graphene by high-temperature electrolysis and its application in supercapacitor.

Science.gov (United States)

Jiao, Chen-Xu; Xing, Bao-Yan; Zhao, Jian-Guo; Geng, Yu; Li, Zuo-Peng

2014-01-01

Graphene is well known owing to its astonishing properties: stronger than diamond, more conductive than copper and more flexible than rubber. Because of its potential uses in industry, researchers have been searching for less toxicity ways to make graphene in large amount with lower cost. We demonstrated an efficient method to prepare graphene by high temperature electrolysis technique. High resolution scanning electron microscopy and raman spectroscopy were used to characterize the microstructure of graphene. Graphene was assembled into the supercapacitor and its performance of electrochemical capacitor was investigated by constant current charge and discharge, cyclic voltammetry and AC impedance. The results showed that the micro-morphology of the prepared graphene was multilayer and it was favorable when the electrolytic voltage was 1.5 V. When the current density is 1 mA/cm(2), the specific capacitance of the graphene supercapacitor can reach 78.01 F/g in 6 mol/L KOH electrolyte, which was an increase of 114% compared with 36.43 F/g of conventional KOH electrolyte.

Effects of current density and electrolyte temperature on the volume expansion factor of anodic alumina formed in oxalic acid

International Nuclear Information System (INIS)

Zhou, F.; Baron-Wiecheć, A.; Garcia-Vergara, S.J.; Curioni, M.; Habazaki, H.; Skeldon, P.; Thompson, G.E.

2012-01-01

The formation of porous anodic alumina in 0.4 M oxalic acid is investigated over a range of current density and electrolyte temperature using sputtering-deposited substrates containing tungsten tracer layers. The findings reveal volume expansion factors and efficiencies of film growth that increase with the increase of the current density and decrease of the temperature. Pore generation by the flow of the anodic alumina in the barrier layer toward the pore walls is proposed to dominate at relatively high current densities (above ∼2 mA cm −2 ), with tungsten tracer species being retained within films. Conversely, losses of tungsten species occur at lower current densities, possibly due to increased field-assisted ejection of Al 3+ ions and/or field-assisted dissolution of the anodic alumina.

Nanostructured Electrolytes for Stable Lithium Electrodeposition in Secondary Batteries

KAUST Repository

Tu, Zhengyuan

2015-11-17

© 2015 American Chemical Society. ConspectusSecondary batteries based on lithium are the most important energy storage technology for contemporary portable devices. The lithium ion battery (LIB) in widespread commercial use today is a compromise technology. It compromises high energy, high power, and design flexibility for long cell operating lifetimes and safety. Materials science, transport phenomena, and electrochemistry in the electrodes and electrolyte that constitute such batteries are areas of active study worldwide because significant improvements in storage capacity and cell lifetime are required to meet new demands, including the electrification of transportation and for powering emerging autonomous aircraft and robotics technologies. By replacing the carbonaceous host material used as the anode in an LIB with metallic lithium, rechargeable lithium metal batteries (LMBs) with higher storage capacity and compatibility with low-cost, high-energy, unlithiated cathodes such as sulfur, manganese dioxide, carbon dioxide, and oxygen become possible. Large-scale, commercial deployment of LMBs are today limited by safety concerns associated with unstable electrodeposition and lithium dendrite formation during cell recharge. LMBs are also limited by low cell operating lifetimes due to parasitic chemical reactions between the electrode and electrolyte. These concerns are greater in rechargeable batteries that utilize other, more earth abundant metals such as sodium and to some extent even aluminum.Inspired by early theoretical works, various strategies have been proposed for alleviating dendrite proliferation in LMBs. A commonly held view among these early studies is that a high modulus, solid-state electrolyte that facilitates fast ion transport, is nonflammable, and presents a strong-enough physical barrier to dendrite growth is a requirement for any commercial LMB. Unfortunately, poor room-temperature ionic conductivity, challenging processing, and the high cost

Corrosion Behavior of Nickel-Plated Alloy 600 in High Temperature Water

International Nuclear Information System (INIS)

Kim, Ji Hyun; Hwang, Il Soon

2008-01-01

In this paper, electrochemical and microstructural characteristics of nickel-plated Alloy 600 wee investigated in order to identify the performance of electroless Ni-plating on Alloy 600 in high-temperature aqueous condition with the comparison of electrolytic nickel-plating. For high temperature corrosion test of nickel-plated Alloy 600, specimens were exposed for 770 hours to typical PWR primary water condition. During the test, open circuit potentials (OCP's) of all specimens were measured using a reference electrode. Also, resistance to flow accelerated corrosion (FAC) test was examined in order to check the durability of plated layers in high-velocity flow environment at high temperature. After exposures to high flow rate aqueous condition, the integrity of surfaces was confirmed by using both scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). For the field application, a remote process for electroless nickel-plating was demonstrated using a plate specimen with narrow gap on a laboratory scale. Finally, a practical seal design was suggested for more convenient application

Study of Stable Cathodes and Electrolytes for High Specific Density Lithium-Air Battery

Science.gov (United States)

Hernandez-Lugo, Dionne M.; Wu, James; Bennett, William; Ming, Yu; Zhu, Yu

2015-01-01

Future NASA missions require high specific energy battery technologies, greater than 400 Wh/kg. Current NASA missions are using "state-of-the-art" (SOA) Li-ion batteries (LIB), which consist of a metal oxide cathode, a graphite anode and an organic electrolyte. NASA Glenn Research Center is currently studying the physical and electrochemical properties of the anode-electrolyte interface for ionic liquid based Li-air batteries. The voltage-time profiles for Pyr13FSI and Pyr14TFSI ionic liquids electrolytes studies on symmetric cells show low over-potentials and no dendritic lithium morphology. Cyclic voltammetry measurements indicate that these ionic liquids have a wide electrochemical window. As a continuation of this work, sp2 carbon cathode and these low flammability electrolytes were paired and the physical and electrochemical properties were studied in a Li-air battery system under an oxygen environment.

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.

US work on technical and economic aspects of electrolytic, thermochemical, and hybrid processes for hydrogen production at temperatures below 550 deg. C

International Nuclear Information System (INIS)

Petri, M.C.; Yyldyz, B.; Klickman, A.E.

2006-01-01

Hydrogen demand is increasing, but there are few options for affordable hydrogen production free of greenhouse gas emissions. Nuclear power is one of the most promising options. Most research is focused on high-temperature electrolytic and thermochemical processes for nuclear-generated hydrogen, but it will be many years before very high temperature reactors become commercially available. For light water reactors or supercritical reactors, low-temperature water electrolysis is a currently available technology for hydrogen production. Higher efficiencies may be gained through thermo-electrochemical hydrogen production cycles, but there are only a limited number that have heat requirements consistent with the lower temperatures of light-water reactor technology. Indeed, active research is ongoing for only three such cycles in the USA. Reductions in electricity and system costs would be needed (or the imposition of a carbon tax) for low-temperature water electrolysis to compete with today's costs for steam methane reformation. The interactions between hydrogen and electricity markets and hydrogen and electricity producers are complex and will evolve as the markets evolve. (author)

Preparation of poly(acrylonitrile-butyl acrylate) gel electrolyte for lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Tian Zheng [Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China); He Xiangming [Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China)]. E-mail: hexm@tsinghua.edu.cn; Pu Weihua [Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China); Wan Chunrong [Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China); Jiang Changyin [Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China)

2006-10-25

Poly(acrylonitrile-butyl acrylate) gel polymer electrolyte was prepared for lithium ion batteries. The preparation started with synthesis of poly(acrylonitrile-butyl acrylate) by radical emulsion polymerization, followed by phase inversion to produce microporous membrane. Then, the microporous gel polymer electrolytes (MGPEs) was prepared with the microporous membrane and LiPF{sub 6} in ethylene carbonate/diethyl carbonate. The dry microporous membrane showed a fracture strength as high as 18.98 MPa. As-prepared gel polymer electrolytes presented ionic conductivity in excess of 3.0 x 10{sup -3} S cm{sup -1} at ambient temperature and a decomposition voltage over 6.6 V. The results showed that the as-prepared gel polymer electrolytes were promising materials for Li-ion batteries.

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.

A Lithium-Air Battery Stably Working at High Temperature with High Rate Performance.

Science.gov (United States)

Pan, Jian; Li, Houpu; Sun, Hao; Zhang, Ye; Wang, Lie; Liao, Meng; Sun, Xuemei; Peng, Huisheng

2018-02-01

Driven by the increasing requirements for energy supply in both modern life and the automobile industry, the lithium-air battery serves as a promising candidate due to its high energy density. However, organic solvents in electrolytes are likely to rapidly vaporize and form flammable gases under increasing temperatures. In this case, serious safety problems may occur and cause great harm to people. Therefore, a kind of lithium-air that can work stably under high temperature is desirable. Herein, through the use of an ionic liquid and aligned carbon nanotubes, and a fiber shaped design, a new type of lithium-air battery that can effectively work at high temperatures up to 140 °C is developed. Ionic liquids can offer wide electrochemical windows and low vapor pressures, as well as provide high thermal stability for lithium-air batteries. The aligned carbon nanotubes have good electric and heat conductivity. Meanwhile, the fiber format can offer both flexibility and weavability, and realize rapid heat conduction and uniform heat distribution of the battery. In addition, the high temperature has also largely improved the specific powers by increasing the ionic conductivity and catalytic activity of the cathode. Consequently, the lithium-air battery can work stably at 140 °C with a high specific current of 10 A g -1 for 380 cycles, indicating high stability and good rate performance at high temperatures. This work may provide an effective paradigm for the development of high-performance energy storage devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Internal-reference solid-electrolyte oxygen sensor

International Nuclear Information System (INIS)

Haaland, D.M.

1977-01-01

A new solid-electrolyte oxygen sensor has been developed that eliminates the conventional oxygen reference in previous solid-electrolyte oxygen sensor designs and is, therefore, ideally suited as an insertion device for remote oxygen monitoring applications. It is constructed with two cells of stabilized zirconia sealed into a small unit using a new high-temperature platinum-zirconia seal. One electrochemical cell monitors the ratio of oxygen partial pressures inside and outside the sensor while the other solid-electrolyte cell is used for quantitative electrochemical pumping of oxygen. The internal oxygen reference is generated by initially pumping all oxygen out of the known internal volume of the sensor and then quantitatively pumping oxygen back in until oxygen partial pressures are equal inside and out. This information is used with the ideal gas law to calculate oxygen partial pressures. Tests were conducted from 400 to 1000 0 C in mixtures of oxygen and nitrogen spanning approximately 0.2 to 21 percent oxygen concentration range. Sensors with sputtered platinum and porous platinum paste electrodes were compared

Extrapolation procedures for calculating high-temperature gibbs free energies of aqueous electrolytes

International Nuclear Information System (INIS)

Tremaine, P.R.

1979-01-01

Methods for calculating high-temprature Gibbs free energies of mononuclear cations and anions from room-temperature data are reviewed. Emphasis is given to species required for oxide solubility calculations relevant to mass transport situations in the nuclear industry. Free energies predicted by each method are compared to selected values calculated from recently reported solubility studies and other literature data. Values for monatomic ions estimated using the assumption anti C 0 p(T) = anti C 0 p(298) agree best with experiment to 423 K. From 423 K to 523 K, free energies from an electrostatic model for ion hydration are more accurate. Extrapolations for hydrolyzed species are limited by a lack of room-temperature entropy data and expressions for estimating these entropies are discussed. (orig.) [de

Electrospun nanocomposite fibrous polymer electrolyte for secondary lithium battery applications

International Nuclear Information System (INIS)

Padmaraj, O.; Rao, B. Nageswara; Jena, Paramananda; Satyanarayana, N.; Venkateswarlu, M.

2014-01-01

Hybrid nanocomposite [poly(vinylidene fluoride -co- hexafluoropropylene) (PVdF-co-HFP)/magnesium aluminate (MgAl 2 O 4 )] fibrous polymer membranes were prepared by electrospinning method. The prepared pure and nanocomposite fibrous polymer electrolyte membranes were soaked into the liquid electrolyte 1M LiPF 6 in EC: DEC (1:1,v/v). XRD and SEM are used to study the structural and morphological studies of nanocomposite electrospun fibrous polymer membranes. The nanocomposite fibrous polymer electrolyte membrane with 5 wt.% of MgAl 2 O 4 exhibits high ionic conductivity of 2.80 × 10 −3 S/cm at room temperature. The charge-discharge capacity of Li/LiCoO 2 coin cells composed of the newly prepared nanocomposite [(16 wt.%) PVdF-co-HFP+(5 wt.%) MgAl 2 O 4 ] fibrous polymer electrolyte membrane was also studied and compared with commercial Celgard separator

Preconceptual design of hyfire. A fusion driven high temperature electrolysis plant

International Nuclear Information System (INIS)

Varljen, T.C.; Chi, J.W.H.; Karbowski, J.S.

1983-01-01

Brookhaven National Laboratory has been engaged in a scoping study to investigate the potential merits of coupling a fusion reactor with a high temperature blanket to a high temperature electrolysis (HTE) process to produce hydrogen and oxygen. Westinghouse is assisting this study in the areas of systems design integration, plasma engineering, balance of plant design and electrolyzer technology. The aim of the work done in the past year has been to focus on a reference design point for the plant, which has been designated HYFIRE. In prior work, the STARFIRE commercial tokamak fusion reactor was directly used as the fusion driver. This report describes a new design obtained by scaling the basic STARFIRE design to permit the achievement of a blanket power of 6000 MWt. The high temperature blanket design employs a thermally insulated refractory oxide region which provides high temperature (>1000 deg. C) steam at moderate pressures to high temperature electrolysis units. The electrolysis process selected is based on the high temperature, solid electrolyte fuel cell technology developed by Westinghouse. An initial process design and plant layout has been completed; component cost and plant economics studies are now underway to develop estimates of hydrogen production costs and to determine the sensitivity of this cost to changes in major design parameters. (author)

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)

Increased Water Retention in Polymer Electrolyte Membranes at Elevated Temperatures Assisted by Capillary Condensation

International Nuclear Information System (INIS)

Park, M.J.; Downing, K.H.; Jackson, A.; Gomez, E.D.; Minor, A.M.; Cookson, D.; Weber, A.Z.; Balsara, N.P.

2007-01-01

We establish a new systematic methodology for controlling the water retention of polymer electrolyte membranes. Block copolymer membranes comprising hydrophilic phases with widths ranging from 2 to 5 nm become wetter as the temperature of the surrounding air is increased at constant relative humidity. The widths of the moist hydrophilic phases were measured by cryogenic electron microscopy experiments performed on humid membranes. Simple calculations suggest that capillary condensation is important at these length scales. The correlation between moisture content and proton conductivity of the membranes is demonstrated.

Increased water retention in polymer electrolyte membranes at elevated temperatures assisted by capillary condensation.

Science.gov (United States)

Park, Moon Jeong; Downing, Kenneth H; Jackson, Andrew; Gomez, Enrique D; Minor, Andrew M; Cookson, David; Weber, Adam Z; Balsara, Nitash P

2007-11-01

We establish a new systematic methodology for controlling the water retention of polymer electrolyte membranes. Block copolymer membranes comprising hydrophilic phases with widths ranging from 2 to 5 nm become wetter as the temperature of the surrounding air is increased at constant relative humidity. The widths of the moist hydrophilic phases were measured by cryogenic electron microscopy experiments performed on humid membranes. Simple calculations suggest that capillary condensation is important at these length scales. The correlation between moisture content and proton conductivity of the membranes is demonstrated.

New Solid Polymer Electrolytes for Improved Lithium Batteries

Science.gov (United States)

Hehemann, David G.

2002-01-01

The objective of this work was to identify, synthesize and incorporate into a working prototype, next-generation solid polymer electrolytes, that allow our pre-existing solid-state lithium battery to function better under extreme conditions. We have synthesized polymer electrolytes in which emphasis was placed on the temperature-dependent performance of these candidate electrolytes. This project was designed to produce and integrate novel polymer electrolytes into a lightweight thin-film battery that could easily be scaled up for mass production and adapted to different applications.

Solvothermal synthesis of gallium-indium-zinc-oxide nanoparticles for electrolyte-gated transistors.

Science.gov (United States)

Santos, Lídia; Nunes, Daniela; Calmeiro, Tomás; Branquinho, Rita; Salgueiro, Daniela; Barquinha, Pedro; Pereira, Luís; Martins, Rodrigo; Fortunato, Elvira

2015-01-14

Solution-processed field-effect transistors are strategic building blocks when considering low-cost sustainable flexible electronics. Nevertheless, some challenges (e.g., processing temperature, reliability, reproducibility in large areas, and cost effectiveness) are requirements that must be surpassed in order to achieve high-performance transistors. The present work reports electrolyte-gated transistors using as channel layer gallium-indium-zinc-oxide nanoparticles produced by solvothermal synthesis combined with a solid-state electrolyte based on aqueous dispersions of vinyl acetate stabilized with cellulose derivatives, acrylic acid ester in styrene and lithium perchlorate. The devices fabricated using this approach display a ION/IOFF up to 1 × 10(6), threshold voltage (VTh) of 0.3-1.9 V, and mobility up to 1 cm(2)/(V s), as a function of gallium-indium-zinc-oxide ink formulation and two different annealing temperatures. These results validates the usage of electrolyte-gated transistors as a viable and promising alternative for nanoparticle based semiconductor devices as the electrolyte improves the interface and promotes a more efficient step coverage of the channel layer, reducing the operating voltage when compared with conventional dielectrics gating. Moreover, it is shown that by controlling the applied gate potential, the operation mechanism of the electrolyte-gated transistors can be modified from electric double layer to electrochemical doping.

Ultrasensitive NO2 Sensor Based on Ohmic Metal-Semiconductor Interfaces of Electrolytically Exfoliated Graphene/Flame-Spray-Made SnO2 Nanoparticles Composite Operating at Low Temperatures.

Science.gov (United States)

Tammanoon, Nantikan; Wisitsoraat, Anurat; Sriprachuabwong, Chakrit; Phokharatkul, Ditsayut; Tuantranont, Adisorn; Phanichphant, Sukon; Liewhiran, Chaikarn

2015-11-04

In this work, flame-spray-made undoped SnO2 nanoparticles were loaded with 0.1-5 wt % electrolytically exfoliated graphene and systematically studied for NO2 sensing at low working temperatures. Characterizations by X-ray diffraction, transmission/scanning electron microscopy, and Raman and X-ray photoelectron spectroscopy indicated that high-quality multilayer graphene sheets with low oxygen content were widely distributed within spheriodal nanoparticles having polycrystalline tetragonal SnO2 phase. The 10-20 μm thick sensing films fabricated by spin coating on Au/Al2O3 substrates were tested toward NO2 at operating temperatures ranging from 25 to 350 °C in dry air. Gas-sensing results showed that the optimal graphene loading level of 0.5 wt % provided an ultrahigh response of 26,342 toward 5 ppm of NO2 with a short response time of 13 s and good recovery stabilization at a low optimal operating temperature of 150 °C. In addition, the optimal sensor also displayed high sensor response and relatively short response time of 171 and 7 min toward 5 ppm of NO2 at room temperature (25 °C). Furthermore, the sensors displayed very high NO2 selectivity against H2S, NH3, C2H5OH, H2, and H2O. Detailed mechanisms for the drastic NO2 response enhancement by graphene were proposed on the basis of the formation of graphene-undoped SnO2 ohmic metal-semiconductor junctions and accessible interfaces of graphene-SnO2 nanoparticles. Therefore, the electrolytically exfoliated graphene-loaded FSP-made SnO2 sensor is a highly promising candidate for fast, sensitive, and selective detection of NO2 at low operating temperatures.

Brightness coatings of zinc-cobalt alloys by electrolytic way

International Nuclear Information System (INIS)

Julve, E.

1993-01-01

Zinc-cobalt alloys provide corrosion resistance for the ferrous based metals. An acidic electrolyte for zinc-cobalt electrodeposition is examined in the present work. The effects of variations in electrolyte composition, in electrolyte temperature, pH and agitation on electrodeposit composition have been studied, as well as the current density influence. It was found that the following electrolyte gave the optimum results: 79 g.1''-1 ZnCl 2 , 15.3 g.1''-1 CoCl 2 .6H 2 O, 160 g.1''-1 KCl, 25 g.1''-1 H 3 BO 3 and 5-10 cm''3.1''-1 of an organic additive (caffeine, coumarin and sodium lauryl-sulphonate). The operating conditions were: pH=5,6 temperature: 30 degree centigree, current density: 0,025-0,035 A. cm''2, anode: pure zinc, agitation: slowly with air and filtration: continuous. The throwing power and cathode current efficiency of the electrolyte were also studied. This electrolyte yielded zinc-cobalt alloys white and lustrous and had a cobalt content of 0,5-0,8% (Author) 3 refs. 5 fig

Novel inorganic materials for polymer electrolyte and alkaline fuel cells

Science.gov (United States)

Tadanaga, Kiyoharu

2012-06-01

Inorganic materials with high ionic conductivity must have big advantages for the thermal and long term stability when the materials are used as the electrolyte of fuel cells. In the present paper, novel ionic conductive inorganic materials for polymer electrolyte fuel cells (PEFCs) and all solid state alkaline fuel cells (AFCs) that have been developed by our group have been reviewed. PEFCs which can operate in temperature range from 100 to 200 °C are intensively studied because of some advantages such as reduction of CO poisoning of Pt catalyst and acceleration of electrode reactions. We showed that the fuel cells using the composite membranes prepared from phosphosilicate gel powder and polyimide precursor can operate in the temperature range from 30 to 180 °C. We also found that the inorganic-organic hybrid membranes with acid-base pairs from 3-aminopropyl triethoxy silane and H2SO4 or H3PO4 show high proton conductivity under dry atmosphere, and the membranes are thermally stable at intermediate temperatures. On the other hand, because the use of noble platinum is the serious problem for the commercialization of PEFCs and because oxidation reactions are usually faster than those of acid-type fuel cells, alkaline type fuel cells, in which a nonplatinum catalyst can be used, are attractive. Recently, we have proposed an alkaline-type direct ethanol fuel cell (DEFC) using a natural clay electrolyte with non-platinum catalysts. So-called hydrotalcite clay, Mg-Al layered double hydroxide intercalated with CO32- (Mg-Al CO32- LDH), has been proved to be a hydroxide ion conductor. An alkalinetype DEFC using Mg-Al CO32- LDH as the electrolyte and aqueous solution of ethanol and potassium hydroxide as a source of fuel exhibited excellent electrochemical performance.

Temperature dependence of water-water and ion-water correlations in bulk water and electrolyte solutions probed by femtosecond elastic second harmonic scattering

Science.gov (United States)

Chen, Yixing; Dupertuis, Nathan; Okur, Halil I.; Roke, Sylvie

2018-06-01

The temperature dependence of the femtosecond elastic second harmonic scattering (fs-ESHS) response of bulk light and heavy water and their electrolyte solutions is presented. We observe clear temperature dependent changes in the hydrogen (H)-bond network of water that show a decrease in the orientational order of water with increasing temperature. Although D2O has a more structured H-bond network (giving rise to more fs-ESHS intensity), the relative temperature dependence is larger in H2O. The changes are interpreted in terms of the symmetry of H-bonds and are indicators of nuclear quantum effects. Increasing the temperature in electrolyte solutions decreases the influence of the total electrostatic field from ions on the water-water correlations, as expected from Debye-Hückel theory, since the Debye length becomes longer. The effects are, however, 1.9 times (6.3 times) larger than those predicted for H2O (D2O). Since fs-ESHS responses can be computed from known molecular coordinates, our observations provide a unique opportunity to refine quantum mechanical models of water.

Composition and particle size of electrolytic copper powders prepared in water-containing dimethyl sulfoxide electrolytes

Science.gov (United States)

Mamyrbekova, Aigul'; Abzhalov, B. S.; Mamyrbekova, Aizhan

2017-07-01

The possibility of the electroprecipitation of copper powder via the cathodic reduction of an electrolyte solution containing copper(II) nitrate trihydrate and dimethyl sulfoxide (DMSO) is shown. The effect electrolysis conditions (current density, concentration and temperature of electrolyte) have on the dimensional characteristics of copper powder is studied. The size and shape of the particles of the powders were determined by means of electron microscopy; the qualitative composition of the powders, with X-ray diffraction.

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

Investigations on the kinetics of the oxygen reduction in high temperature fuel cells

International Nuclear Information System (INIS)

Erning, J.W.

1998-07-01

Lanthan-Strontium-Manganite perowskites are the most widespread materials in use for solid oxide fuel cell cathodes. The electrode reaction taking place, i.e. the reduction of oxygen supplied by air, was investigated by electrochemical means to obtain further knowledge about the electrode processes. The high activation energy of this reaction (200 kJ/mol), preventing lower operation temperatures of the SOFC, was the starting point for the investigation. Quasi steady state current voltage measurements and impedance spectroscopy were performed in a three electrode configuration. The electrodes were of circular shape with a diameter of 10 mm. The preparation was made by screen printing as well as wet powder spraying onto plates made of Yttria-stabilized zirconia. Perowskite powders of varying chemical and stoichiometric composition were used. To obtain higher power densities and, more important, lower apparent activation energies, catalytic layers were added at the interface electrode/electrolyte. Additionally, a less complex system, a model electrode/electrolyte setup made from single-crystal YSZ as electrolyte and gold in liquid and solid state as electrode was developed to create a better defined system. This setup was used to investigate the behaviour of the electrode/electrolyte interface. Reliable, reproducible results could be obtained using either setup. The experimental conditions i.e. oxygen partial pressure, temperature and overpotential were varied in order to determine the kinetic properties of the electrodes. Apparent activation energies, pre-exponential factors, apparent charge-transfer coefficients and electrochemical orders of reaction were calculated from the current-voltage data in order to propose possible reaction steps. (orig.)

Nanoporous Polymer-Ceramic Composite Electrolytes for Lithium Metal Batteries

KAUST Repository

Tu, Zhengyuan

2013-09-16

A nanoporous composite material that offers the unique combination of high room-temperature ionic conductivity and high mechanical modulus is reported. When used as the separator/electrolyte in lithium batteries employing metallic lithium as anode, the material displays unprecedented cycling stability and excellent ability to prevent premature cell failure by dendrite-induced short circuits © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Restricted lithium ion dynamics in PEO-based block copolymer electrolytes measured by high-field nuclear magnetic resonance relaxation

Science.gov (United States)

Huynh, Tan Vu; Messinger, Robert J.; Sarou-Kanian, Vincent; Fayon, Franck; Bouchet, Renaud; Deschamps, Michaël

2017-10-01

The intrinsic ionic conductivity of polyethylene oxide (PEO)-based block copolymer electrolytes is often assumed to be identical to the conductivity of the PEO homopolymer. Here, we use high-field 7Li nuclear magnetic resonance (NMR) relaxation and pulsed-field-gradient (PFG) NMR diffusion measurements to probe lithium ion dynamics over nanosecond and millisecond time scales in PEO and polystyrene (PS)-b-PEO-b-PS electrolytes containing the lithium salt LiTFSI. Variable-temperature longitudinal (T1) and transverse (T2) 7Li NMR relaxation rates were acquired at three magnetic field strengths and quantitatively analyzed for the first time at such fields, enabling us to distinguish two characteristic time scales that describe fluctuations of the 7Li nuclear electric quadrupolar interaction. Fast lithium motions [up to O (ns)] are essentially identical between the two polymer electrolytes, including sub-nanosecond vibrations and local fluctuations of the coordination polyhedra between lithium and nearby oxygen atoms. However, lithium dynamics over longer time scales [O (10 ns) and greater] are slower in the block copolymer compared to the homopolymer, as manifested experimentally by their different transverse 7Li NMR relaxation rates. Restricted dynamics and altered thermodynamic behavior of PEO chains anchored near PS domains likely explain these results.

Double-membrane triple-electrolyte redox flow battery design

Science.gov (United States)

Yushan, Yan; Gu, Shuang; Gong, Ke

2018-03-13

A redox flow battery is provided having a double-membrane (one cation exchange membrane and one anion exchange membrane), triple-electrolyte (one electrolyte in contact with the negative electrode, one electrolyte in contact with the positive electrode, and one electrolyte positioned between and in contact with the two membranes). The cation exchange membrane is used to separate the negative or positive electrolyte and the middle electrolyte, and the anion exchange membrane is used to separate the middle electrolyte and the positive or negative electrolyte. This design physically isolates, but ionically connects, the negative electrolyte and positive electrolyte. The physical isolation offers great freedom in choosing redox pairs in the negative electrolyte and positive electrolyte, making high voltage of redox flow batteries possible. The ionic conduction drastically reduces the overall ionic crossover between negative electrolyte and positive one, leading to high columbic efficiency.

Stretchable supercapacitors based on highly stretchable ionic liquid incorporated polymer electrolyte

Energy Technology Data Exchange (ETDEWEB)

Tamilarasan, P.; Ramaprabhu, S., E-mail: ramp@iitm.ac.in

2014-11-14

Mechanical stability of electrolyte in all-solid-state supercapacitor attains immense attention as it addresses safety aspects. In this study, we have demonstrated, the fabrication of stretchable supercapacitor based on stretchable electrolyte and hydrogen exfoliated graphene electrode. We synthesized ionic liquid incorporated stretchable Poly(methyl methacrylate) electrolyte which plays dual role as electrolyte and stretchable support for electrode material. The molecular vibration studies show composite nature of the electrolyte. At least four-fold stretchability has been observed along with good ionic conductivity (0.78 mS cm{sup −1} at 28 °C) for this polymer electrolyte. This stretchable supercapacitor shows a low equivalent series resistance (16 Ω) due to the compatibility at electrode–electrolyte interface. The performance of the device has been determined under strain as well. - Highlights: • A stretchable supercapacitor has been fabricated using stretchable electrolyte. • Here ionic liquid incorporated polymer plays dual role as electrolyte and stretchable support. • The developed device shows low equivalent series resistance. • The device has specific capacitance of 83 F g{sup −1}, at the specific current of 2.67 A g{sup −1}. • The energy density and power density of 25.7 Wh kg{sup −1} and 35.2 kW kg{sup −1}, respectively.

Electrochemical behavior of high performance on-chip porous carbon films for micro-supercapacitors applications in organic electrolytes

Science.gov (United States)

Brousse, K.; Huang, P.; Pinaud, S.; Respaud, M.; Daffos, B.; Chaudret, B.; Lethien, C.; Taberna, P. L.; Simon, P.

2016-10-01

Carbide derived carbons (CDCs) are promising materials for preparing integrated micro-supercapacitors, as on-chip CDC films are prepared via a process fully compatible with current silicon-based device technology. These films show good adherence on the substrate and high capacitance thanks to their unique nanoporous structure which can be fine-tuned by adjusting the synthesis parameters during chlorination of the metallic carbide precursor. The carbon porosity is mostly related to the synthesis temperature whereas the thickness of the films depends on the chlorination duration. Increasing the pore size allows the adsorption of large solvated ions from organic electrolytes and leads to higher energy densities. Here, we investigated the electrochemical behavior and performance of on-chip TiC-CDC in ionic liquid solvent mixtures of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF4) diluted in either acetonitrile or propylene carbonate via cyclic voltammetry and electrochemical impedance spectroscopy. Thin CDC films exhibited typical capacitive signature and achieved 169 F cm-3 in both electrolytes; 65% of the capacitance was still delivered at 1 V s-1. While increasing the thickness of the films, EMI+ transport limitation was observed in more viscous PC-based electrolyte. Nevertheless, the energy density reached 90 μW h cm-2 in 2M EMIBF4/ACN, confirming the interest of these CDC films for micro-supercapacitors applications.

Detonation nanodiamond introduced into samarium doped ceria electrolyte improving performance of solid oxide fuel cell

Science.gov (United States)

Pei, Kai; Li, Hongdong; Zou, Guangtian; Yu, Richeng; Zhao, Haofei; Shen, Xi; Wang, Liying; Song, Yanpeng; Qiu, Dongchao

2017-02-01

A novel electrolyte materials of introducing detonation nanodiamond (DNDs) into samarium doped ceria (SDC) is reported here. 1%wt. DNDs doping SDC (named SDC/ND) can enlarge the electrotyle grain size and change the valence of partial ceria. DNDs provide the widen channel to accelerate the mobility of oxygen ions in electrolyte. Larger grain size means that oxygen ions move easier in electrolyte, it can also reduce the alternating current (AC) impedance spectra of internal grains. The lower valence of partial Ce provides more oxygen vacancies to enhance mobility rate of oxygen ions. Hence all of them enhance the transportation of oxygen ions in SDC/ND electrolyte and the OCV. Ultimately the power density of SOFC can reach 762 mw cm-2 at 800 °C (twice higher than pure SDC, which is 319 mw cm-2 at 800 °C), and it remains high power density in the intermediate temperature (600-800 °C). It is relatively high for the electrolyte supported (300 μm) cells.

SmBaCoCuO5+x as cathode material based on GDC electrolyte for intermediate-temperature solid oxide fuel cells

International Nuclear Information System (INIS)

Lue Shiquan; Long, Guohui; Ji Yuan; Meng Xiangwei; Zhao Hongyuan; Sun Cuicui

2011-01-01

Research highlights: → We synthesize a new kind of layered perovskite SmBaCoCuO 5+x (SBCCO) as a cathode material of a solid oxide fuel cell. → There are some reports on the performance of cathodes in proton-conducting SOFCs based on BaCe 0.8 Sm 0.2 O 3-δ electrolyte. → However, to the best of our knowledge, the performance of SBCCO cathodes in oxygen-ion conducting SOFCs has not been reported to date. → In this work, the ceramic powder SBCCO is examined as a cathode for IT-SOFCs based on Ce 0.9 Gd 0.1 O 1.95 (GDC) electrolyte. - Abstract: The performance of SmBaCoCuO 5+x (SBCCO) cathode has been investigated for their potential utilization in intermediate-temperature solid oxide fuel cells (IT-SOFCs). The powder X-ray diffraction (XRD), thermal expansion and electrochemical performance on Ce 0.9 Gd 0.1 O 1.95 (GDC) electrolyte are evaluated. XRD results show that there is no chemical reaction between SBCCO cathode and GDC electrolyte when the temperature is below 950 o C. The thermal expansion coefficient (TEC) value of SBCCO is 15.53 x 10 -6 K -1 , which is ∼23% lower than the TEC of the SmBaCo 2 O 5+x (SBCO) sample. The electrochemical impedance spectra reveals that SBCCO symmetrical half-cells by sintering at 950 deg. C has the best electrochemical performance and the area specific resistance (ASR) of SBCCO cathode is as low as 0.086 Ω cm 2 at 800 o C. An electrolyte-supported fuel cell generates good performance with the maximum power density of 517 mW cm -2 at 800 deg. C in H 2 . Preliminary results indicate that SBCCO is promising as a cathode for IT-SOFCs.

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.

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.

Searching for electrolytes and electrodes for CO₂ reduction below 300 °C

DEFF Research Database (Denmark)

Vico, Federica

Electrochemical CO2 reduction research is driven by the desire to reduce reliance on fossil fuels and lower greenhouse gas emissions. The conversion of CO2 into fuels and chemicals using energy derived from a renewable source, such as wind or solar, could replace the use of fossil fuels...... practical application for carbon dioxide reduction at high pressure. K-doped BaZr1-xYxO3-δ was successfully synthesized by hydrothermal technique, but the conductivity recorded in high pH2O and at 240 °C was too low (3 · 10-5 S/cm) to be considered as a suitable electrolyte. A literature survey showed...... and temperatures. A foam based CO2 conversion cell with gas diffusion electrodes and a ceramic porous structure in which the liquid electrolyte is immobilized by capillary forces was developed and tested up to 20 bar and to a maximum temperature of 50 °C. Potassium carbonate was selected as aqueous electrolyte...

Further Improvement and System Integration of High Temperature Polymer Electrolyte Membrane Fuel Cells

DEFF Research Database (Denmark)

Li, Qingfeng; Jensen, Jens Oluf

The strategic developments of the FURIM are in three steps: (1) further improvement of the high temperature polymer membranes and related materials; (2) development of technological units including fuel cell stack, hydrocarbon reformer and afterburner, that are compatible with the HT-PEMFC; and (3......) integration of the HT-PEMFC stack with these compatible subunits. The main goal of the project is a 2kWel HT-PEMFC stack operating in a temperature range of 150-200°C, with a single cell performance target of 0.7 A/cm² at a cell voltage around 0.6 V. The target durability is more than 5,000 hours...

Yttrium and Nickel Co-Doped BaZrO3 as a Proton-Conducting Electrolyte for Intermediate Temperature Solid Oxide Fuel Cells

KAUST Repository

Shafi, S. P.

2015-07-17

High temperature proton conducting oxides, due to their lower activation energy for proton conduction, can achieve high conductivity at relatively low temperatures (500-700°C). Though BaZr0.8Y0.2O3-δ (BZY) perovskite exhibits good chemical stability and high bulk conductivity, high grain boundary resistance decreases its total conductivity. This work focuses on substitution of Zr4+ with Ni2+ in the perovskite B-site in a targeted fashion in order to promote the sinterability of BZY. Powder X-ray diffraction analysis showed the formation of single phases for Ba0.8-xY0.2NixO3-δ compositions up to x = 0.04. Scanning electron microscopy (SEM) image analysis demonstrated that densification is promoted by increasing the Ni-content, reaching a fully dense microstructure for Ba0.76Y0.2Ni0.04O3-δ (BZYNi04). An anode supported single cell based on BZYNi04 electrolyte showed superior power performance, achieving 240 and 428 mW cm-2 at 600 and 700°C, respectively. © The Electrochemical Society.

Yttrium and Nickel Co-Doped BaZrO3 as a Proton-Conducting Electrolyte for Intermediate Temperature Solid Oxide Fuel Cells

KAUST Repository

Shafi, S. P.; Bi, Lei; Boulfrad, S.; Traversa, Enrico

2015-01-01

High temperature proton conducting oxides, due to their lower activation energy for proton conduction, can achieve high conductivity at relatively low temperatures (500-700°C). Though BaZr0.8Y0.2O3-δ (BZY) perovskite exhibits good chemical stability and high bulk conductivity, high grain boundary resistance decreases its total conductivity. This work focuses on substitution of Zr4+ with Ni2+ in the perovskite B-site in a targeted fashion in order to promote the sinterability of BZY. Powder X-ray diffraction analysis showed the formation of single phases for Ba0.8-xY0.2NixO3-δ compositions up to x = 0.04. Scanning electron microscopy (SEM) image analysis demonstrated that densification is promoted by increasing the Ni-content, reaching a fully dense microstructure for Ba0.76Y0.2Ni0.04O3-δ (BZYNi04). An anode supported single cell based on BZYNi04 electrolyte showed superior power performance, achieving 240 and 428 mW cm-2 at 600 and 700°C, respectively. © The Electrochemical Society.

Interaction between cobalt-containing materials and solid electrolyte on the basis of lanthanum gallate

International Nuclear Information System (INIS)

Bronin, D.I.; Kuzin, B.L.; Sokolova, Yu.V.; Polyakova, N.V.

2000-01-01

High-temperature interaction of solid electrolyte La 0.88 Sr 0.12 Mg 0.18 Ga 0.82 O 3-α with material of oxygen electrode La 0.7 Sr 0.3 CoO 3-δ (LSC) and with Co 3 O 4 and its influence on electrochemical activity of oxygen electrodes made of LSO and Pt were studied using the methods of X-ray microanalysis, conductometry and impedance-spectroscopy. It was ascertained that the surface of the solid electrolyte contacting LSC or Co 3 O 4 at a temperature of 1100 Deg C and higher is enriched by cobalt. Electric conductivity of the electrolyte layer modified by cobalt is noticeably higher than that of the initial one. Electrochemical activity of oxygen electrodes made of LSC is 1-2 ordered higher than the one characteristic of platinum electrode [ru

A facile prestrain-stick-release assembly of stretchable supercapacitors based on highly stretchable and sticky hydrogel electrolyte

Science.gov (United States)

Tang, Qianqiu; Chen, Mingming; Wang, Gengchao; Bao, Hua; Saha, Petr

2015-06-01

A facile prestrain-stick-release assembly strategy for the stretchable supercapacitor device is developed based on a novel Na2SO4-aPUA/PAAM hydrogel electrolyte, saving the stretchable rubber base conventionally used. The Na2SO4-aPUA/PAAM hydrogel electrolyte exhibits high stretchability (>1000%), electrical conductivity (0.036 S cm-1) and stickiness. Due to the unique features of the hydrogel electrolyte, the carbon nanotube@MnO2 film electrodes can be firmly stuck to two sides of the prestrained hydrogel electrolyte. Then, by releasing the hydrogel electrolyte, homogenous buckles are formed for the film electrodes to get a full stretchable supercapacitor device. Besides, the high stickiness of the hydrogel electrolyte ensures its strong adhesion with the film electrodes, facilitating ion and electronic transfer of the supercapacitor. As a result, excellent electrochemical performance is achieved with the specific capacitance of 478.6 mF cm-2 at 0.5 mA cm-2 (corresponding to 201.1 F g-1) and capacitance retention of 91.5% after 3000 charging-discharging cycles under 150% strain, which is the best for the stretchable supercapacitors.

High temperature electrolyte supported Ni-GDC/YSZ/LSM SOFC operation on two-stage Viking gasifier product gas

DEFF Research Database (Denmark)

Hofmann, P.; Schweiger, A.; Fryda, L.

2007-01-01

and tar traces. The chosen SOFC was electrolyte supported with a nickel/gadolinium-doped cerium oxide (Ni-GDC) anode, known for its carbon deposition resistance. Through humidification the steam to carbon ratio (S/C) was adjusted to 0.5, which results in a thermodynamically carbon free condition...

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.

Substituted Quaternary Ammonium Salts Improve Low-Temperature Performance of Double-Layer Capacitors

Science.gov (United States)

Brandon, Erik J.; Smart, Marshall C.; West, William C.

2011-01-01

Double-layer capacitors are unique energy storage devices, capable of supporting large current pulses as well as a very high number of charging and discharging cycles. The performance of doublelayer capacitors is highly dependent on the nature of the electrolyte system used. Many applications, including for electric and fuel cell vehicles, back-up diesel generators, wind generator pitch control back-up power systems, environmental and structural distributed sensors, and spacecraft avionics, can potentially benefit from the use of double-layer capacitors with lower equivalent series resistances (ESRs) over wider temperature limits. Higher ESRs result in decreased power output, which is a particular problem at lower temperatures. Commercially available cells are typically rated for operation down to only 40 C. Previous briefs [for example, Low Temperature Supercapacitors (NPO-44386), NASA Tech Briefs, Vol. 32, No. 7 (July 2008), p. 32, and Supercapacitor Electrolyte Solvents With Liquid Range Below 80 C (NPO-44855), NASA Tech Briefs, Vol. 34, No. 1 (January 2010), p. 44] discussed the use of electrolytes that employed low-melting-point co-solvents to depress the freezing point of traditional acetonitrile-based electrolytes. Using these modified electrolyte formulations can extend the low-temperature operational limit of double-layer capacitors beyond that of commercially available cells. This previous work has shown that although the measured capacitance is relatively insensitive to temperature, the ESR can rise rapidly at low temperatures, due to decreased electrolyte conductance within the pores of the high surface- area carbon electrodes. Most of these advanced electrolyte systems featured tetraethylammonium tetrafluoroborate (TEATFB) as the salt. More recent work at JPL indicates the use of the asymmetric quaternary ammonium salt triethylmethylammonium tetrafluoroborate (TEMATFB) or spiro-(l,l')-bipyrrolidium tetrafluoroborate (SBPBF4) in a 1:1 by volume solvent

How Solid-Electrolyte Interphase Forms in Aqueous Electrolytes.

Science.gov (United States)

Suo, Liumin; Oh, Dahyun; Lin, Yuxiao; Zhuo, Zengqing; Borodin, Oleg; Gao, Tao; Wang, Fei; Kushima, Akihiro; Wang, Ziqiang; Kim, Ho-Cheol; Qi, Yue; Yang, Wanli; Pan, Feng; Li, Ju; Xu, Kang; Wang, Chunsheng

2017-12-27

Solid-electrolyte interphase (SEI) is the key component that enables all advanced electrochemical devices, the best representative of which is Li-ion battery (LIB). It kinetically stabilizes electrolytes at potentials far beyond their thermodynamic stability limits, so that cell reactions could proceed reversibly. Its ad hoc chemistry and formation mechanism has been a topic under intensive investigation since the first commercialization of LIB 25 years ago. Traditionally SEI can only be formed in nonaqueous electrolytes. However, recent efforts successfully transplanted this concept into aqueous media, leading to significant expansion in the electrochemical stability window of aqueous electrolytes from 1.23 V to beyond 4.0 V. This not only made it possible to construct a series of high voltage/energy density aqueous LIBs with unprecedented safety, but also brought high flexibility and even "open configurations" that have been hitherto unavailable for any LIB chemistries. While this new class of aqueous electrolytes has been successfully demonstrated to support diversified battery chemistries, the chemistry and formation mechanism of the key component, an aqueous SEI, has remained virtually unknown. In this work, combining various spectroscopic, electrochemical and computational techniques, we rigorously examined this new interphase, and comprehensively characterized its chemical composition, microstructure and stability in battery environment. A dynamic picture obtained reveals how a dense and protective interphase forms on anode surface under competitive decompositions of salt anion, dissolved ambient gases and water molecule. By establishing basic laws governing the successful formation of an aqueous SEI, the in-depth understanding presented in this work will assist the efforts in tailor-designing better interphases that enable more energetic chemistries operating farther away from equilibria in aqueous media.

Preparation of activated carbon aerogel and its application to electrode material for electric double layer capacitor in organic electrolyte: Effect of activation temperature

Energy Technology Data Exchange (ETDEWEB)

Kwon, Soon Hyung; Lee, Eunji; Kim, Myung-Soo; Jung, Ji Chul [Myongji University, Yongin (Korea, Republic of); Kim, Bum-Soo; Kim, Sang-Gil; Lee, Byung-Jun [Vitzrocell Co., Yesan (Korea, Republic of)

2015-02-15

Carbon aerogel was chemically activated with KOH at various activation temperatures with the aim of improving the electrochemical performance of carbon aerogel for EDLC electrode. Electrochemical performance of activated carbon aerogel electrode was determined by cyclic voltammetry and galvanostatic charge/discharge methods using coin-type EDLC cell in organic electrolyte. Activation temperature played an important role in determining the electrochemical performance of activated carbon aerogel for EDLC electrode. Specific capacitance of activated carbon aerogel at a high current density (5 A/g) showed a volcano-shaped curve with respect to activation temperature. Excessively high activation temperature could have an adverse effect on the electrochemical properties of activated carbon aerogel due to the low electrical conductivity caused by a collapse of characteristic structure of carbon aerogel. Among the carbon samples, carbon aerogel activated at 800 .deg. C with a high surface area and a well-developed porous structure exhibited the highest specific capacitance. In addition, carbon aerogel activated at 800 .deg. C retained a considerable specific capacitance at a high current density even after 1000 cycles of charge/discharge. Therefore, it is concluded that carbon aerogel activated with KOH at 800 .deg. C can serve as an efficient electrode material for commercial EDLC with a high power density.

Electrolytic coloration of air-grown sodium fluoride crystals

International Nuclear Information System (INIS)

Gu Hongen; Han Li; Song Cuiying; Guo Meili; Wang Na

2007-01-01

Air-grown sodium fluoride crystals were colored electrolytically by using a pointed cathode at various temperatures and electric field strengths, which should mainly benefit appropriate coloration temperatures and electric field strengths. O 2 - , F, M, N 1 , N 2 color centers and O 2- -F + complexes were produced in the colored crystals. Current-time curves for the electrolytic colorations were given, and activation energy for the V color center migration was determined. The formation of the color centers was explained

High-Performance Lithium-Oxygen Battery Electrolyte Derived from Optimum Combination of Solvent and Lithium Salt.

Science.gov (United States)

Ahn, Su Mi; Suk, Jungdon; Kim, Do Youb; Kang, Yongku; Kim, Hwan Kyu; Kim, Dong Wook

2017-10-01

To fabricate a sustainable lithium-oxygen (Li-O 2 ) battery, it is crucial to identify an optimum electrolyte. Herein, it is found that tetramethylene sulfone (TMS) and lithium nitrate (LiNO 3 ) form the optimum electrolyte, which greatly reduces the overpotential at charge, exhibits superior oxygen efficiency, and allows stable cycling for 100 cycles. Linear sweep voltammetry (LSV) and differential electrochemical mass spectrometry (DEMS) analyses reveal that neat TMS is stable to oxidative decomposition and exhibit good compatibility with a lithium metal. But, when TMS is combined with typical lithium salts, its performance is far from satisfactory. However, the TMS electrolyte containing LiNO 3 exhibits a very low overpotential, which minimizes the side reactions and shows high oxygen efficiency. LSV-DEMS study confirms that the TMS-LiNO 3 electrolyte efficiently produces NO 2 - , which initiates a redox shuttle reaction. Interestingly, this NO 2 - /NO 2 redox reaction derived from the LiNO 3 salt is not very effective in solvents other than TMS. Compared with other common Li-O 2 solvents, TMS seems optimum solvent for the efficient use of LiNO 3 salt. Good compatibility with lithium metal, high dielectric constant, and low donicity of TMS are considered to be highly favorable to an efficient NO 2 - /NO 2 redox reaction, which results in a high-performance Li-O 2 battery.

Dimethylacetamide as a film-forming additive for improving the cyclic stability of high voltage lithium-rich cathode at room and elevated temperature

International Nuclear Information System (INIS)

Tu, Wenqiang; Xing, Lidan; Xia, Pan; Xu, Mengqing; Liao, Youhao; Li, Weishan

2016-01-01

Highlights: • Addition of 1% DMAc improves the cyclic performances of LLO at room and elevated temperature. • DMAc oxidizes previously to the STD electrolyte and generates a protective film on the LLO surface. • The protective film is thin and uniform. - Abstract: In this work, dimethylacetamide (DMAc) was investigated as an electrolyte film-forming additive to improve the cyclic stability of high voltage Lithium-rich layered nickel manganese cobalt oxide (LLO) cathode at room (25 °C) and elevated (55 °C) temperature. At 0.5C rate, addition of 1% DMAc slightly decreases the initial discharge capacity of LLO from 187 to 179 mAh g −1 at room temperature and 255 to 246 mAh g −1 at elevated temperature, while significantly improves the capacity retention of LLO from 65.8% to 80.2% after 200 cycles at room temperature and from 21.1% to 66.7% after 150 cycles at elevated temperature. The mechanism of DMAc improving the cyclic stability of LLO was investigated via theoretical calculation and experimental characterizations, which demonstrated that DMAc oxidized preferential to the STD (1.0 M LiPF 6 in a mixed solvent of ethylene carbonate/ethyl methyl carbonate/diethyl carbonate) electrolyte, generating a thin and uniform film on the LLO surface. This film effectively suppresses the subsequent decomposition of STD electrolyte and further degradation of spinel phase converted from the layered structure of LLO, resulting in improved cyclic stability of LLO at room and elevated temperature.

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 ...

Outstanding features of alginate-based gel electrolyte with ionic liquid for electric double layer capacitors

Science.gov (United States)

Soeda, Kazunari; Yamagata, Masaki; Ishikawa, Masashi

2015-04-01

An alginate-based gel electrolyte with an ionic liquid (Alg/IL) is investigated for electric double-layer capacitors (EDLCs) by using physicochemical and electrochemical measurements. The Alg/EMImBF4 (EMImBF4 = 1-ethyl-3-methylimidazolium tetrafluoroborate) gel electrolyte is thermally stable up to 280 °C, where EMImBF4 decomposes. Furthermore, the EDLC with the gel electrolyte can be operated even at high temperature. The cell containing Alg/EMImBF4 is also electrochemically stable even under high voltage (∼3.5 V) operation. Thus, the alginate is a suitable host polymer for the gel electrolyte for EDLCs. According to the result of charge-discharge characteristics, the voltage drop in the charge-discharge curve for the cell with Alg/EMImBF4 gel electrolyte is considerably smaller than that with liquid-phase EMImBF4 electrolyte. To clarify the effect of Alg in contact with the activated carbon electrode, we also prepared an Alg-containing ACFC electrode (Alg + ACFC), and evaluated its EDLC characteristics in liquid EMImBF4. The results prove that the presence of Alg close to the active materials significantly reduces the internal resistance of the EDLC cell, which may be attributed to the high affinity of Alg to activated carbon.

Challenge in manufacturing electrolyte solutions for lithium and lithium ion batteries quality control and minimizing contamination level

Science.gov (United States)

Heider, U.; Oesten, R.; Jungnitz, M.

The quality of electrolytes for lithium batteries are a major topic in science and battery industries. The solvents and lithium salts should be of highest purity. Therefore, during preparation and handling of electrolyte solutions, the contamination level has to be minimized and the quality during packaging, storage and transportation has to be guaranteed. Especially, protic impurities are found to be very critical for LiPF 6-based electrolytes. The influence of water is reported to be tremendous. But also other protic impurities like alcohols are considered to play an important role in the electrolyte quality. The reaction of the protic impurities with LiPF 6 leads to the formation of HF which further reacts with cathode active materials (e.g., spinel) and the passivating films of the cathode and anode. For a better understanding of the protic impurities and their role in the electrolyte quality a systematic investigation of different impurities was carried out. Electrolytes were doped with different protic compounds. Then the electrolyte was analyzed for protic impurities and HF in dependence of time. First results showing the relation between protic impurities and HF are presented and discussed. In addition, different packaging materials for the electrolyte solutions were investigated. Storage tests were carried out at different temperatures and in different atmospheres. Results on contamination levels, influence of packaging, high temperature storage and handling are addressed.

Interaction and dynamics of (alkylamide + electrolyte) deep eutectics: Dependence on alkyl chain-length, temperature, and anion identity

International Nuclear Information System (INIS)

Guchhait, Biswajit; Das, Suman; Daschakraborty, Snehasis; Biswas, Ranjit

2014-01-01

Here we investigate the solute-medium interaction and solute-centered dynamics in (RCONH 2 + LiX) deep eutectics (DEs) via carrying out time-resolved fluorescence measurements and all-atom molecular dynamics simulations at various temperatures. Alkylamides (RCONH 2 ) considered are acetamide (CH 3 CONH 2 ), propionamide (CH 3 CH 2 CONH 2 ), and butyramide (CH 3 CH 2 CH 2 CONH 2 ); the electrolytes (LiX) are lithium perchlorate (LiClO 4 ), lithium bromide (LiBr), and lithium nitrate (LiNO 3 ). Differential scanning calorimetric measurements reveal glass transition temperatures (T g ) of these DEs are ∼195 K and show a very weak dependence on alkyl chain-length and electrolyte identity. Time-resolved and steady state fluorescence measurements with these DEs have been carried out at six-to-nine different temperatures that are ∼100–150 K above their individual T g s. Four different solute probes providing a good spread of fluorescence lifetimes have been employed in steady state measurements, revealing strong excitation wavelength dependence of probe fluorescence emission peak frequencies. Extent of this dependence, which shows sensitivity to anion identity, has been found to increase with increase of amide chain-length and decrease of probe lifetime. Time-resolved measurements reveal strong fractional power dependence of average rates for solute solvation and rotation with fraction power being relatively smaller (stronger viscosity decoupling) for DEs containing longer amide and larger (weaker decoupling) for DEs containing perchlorate anion. Representative all-atom molecular dynamics simulations of (CH 3 CONH 2 + LiX) DEs at different temperatures reveal strongly stretched exponential relaxation of wavevector dependent acetamide self dynamic structure factor with time constants dependent both on ion identity and temperature, providing justification for explaining the fluorescence results in terms of temporal heterogeneity and amide clustering in these multi

REMOVAL OF COPPER ELECTROLYTE CONTAMINANTS BY ADSORPTION

Directory of Open Access Journals (Sweden)

B Gabai

1997-09-01

Full Text Available Abstract - Selective adsorbents have become frequently used in industrial processes. Recent studies have shown the possibility of using adsorption to separate copper refinery electrolyte contaminants, with better results than those obtained with conventional techniques. During copper electrorefinning, many impurities may be found as dissolved metals present in the anode slime which forms on the electrode surface, accumulated in the electrolyte or incorporated into the refined copper on the cathode by deposition. In this study, synthetic zeolites, chelating resins and activated carbons were tested as adsorbents to select the best adsorbent performance, as well as the best operating temperature for the process. The experimental method applied was the finite bath, which consists in bringing the adsorbent into contact with a finite volume of electrolyte while controlling the temperature. The concentration of metals in the liquid phase was continuously monitored by atomic absorption spectrophotometry (AAS

Application of sol gel spin coated yttria-stabilized zirconia layers for the improvement of solid oxide fuel cell electrolytes produced by atmospheric plasma spraying

Energy Technology Data Exchange (ETDEWEB)

Rose, Lars [University of British Columbia, Department of Materials Engineering, 309-6350 Stores Road, Vancouver, British Columbia, V6T 1Z4 (Canada); National Research Council, Institute for Fuel Cell Innovation, 4250 Wesbrook Mall, Vancouver, British Columbia, V6T 1W5 (Canada); Kesler, Olivera [National Research Council, Institute for Fuel Cell Innovation, 4250 Wesbrook Mall, Vancouver, British Columbia, V6T 1W5 (Canada); University of British Columbia, Department of Mechanical Engineering, 2054-6250 Applied Science Lane, Vancouver, British Columbia, V6T 1Z4 (Canada); Tang, Zhaolin; Burgess, Alan [Northwest Mettech Corp., 467 Mountain Hwy, North Vancouver, British Columbia, V7J 2L3 (Canada)

2007-05-15

Due to its high thermal stability and purely oxide ionic conductivity, yttria-stabilized zirconia (YSZ) is the most commonly used electrolyte material for solid oxide fuel cells (SOFCs). Standard electrolyte fabrication techniques for planar SOFCs involve wet ceramic techniques such as tape-casting or screen printing, requiring sintering steps at temperatures above 1300 C. Plasma spraying (PS) may provide a more rapid and cost efficient method to produce SOFCs without sintering. High-temperature sintering requires long processing times and can lead to oxidation of metal alloys used as mechanical supports, or to detrimental interreactions between the electrolyte and adjacent electrode layers. This study investigates the use of spin coated sol gel derived YSZ precursor solutions to fill the pores present in plasma sprayed YSZ layers, and to enhance the surface area for reaction at the electrolyte-cathode interface, without the use of high-temperature firing steps. The effects of different plasma conditions and sol concentrations and solid loadings on the gas permeability and fuel cell performance have been investigated. (author)

Highly Stable Lithium Metal Batteries Enabled by Regulating the Solvation of Lithium Ions in Nonaqueous Electrolytes.

Science.gov (United States)

Zhang, Xue-Qiang; Chen, Xiang; Cheng, Xin-Bing; Li, Bo-Quan; Shen, Xin; Yan, Chong; Huang, Jia-Qi; Zhang, Qiang

2018-05-04

Safe and rechargeable lithium metal batteries have been difficult to achieve because of the formation of lithium dendrites. Herein an emerging electrolyte based on a simple solvation strategy is proposed for highly stable lithium metal anodes in both coin and pouch cells. Fluoroethylene carbonate (FEC) and lithium nitrate (LiNO 3 ) were concurrently introduced into an electrolyte, thus altering the solvation sheath of lithium ions, and forming a uniform solid electrolyte interphase (SEI), with an abundance of LiF and LiN x O y on a working lithium metal anode with dendrite-free lithium deposition. Ultrahigh Coulombic efficiency (99.96 %) and long lifespans (1000 cycles) were achieved when the FEC/LiNO 3 electrolyte was applied in working batteries. The solvation chemistry of electrolyte was further explored by molecular dynamics simulations and first-principles calculations. This work provides insight into understanding the critical role of the solvation of lithium ions in forming the SEI and delivering an effective route to optimize electrolytes for safe lithium metal batteries. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Network type sp3 boron-based single-ion conducting polymer electrolytes for lithium ion batteries

Science.gov (United States)

Deng, Kuirong; Wang, Shuanjin; Ren, Shan; Han, Dongmei; Xiao, Min; Meng, Yuezhong

2017-08-01

Electrolytes play a vital role in modulating lithium ion battery performance. An outstanding electrolyte should possess both high ionic conductivity and unity lithium ion transference number. Here, we present a facile method to fabricate a network type sp3 boron-based single-ion conducting polymer electrolyte (SIPE) with high ionic conductivity and lithium ion transference number approaching unity. The SIPE was synthesized by coupling of lithium bis(allylmalonato)borate (LiBAMB) and pentaerythritol tetrakis(2-mercaptoacetate) (PETMP) via one-step photoinitiated in situ thiol-ene click reaction in plasticizers. Influence of kinds and content of plasticizers was investigated and the optimized electrolytes show both outstanding ionic conductivity (1.47 × 10-3 S cm-1 at 25 °C) and high lithium transference number of 0.89. This ionic conductivity is among the highest ionic conductivity exhibited by SIPEs reported to date. Its electrochemical stability window is up to 5.2 V. More importantly, Li/LiFePO4 cells with the prepared single-ion conducting electrolytes as the electrolyte as well as the separator display highly reversible capacity and excellent rate capacity under room temperature. It also demonstrates excellent long-term stability and reliability as it maintains capacity of 124 mA h g-1 at 1 C rate even after 500 cycles without obvious decay.

Cross-linking of polymer and ionic liquid as high-performance gel electrolyte for flexible solid-state supercapacitors

International Nuclear Information System (INIS)

Zhong, Xiongwei; Tang, Jun; Cao, Lujie; Kong, Weiguang; Sun, Zheng; Cheng, Hua; Lu, Zhouguang; Pan, Hui; Xu, Baomin

2017-01-01

Highlights: •A facile method to prepare gel polymer electrolyte with high conductivity is proposed. •A flexible symmetric capacitor based on the prepared GPE shows ultra-flexibility. •The capacitor with high voltage can power up a 3.0 V LED even bended to a angle of 180°. -- Abstract: It is highly desirable to develop flexible solid-state electrochemical double-layer capacitors (EDLCs) with non-liquid electrolyte. However, it is still a great challenge to prepare gel polymer electrolyte (GPE) possessing high ionic conductivity and good mechanical property. In this work, a simple and novel method to improve the conductivity and mechanical properties of GPE film for their applications as electrolyte and separator in EDLC is presented. The GPE film is prepared by cross-linking ionic liquid (IL) with poly (ethylene oxide) (PEO) and benzophenone (Bp) followed by ultraviolet (UV) irradiation. Then, a non-woven cellulose separator (FPC) is used to absorb the GPE. By tuning the mass ratio (n) between IL and PEO, the flexible EDLC cooperated with low-cost active carbon and the electrolyte film with n = 10 has a high capacitance of 70.84 F∙g −1 , a wide and stable electrochemical window of 3.5 V, an energy density of 30.13 Wh∙kg −1 and a power density of 874.8 W∙kg −1 at a current density of 1 A∙g −1 , which can drive a 3.0 V light-emitting diode (LED). Importantly, the excellent performance of the flexible and low-cost EDLC can be maintained at a bending angle up to 180°, indicating the ultra-flexibility. It is expected that the IL-PEO-FPC electrolyte film is a promising candidate of GPE for flexible devices and energy storage systems.

The effect of porosity on performance of phosphoric acid doped polybenzimidazole polymer electrolyte membrane fuel cell

Directory of Open Access Journals (Sweden)

Celik Muhammet

2016-01-01

Full Text Available A polybenzimidazole (PBI based polymer electrolyte fuel cells, which called high temperature polymer electrolyte fuel cells (HT-PEMS, operate at higher temperatures (120-200°C than conventional PEM fuel cells. Although it is known that HT-PEMS have some of the significant advantages as non-humidification requirements for membrane and the lack of liquid water at high temperature in the fuel cell, the generated water as a result of oxygen reduction reaction causes in the degradation of these systems. The generated water absorbed into membrane side interacts with the hydrophilic PBI matrix and it can cause swelling of membrane, so water transport mechanism in a membrane electrode assembly (MEA needs to be well understood and water balance must be calculated in MEA. Therefore, the water diffusion transport across the electrolyte should be determined. In this study, various porosity values of gas diffusion layers are considered in order to investigate the effects of porosity on the water management for two phase flow in fuel cell. Two-dimensional fuel cell with interdigitated flow-field is modelled using COMSOL Multiphysics 4.2a software. The operating temperature and doping level is selected as 160°C and 6.75mol H3PO4/PBI, respectively.

Enhanced performance of ultracapacitors using redox additive-based electrolytes

Science.gov (United States)

Jain, Dharmendra; Kanungo, Jitendra; Tripathi, S. K.

2018-05-01

Different concentrations of potassium iodide (KI) as redox additive had been added to 1 M sulfuric acid (H2SO4) electrolyte with an aim of enhancing the capacitance and energy density of ultracapacitors via redox reactions at the interfaces of electrode-electrolyte. Ultracapacitors were fabricated using chemically treated activated carbon as electrode with H2SO4 and H2SO4-KI as an electrolyte. The electrochemical performances of fabricated supercapacitors were investigated by impedance spectroscopy, cyclic voltammetry and charge-discharge techniques. The maximum capacitance ` C' was observed with redox additives-based electrolyte system comprising 1 M H2SO4-0.3 M KI (1072 F g- 1), which is very much higher than conventional 1 M H2SO4 (61.3 F g- 1) aqueous electrolyte-based ultracapacitors. It corresponds to an energy density of 20.49 Wh kg- 1 at 2.1 A g- 1 for redox additive-based electrolyte, which is six times higher as compared to that of pristine electrolyte (1 M H2SO4) having energy density of only 3.36 Wh kg- 1. The temperature dependence behavior of fabricated cell was also analyzed, which shows increasing pattern in its capacitance values in a temperature range of 5-70 °C. Under cyclic stability test, redox electrolyte-based system shows almost 100% capacitance retention up to 5000 cycles and even more. For comparison, ultracapacitors based on polymer gel electrolyte polyvinyl alcohol (PVA) (10 wt%)—{H2SO4 (1 M)-KI (0.3 M)} (90 wt%) have been fabricated and characterized with the same electrode materials.

Electrochemical Synthesis of Ammonia in Solid Electrolyte Cells

Directory of Open Access Journals (Sweden)

Ioannis eGaragounis

2014-01-01

Full Text Available Developed in the early 1900's, the Haber-Bosch synthesis is the dominant NH3 synthesis process. Parallel to catalyst optimization, current research efforts are also focused on the investigation of new methods for ammonia synthesis, including the electrochemical synthesis with the use of solid electrolyte cells. Since the first report on Solid State Ammonia Synthesis (SSAS, more than 30 solid electrolyte materials were tested and at least 15 catalysts were used as working electrodes. Thus far, the highest rate of ammonia formation reported is 1.13×10−8 mol s−1 cm−2, obtained at 80°C with a Nafion solid electrolyte and a mixed oxide, SmFe0.7Cu0.1Ni0.2O3, cathode. At high temperatures (>500oC the maximum rate was 9.5*10-9 mol s−1 cm−2 using Ce0.8Y0.2O2-δ -[Ca3(PO42 -K3PO4] as electrolyte and Ag-Pd as cathode. In this paper, the advantages and the disadvantages of SSAS vs the conventional process and the requirements that must be met in order to promote the electrochemical process into an industrial level, are discussed.

Electrochemical Synthesis of Ammonia in Solid Electrolyte Cells

International Nuclear Information System (INIS)

Garagounis, Ioannis; Kyriakou, Vasileios; Skodra, Aglaia; Vasileiou, Eirini; Stoukides, Michael

2014-01-01

Developed in the early 1900s, the “Haber–Bosch” synthesis is the dominant NH 3 synthesis process. Parallel to catalyst optimization, current research efforts are also focused on the investigation of new methods for ammonia synthesis, including the electrochemical synthesis with the use of solid electrolyte cells. Since the first report on Solid State Ammonia Synthesis (SSAS), more than 30 solid electrolyte materials were tested and at least 15 catalysts were used as working electrodes. Thus far, the highest rate of ammonia formation reported is 1.13 × 10 -8 mol s -1 cm -2 , obtained at 80°C with a Nafion solid electrolyte and a mixed oxide, SmFe 0.7 Cu 0.1 Ni 0.2 O 3 , cathode. At high temperatures (>500°C), the maximum rate was 9.5 × 10 −9 mol s -1 cm -2 using Ce 0.8 Y 0.2 O 2-δ –[Ca 3 (PO 4 ) 2 –K 3 PO 4 ] as electrolyte and Ag–Pd as cathode. In this paper, the advantages and the disadvantages of SSAS vs. the conventional process and the requirements that must be met in order to promote the electrochemical process into an industrial level are discussed.

Electrochemical performances of LSM/YSZ composite electrode for high temperature steam electrolysis

International Nuclear Information System (INIS)

Kyu-Sung Sim; Ki-Kwang Bae; Chang-Hee Kim; Ki-Bae Park

2006-01-01

The (La 0.8 Sr 0.2 ) 0.95 MnO 3 /Yttria-stabilized Zirconia composite electrodes were investigated as anode materials for high temperature steam electrolysis using X-ray diffractometry, scanning electron microscopy, galvano-dynamic and galvano-static polarization method. For this study, the LSM perovskites were fabricated in powders by the co-precipitation method and then were mixed with 8 mol% YSZ powders in different molar ratios. The LSM/YSZ composite electrodes were deposited on 8 mol% YSZ electrolyte disks by screen printing method, followed by sintering at temperature above 1100 C. From the experimental results, it is concluded that the electrochemical properties of pure and composite electrodes are closely related to their micro-structure and operating temperature. (authors)

Preparation and Characterization of PVC-Al2O3-LiClO4 Composite Polymeric Electrolyte

International Nuclear Information System (INIS)

Azizan Ahmad; Mohd Yusri Abdul Rahman; Siti Aminah Mohd Noor; Mohd Reduan Abu Bakar

2009-01-01

Ionic conductivity of composite polymer electrolyte PVC-Al 2 O 3 -LiClO 4 as a function of Al 2 O 3 concentration has been studied. The electrolyte samples were prepared by solution casting technique. Their ionic conductivity was measured using impedance spectroscopy technique. It was observed that the conductivity of the electrolyte varies with Al 2 O 3 concentration. The highest room temperature conductivity of the electrolyte of 3.43 x 10 -10 S.cm -1 was obtain at 25 % by weight of Al 2 O 3 and that without Al 2 O 3 filler was found to be 2.43 x 10 -11 S.cm -1 . The glass transition temperature decreases with the increase of Al 2 O 3 percentage due to the increasing amorphous state, meanwhile the degradation temperature increases with the increase of Al 2 O 3 percentage. Both of these thermal properties influence the enhancement of the conductivity value. The morphology of the samples shows the even distribution of the Al 2 O 3 filler in the samples. However, the filler starts to agglomerate in the sample when high percentage of Al 2 O 3 is being used. In conclusion, the addition of Al 2 O 3 filler improves the ionic conductivity of PVC- Al 2 O 3 -LiCIO 4 solid polymer electrolyte. (author)

Preparation and characterization of poly(vinyl sulfone)- and poly(vinylidene fluoride)-based electrolytes

Energy Technology Data Exchange (ETDEWEB)

Choe, H.S.; Giaccai, J.; Alamgir, M.; Abraham, K.M. [EIC Labs., Inc., Norwood, MA (United States)

1995-10-01

A novel group of polymer electrolytes based on poly(vinyl sulfone) (PVS) and poly(vinylidene fluoride) (PVdF) polymers, plasticized with highly conductive solutions of LiClO{sub 4}, LiN(CF{sub 3}SO{sub 2}){sub 2} or LiAsF{sub 6} dissolved in ethylene carbonate, propylene carbonate, sulfolane, or mixtures thereof, was prepared via in situ photopolymerization and solution casting, respectively. The polymer electrolytes were characterized from conductivity and cyclic voltammetry data. It was found that solutions of Li salts in the vinyl sulfone monomer were highly conductive at room temperature with conductivities of 0.6 to 1.3 x 10{sup -3} {Omega}{sup -1}cm{sup -1} at 30{sup o}C, but the conductivities decreased by about 10{sup 3} times on polymerizing. Conversely, the conductivities increased by about 10{sup 2} to 10{sup 4} times on incorporating plasticizing solvents into the solid polymer electrolytes, suggesting that ionic mobility is the primary factor affecting the conductivities of solid polymer electrolytes. The highest conductivity exhibited by PVS-based electrolyte was 3.74 x 10{sup -4} {Omega}{sup -1}cm{sup -1} and that by PVdF-based electrolyte was 1.74 x 10{sup -3} {Omega}{sup -1}cm{sup -1}, at 30{sup o}C. The PVS-based electrolytes were found to be stable to oxidation up to potentials ranging between 4.5 and 4.8 V, while the stable potential limits for PVdF-based electrolytes were between 3.9 and 4.3 V vs. Li{sup +}/Li. (author)

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.

Electrolyte Engineering: Optimizing High-Rate Double-Layer Capacitances of Micropore- and Mesopore-Rich Activated Carbon.

Science.gov (United States)

Chen, Ting-Hao; Yang, Cheng-Hsien; Su, Ching-Yuan; Lee, Tai-Chou; Dong, Quan-Feng; Chang, Jeng-Kuei

2017-09-22

Various types of electrolyte cations as well as binary cations are used to optimize the capacitive performance of activated carbon (AC) with different pore structures. The high-rate capability of micropore-rich AC, governed by the mobility of desolvated cations, can outperform that of mesopore-rich AC, which essentially depends on the electrolyte conductivity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

KAUST Repository

Schaefer, Jennifer L.; Yanga, Dennis A.; Archer, Lynden A.

2013-01-01

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

Lithium carbon batteries with solid polymer electrolyte; Accumulateur lithium carbone a electrolyte solide polymere

Energy Technology Data Exchange (ETDEWEB)

Andrieu, X.; Boudin, F. [Alcatel Alsthom Recherche, 91 - Marcoussis (France)

1996-12-31

The lithium carbon batteries studied in this paper use plasticized polymer electrolytes made with passive polymer matrix swollen by a liquid electrolyte with a high ionic conductivity (> 10{sup -3} S/cm at 25 deg. C). The polymers used to prepare the gels are polyacrylonitrile (PAN) and vinylidene poly-fluoride (PVdF). The electrochemical and physical properties of these materials are analyzed according to their composition. The behaviour of solid electrolytes with different materials of lithium ion insertion (graphite and LiNiO{sub 2}) are studied and compared to liquid electrolytes. The parameters taken into account are the reversible and irreversible capacities, the cycling performance and the admissible current densities. Finally, complete lithium ion batteries with gelled electrolytes were manufactured and tested. (J.S.) 2 refs.

Lithium carbon batteries with solid polymer electrolyte; Accumulateur lithium carbone a electrolyte solide polymere

Energy Technology Data Exchange (ETDEWEB)

Andrieu, X; Boudin, F [Alcatel Alsthom Recherche, 91 - Marcoussis (France)

1997-12-31

The lithium carbon batteries studied in this paper use plasticized polymer electrolytes made with passive polymer matrix swollen by a liquid electrolyte with a high ionic conductivity (> 10{sup -3} S/cm at 25 deg. C). The polymers used to prepare the gels are polyacrylonitrile (PAN) and vinylidene poly-fluoride (PVdF). The electrochemical and physical properties of these materials are analyzed according to their composition. The behaviour of solid electrolytes with different materials of lithium ion insertion (graphite and LiNiO{sub 2}) are studied and compared to liquid electrolytes. The parameters taken into account are the reversible and irreversible capacities, the cycling performance and the admissible current densities. Finally, complete lithium ion batteries with gelled electrolytes were manufactured and tested. (J.S.) 2 refs.

Highly Stable Sr-Free Cobaltite-Based Perovskite Cathodes Directly Assembled on a Barrier-Layer-Free Y2 O3 -ZrO2 Electrolyte of Solid Oxide Fuel Cells.

Science.gov (United States)

Ai, Na; Li, Na; Rickard, William D A; Cheng, Yi; Chen, Kongfa; Jiang, San Ping

2017-03-09

Direct assembly is a newly developed technique in which a cobaltite-based perovskite (CBP) cathode can be directly applied to a barrier-layer-free Y 2 O 3 -ZrO 2 (YSZ) electrolyte with no high-temperature pre-sintering steps. Solid oxide fuel cells (SOFCs) based on directly assembled CBPs such as La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ show high performance initially but degrade rapidly under SOFC operation conditions at 750 °C owing to Sr segregation and accumulation at the electrode/electrolyte interface. Herein, the performance and interface of Sr-free CBPs such as LaCoO 3-δ (LC) and Sm 0.95 CoO 3-δ (SmC) and their composite cathodes directly assembled on YSZ electrolyte was studied systematically. The LC electrode underwent performance degradation, most likely owing to cation demixing and accumulation of La on the YSZ electrolyte under polarization at 500 mA cm -2 and 750 °C. However, the performance and stability of LC electrodes could be substantially enhanced by the formation of LC-gadolinium-doped ceria (GDC) composite cathodes. Replacement of La by Sm increased the cell stability, and doping of 5 % Pd to form Sm 0.95 Co 0.95 Pd 0.05 O 3-δ (SmCPd) significantly improved the electrode activity. An anode-supported YSZ-electrolyte cell with a directly assembled SmCPd-GDC composite electrode exhibited a peak power density of 1.4 W cm -2 at 750 °C, and an excellent stability at 750 °C for over 240 h. The higher stability of SmC as compared to that of LC is most likely a result of the lower reactivity of SmC with YSZ. This study demonstrates the new opportunities in the design and development of intermediate-temperature SOFCs based on the directly assembled high-performance and durable Sr-free CBP cathodes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical behavior of sebaconitrile as a cosolvent in the formulation of electrolytes at high potentials for lithium-ion batteries

International Nuclear Information System (INIS)

Nanini-Maury, Elise; Światowska, Jolanta; Chagnes, Alexandre; Zanna, Sandrine; Tran-Van, Pierre; Marcus, Philippe; Cassir, Michel

2014-01-01

The electrochemical behavior of new high potential electrolyte containing sebaconitrile in LiPF 6 /EC:DMC or LiBF 4 was studied on glassy carbon and LiCoO 2 , LiCoPO 4 as positive electrode materials. The increase of sebaconitrile concentration in EC:DMC electrolyte provides better electrolyte stability at higher potentials on glassy carbon as observed by cyclic voltammetry. Promising electrochemical results showing good reversibility and insertion/deinsertion efficiency have been also obtained on LiCoPO 4 electrode cycled up to 5.3 V vs Li + /Li as upper potential limit. However, the cycling of LiCoPO 4 at higher potential (6 V vs Li + /Li) shows lower reversibility and efficiency of insertion/deinsertion process due to the oxidative decomposition of the electrolyte at high potentials. The surface analysis performed by X-ray photoelectron spectroscopy confirms the formation of a surface layer induced by electrolyte degradation on both types of positive electrodes, which hinder the Li diffusion. The layer composition and morphology vary as a function of electrolyte composition and type of electrode

Increasing the operation temperature of polymer electrolyte membranes for fuel cells: From nanocomposites to hybrids

Science.gov (United States)

Licoccia, Silvia; Traversa, Enrico

Among the possible systems investigated for energy production with low environmental impact, polymeric electrolyte membrane fuel cells (PEMFCs) are very promising as electrochemical power sources for application in portable technology and electric vehicles. For practical applications, operating FCs at temperatures above 100 °C is desired, both for hydrogen and methanol fuelled cells. When hydrogen is used as fuel, an increase of the cell temperature produces enhanced CO tolerance, faster reaction kinetics, easier water management and reduced heat exchanger requirement. The use of methanol instead of hydrogen as a fuel for vehicles has several practical benefits such as easy transport and storage, but the slow oxidation kinetics of methanol needs operating direct methanol fuel cells (DMFCs) at intermediate temperatures. For this reason, new membranes are required. Our strategy to achieve the goal of operating at temperatures above 120 °C is to develop organic/inorganic hybrid membranes. The first approach was the use of nanocomposite class I hybrids where nanocrystalline ceramic oxides were added to Nafion. Nanocomposite membranes showed enhanced characteristics, hence allowing their operation up to 130 °C when the cell was fuelled with hydrogen and up to 145 °C in DMFCs, reaching power densities of 350 mW cm -2. The second approach was to prepare Class II hybrids via the formation of covalent bonds between totally aromatic polymers and inorganic clusters. The properties of such covalent hybrids can be modulated by modifying the ratio between organic and inorganic groups and the nature of the chemical components allowing to reach high and stable conductivity values up to 6.4 × 10 -2 S cm -1 at 120 °C.

Low temperature solid oxide fuel cells with proton-conducting Y:BaZrO{sub 3} electrolyte on porous anodic aluminum oxide substrate

Energy Technology Data Exchange (ETDEWEB)

Ha, Seungbum [School of Mechanical and Aerospace Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); School of Mechanical and Aerospace Engineering, Seoul National University, Daehak-dong, Gwanak-gu, Seoul 151–742 (Korea, Republic of); Su, Pei-Chen [School of Mechanical and Aerospace Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); Ji, Sanghoon [Graduate School of Convergence Science and Technology, Seoul National University, Daehak-dong, Gwanak-gu, Seoul 151–742 (Korea, Republic of); Cha, Suk Won, E-mail: swcha@snu.ac.kr [School of Mechanical and Aerospace Engineering, Seoul National University, Daehak-dong, Gwanak-gu, Seoul 151–742 (Korea, Republic of)

2013-10-01

This paper presents the architecture of a nano thin-film yttrium-doped barium zirconate (BYZ) solid-oxide fuel cell that uses nanoporous anodic aluminum oxide (AAO) as a supporting and gas-permeable substrate. The anode was fabricated by sputtering 300 nm platinum thin film that partially covered the AAO surface pores, followed by an additional conformal platinum coating to tune the pore size by atomic layer deposition. Two different nano-porous anode structures with a pore size of 10 nm or 50 nm were deposited. Proton-conducting BYZ ceramic electrolyte with increasing thicknesses of 300, 600, and 900 nm was deposited on top of the platinum anode by pulsed laser deposition, followed by a 200 nm layer of porous Pt sputtered on BYZ electrolyte as a cathode. The open circuit voltage (OCV) of the fuel cells was characterized at 250 °C with 1:1 volumetric stoichiometry of a methanol/water vapor mixture as the fuel. The OCVs were 0.17 V with a 900 nm-thick BYZ electrolyte on 50 nm pores and 0.3 V with a 600 nm-thick BYZ electrolyte on 10 nm pores, respectively, but it increased to 0.8 V for a 900 nm-thick BYZ electrolyte on 10 nm pores, indicating that increasing the film thickness and decreasing a surface pore size help to reduce the number of electrolyte pinholes and the gas leakage through the electrolyte. A maximum power density of 5.6 mW/cm{sup 2} at 250 °C was obtained from the fuel cell with 900 nm of BYZ electrolyte using methanol vapor as a fuel. - Highlights: • A low temperature ceramic fuel cell on nano-porous substrate was demonstrated. • A thin-film yttrium doped barium zirconate (BYZ) was deposited as an electrolyte. • An open circuit voltage (OCV) was measured to verify the BYZ film quality. • An OCV increased by increasing BYZ film thickness and decreasing pore size of anode. • The current–voltage performance was measured using vaporized methanol fuel at 250 °C.

Operating mechanisms of electrolytes in magnesium ion batteries: chemical equilibrium, magnesium deposition, and electrolyte oxidation.

Science.gov (United States)

Kim, Dong Young; Lim, Younhee; Roy, Basab; Ryu, Young-Gyoon; Lee, Seok-Soo

2014-12-21

Since the early nineties there have been a number of reports on the experimental development of Mg electrolytes based on organo/amide-magnesium chlorides and their transmetalations. However, there are no theoretical papers describing the underlying operating mechanisms of Mg electrolytes, and there is no clear understanding of these mechanisms. We have therefore attempted to clarify the operating mechanisms of Mg electrolytes by studying the characteristics of Mg complexes, solvation, chemical equilibrium, Mg-deposition processes, electrolyte-oxidation processes, and oxidative degradation mechanism of RMgCl-based electrolytes, using ab initio calculations. The formation and solvation energies of Mg complexes highly depend on the characteristics of R groups. Thus, changes in R groups of RMgCl lead to changes in the equilibrium position and the electrochemical reduction and oxidation pathways and energies. We first provide a methodological scheme for calculating Mg reduction potential values in non-aqueous electrolytes and electrochemical windows. We also describe a strategy for designing Mg electrolytes to maximize the electrochemical windows and oxidative stabilities. These results will be useful not only for designing improved Mg electrolytes, but also for developing new electrolytes in the future.

Polybenzimidazole/Mxene composite membranes for intermediate temperature polymer electrolyte membrane fuel cells

Science.gov (United States)

Fei, Mingming; Lin, Ruizhi; Deng, Yuming; Xian, Hongxi; Bian, Renji; Zhang, Xiaole; Cheng, Jigui; Xu, Chenxi; Cai, Dongyu

2018-01-01

This report demonstrated the first study on the use of a new 2D nanomaterial (Mxene) for enhancing membrane performance of intermediate temperature (>100 °C) polymer electrolyte membrane fuel cells (ITPEMFCs). In this study, a typical Ti3C2T x -MXene was synthesized and incorporated into polybenzimidazole (PBI)-based membranes by using a solution blending method. The composite membrane with 3 wt% Ti3C2T x -MXene showed the proton conductivity more than 2 times higher than that of pristine PBI membrane at the temperature range of 100 °C-170 °C, and led to substantial increase in maximum power density of fuel cells by ˜30% tested at 150 °C. The addition of Ti3C2T x -MXene also improved the mechanical properties and thermal stability of PBI membranes. At 3 wt% Ti3C2T x -MXene, the elongation at break of phosphoric acid doped PBI remained unaffected at 150 °C, and the tensile strength and Young’s modulus was increased by ˜150% and ˜160%, respectively. This study pointed out promising application of MXene in ITPEMFCs.

Structural and morphological analysis of barium cerate electrolyte for SOFC application

Directory of Open Access Journals (Sweden)

Senthil Kumar A.

2017-02-01

Full Text Available Gadolinium doped barium cerate (BCG electrolytes Ce0.8Gd0.2O1.9 + xBaO (x = 0.1 and 0.4 were prepared by wet chemical method for the use in solid oxide fuel cells operating at intermediate temperatures (600 °C to 800 °C. The as-prepared powder sample was calcined at 900 °C. The calcination temperature was identified using differential scanning calorimetry (DSC analysis. The orthorhombic perovskite phase formation was confirmed by XRD analysis. From TEM results, the particle size was found to be about 32 nm which is in a good agreement with XRD results. BCG nanoparticles were formed at lower sintering temperature due to using microwave furnace. By reducing the sintering temperature of solid electrolyte through microwave technique, the percentage of barium loss was successfully reduced and the prepared electrolyte can be a good choice for solid oxide fuel cells operating at intermediate temperatures.

High temperatures and nephrology: The climate change problem

Directory of Open Access Journals (Sweden)

Alberto de Lorenzo

2017-09-01

Full Text Available It is well known that climate change greatly affects human health, even though there are few studies on renal outcomes. Heat waves have been found to increase cardiovascular and respiratory morbidity and mortality, as well as the risk of acute renal failure and hospitalisation due to renal diseases, with related mortality. Recurrent dehydration in people regularly exposed to high temperatures seems to be resulting in an unrecognised cause of proteinuric chronic kidney disease, the underlying pathophysiological mechanism of which is becoming better understood. However, beyond heat waves and extreme temperatures, there is a seasonal variation in glomerular filtration rate that may contribute to the onset of renal failure and electrolyte disorders during extremely hot periods. Although there are few references in the literature, serum sodium disorders seem to increase. The most vulnerable population to heat-related disease are the elderly, children, chronic patients, bedridden people, disabled people, people living alone or with little social contact, and socioeconomically disadvantaged people.

A method for producing electrolyte and heat resistant drilling muds from bentonite clays

Energy Technology Data Exchange (ETDEWEB)

Koyev, K; Bedelcheva, A; Uzunova, I

1979-01-01

A method is developed for producing clay suspensions, which are resistant to electrolytes, high temperature and pressure, on the basis of bentonite clays with a high content of montmorillonite. The method is based on the subsequent introduction into the suspension of magnesium chloride (calcium chloride) and sodium chloride with intense mixing and maintenance of the high viscosity of the clay mass. The electrolytes are added in a specific order and volume: the magnesium chloride or calcium chloride at 1-3% and the sodium chloride at approximately 30%. The clay suspensions are characterized by high SNS and filtration (40 cm/sup 3/ in 30 min). The operational indicators may be regulated so that they remain in accordance with the required standards.

A new three-particle-interaction model to predict the thermodynamic properties of different electrolytes

International Nuclear Information System (INIS)

Ge Xinlei; Wang Xidong; Zhang Mei; Seetharaman, Seshadri

2007-01-01

In this study, Guggenheim charging process, which involves the radial Boltzmann distribution, was introduced to develop a new predictive model with three parameters, ion-ion distance parameter, ion-solvent parameter, and solvation parameter. In this model, the ion-ion and ion-solvent molecule interaction are all included in the charging process, and it is independent of the temperature and solvent. This new model was applied to correlate the experimental data from literatures for 208 electrolytes aqueous solution at T = 298.15 K of which the concentration range is wide. The calculated results agreed well with the experimental ones for most electrolytes, especially for the prediction in high ionic strength. The estimation of solvation parameter S also gave that the solvation tendency for cations and anions follow a trend, which is in consistent with results published in literature. Investigations were also been made in calculations for electrolytes solutions at other temperatures and non-aqueous system, which proved this model was also feasible

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.

Effect of microstructure on the high temperature mechanical properties of (CeO{sub 2}){sub 0.8}(GdO{sub 1.5}){sub 0.2} electrolytes

Energy Technology Data Exchange (ETDEWEB)

Sammes, N.M.; Zhang, Y. [Univ. of Waikato, Hamilton (New Zealand)

1996-12-31

CeO{sub 2}-based oxides have recently been shown to have great potential as electrolytes in medium temperature solid oxide fuel cell applications, primarily due to their high ionic conductivity. Steele et al., for example, have examined a cell of the type: O{sub 2}, La{sub 0.6}Sr{sub 0.4}Fe{sub 0.8}Co{sub 0.2}O{sub 3}{vert_bar}Ce{sub 0.9}Gd{sub 0.1}O{sub 1.95}{vert_bar}Ni-ZrO{sub 2}, H{sub 2}/H{sub 2}O at 715{degrees}C. Gd{sub 2}O{sub 3} doped CeO{sub 2} has been reported as having one of the highest oxygen ion conductivities of the ceria-based materials. An ionic conductivity of 8.3 x 10{sup -2} s/cm has been reported for (CeO{sub 2}){sub 0.8}(GdO{sub 1.5}){sub 0.2} at 800{degrees}C, which is approximately four times that of Y{sub 2}O{sub 3}-doped ZrO{sub 2}, at the same temperature. Although the electrical properties of the material have been examined in detail, very little work has considered the microstructural/property relationships, particularly in relation to the mechanical properties. It is well know that CeO{sub 2}-based materials are difficult to density and attempts have been performed to examine this. Preliminary studies have also been undertaken to examine the effect of sintering on the mechanical properties of the material. In this paper we examine the effect of microstructure on the high temperature mechanical properties of (CeO{sub 2}){sub 0.8}(GdO{sub 1.5}){sub 0.2}.

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.

Electrolytic Preparation of High Dielectric Thin Films

National Research Council Canada - National Science Library

Hultquist, A. E; Sibert, M. E

1966-01-01

.... Some attention is devoted to zirconates, niobates, and tantalates. In addition to barium compounds, the comparable calcium, magnesium, strontium and potassium double oxides are evaluated by the appropriate electrolytic techniques...

Anhydrous hydrogen fluoride electrolyte battery. [Patent application

Science.gov (United States)

Not Available

1972-06-26

It is an object of the invention to provide a primary cell or battery using ammonium fluoride--anhydrous hydrogen fluoride electrolyte having improved current and power production capabilities at low temperatures. It is operable at temperatures substantially above the boiling point of hydrogen fluoride. (GRA)

based gel polymer electrolytes

Indian Academy of Sciences (India)

(PVdF) as a host polymer, lithium perchlorate (LiClO4), lithium triflate ... TG/DTA studies showed the thermal stability of the polymer electrolytes. .... are observed while comparing pure XRD spectra with .... batteries as its operating temperature is normally in the .... chain ion movements and the conductivity of the polymer.

Chemical Passivation of Li(exp +)-Conducting Solid Electrolytes

Science.gov (United States)

West, William; Whitacre, Jay; Lim, James

2008-01-01

Plates of a solid electrolyte that exhibits high conductivity for positive lithium ions can now be passivated to prevent them from reacting with metallic lithium. Such passivation could enable the construction and operation of high-performance, long-life lithium-based rechargeable electrochemical cells containing metallic lithium anodes. The advantage of this approach, in comparison with a possible alternative approach utilizing lithium-ion graphitic anodes, is that metallic lithium anodes could afford significantly greater energy-storage densities. A major impediment to the development of such cells has been the fact that the available solid electrolytes having the requisite high Li(exp +)-ion conductivity are too highly chemically reactive with metallic lithium to be useful, while those solid electrolytes that do not react excessively with metallic lithium have conductivities too low to be useful. The present passivation method exploits the best features of both extremes of the solid-electrolyte spectrum. The basic idea is to coat a higher-conductivity, higher-reactivity solid electrolyte with a lower-conductivity, lower-reactivity solid electrolyte. One can then safely deposit metallic lithium in contact with the lower-reactivity solid electrolyte without incurring the undesired chemical reactions. The thickness of the lower-reactivity electrolyte must be great enough to afford the desired passivation but not so great as to contribute excessively to the electrical resistance of the cell. The feasibility of this method was demonstrated in experiments on plates of a commercial high-performance solid Li(exp +)- conducting electrolyte. Lithium phosphorous oxynitride (LiPON) was the solid electrolyte used for passivation. LiPON-coated solid-electrolyte plates were found to support electrochemical plating and stripping of Li metal. The electrical resistance contributed by the LiPON layers were found to be small relative to overall cell impedances.

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

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

Ultraflexible and tailorable all-solid-state supercapacitors using polyacrylamide-based hydrogel electrolyte with high ionic conductivity.

Science.gov (United States)

Li, Huili; Lv, Tian; Li, Ning; Yao, Yao; Liu, Kai; Chen, Tao

2017-11-30

Hydrogels with high ionic conductivity consisting of a cross-linked polymer network swollen in water are very promising to be used as an electrolyte for all-solid-state supercapacitors. However, there are rather few flexible supercapacitors using ionic conducting hydrogel electrolytes reported to date. In this work, highly flexible and ionic conducting polyacrylamide hydrogels were synthesized through a simple approach. On using the ionic hydrogels as the electrolyte, the resulting supercapacitors not only exhibited a high specific capacitance but also showed a long self-discharge time (over 10 hours to the half of original open-circuit voltage) and a low leakage current. These newly-developed all-solid-state supercapacitors can be bent, knot, and kneaded for 5000 cycles without performance decay, suggesting excellent flexibility and mechanical stability. These all-solid-state supercapacitors can also be easily tailored into strip-like supercapacitors without a short circuit, which provides an efficient approach to fabricate wearable energy storage devices.

Electrolytic hydriding of LaFe{sub 13-x}Si{sub x} alloys for energy efficient magnetic cooling

Energy Technology Data Exchange (ETDEWEB)

Lyubina, Julia; Hannemann, Ullrich; Ryan, Mary P. [Department of Materials, Imperial College London (United Kingdom); Cohen, Lesley F. [Department of Physics, Imperial College London (United Kingdom)

2012-04-17

An effective, low-temperature and readily available electrochemical method for tuning the operation temperature of LaFe{sub 13-x}Si{sub x}-type alloys is demonstrated. Electrolytically hydrided materials have the same high level magnetic properties as in high temperature gas-phase processed materials and offer an advantage of higher hydrogen absorption rate in the ferromagnetic state. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Transport and spectroscopic studies of liquid and polymer electrolytes

Science.gov (United States)

Bopege, Dharshani Nimali

Liquid and polymer electrolytes are interesting and important materials to study as they are used in Li rechargeable batteries and other electrochemical devices. It is essential to investigate the fundamental properties of electrolytes such as ionic conductivity, diffusion, and ionic association to enhance battery performance in different battery markets. This dissertation mainly focuses on the temperature-dependent charge and mass transport processes and ionic association of different electrolyte systems. Impedance spectroscopy and pulsed field gradient nuclear magnetic resonance spectroscopy were used to measure the ionic conductivity and diffusion coefficients of ketone and acetate based liquid electrolytes. In this study, charge and mass transport in non-aqueous liquid electrolytes have been viewed from an entirely different perspective by introducing the compensated Arrhenius formalism. Here, the conductivity and diffusion coefficient are written as an Arrhenius-like expression with a temperature-dependent static dielectric constant dependence in the exponential prefactor. The compensated Arrhenius formalism reported in this dissertation very accurately describes temperature-dependent conductivity data for acetate and ketone-based electrolytes as well as temperature-dependent diffusion data of pure solvents. We found that calculated average activation energies of ketone-based electrolytes are close to each other for both conductivity and diffusion data (in the range 24-26 kJ/mol). Also, this study shows that average activation energies of acetate-based electrolytes are higher than those for the ketone systems (in the range 33-37 kJ/mol). Further, we observed higher dielectric constants and ionic conductivities for both dilute and concentrated ketone solutions with temperature. Vibrational spectroscopy (Infrared and Raman) was used to probe intermolecular interactions in both polymer and liquid electrolytes, particularly those which contain lithium

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.

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).

Composite, Polymer-Based Electrolytes for Advanced Batteries

National Research Council Canada - National Science Library

Ratner, Mark A

2001-01-01

.... Several substantive advances towards new, improved performance electrolyte materials both for low temperature fuel cell applications and for advanced secondary lithium battery materials have been reported...

Final Technical Report Microwave Assisted Electrolyte Cell for Primary Aluminum Production

Energy Technology Data Exchange (ETDEWEB)

Xiaodi Huang; J.Y. Hwang

2007-04-18

This research addresses the high priority research need for developing inert anode and wetted cathode technology, as defined in the Aluminum Industry Technology Roadmap and Inert Anode Roadmap, with the performance targets: a) significantly reducing the energy intensity of aluminum production, b) ultimately eliminating anode-related CO2 emissions, and c) reducing aluminum production costs. This research intended to develop a new electrometallurgical extraction technology by introducing microwave irradiation into the current electrolytic cells for primary aluminum production. This technology aimed at accelerating the alumina electrolysis reduction rate and lowering the aluminum production temperature, coupled with the uses of nickel based superalloy inert anode, nickel based superalloy wetted cathode, and modified salt electrolyte. Michigan Technological University, collaborating with Cober Electronic and Century Aluminum, conducted bench-scale research for evaluation of this technology. This research included three sub-topics: a) fluoride microwave absorption; b) microwave assisted electrolytic cell design and fabrication; and c) aluminum electrowinning tests using the microwave assisted electrolytic cell. This research concludes that the typically used fluoride compound for aluminum electrowinning is not a good microwave absorbing material at room temperature. However, it becomes an excellent microwave absorbing material above 550°C. The electrowinning tests did not show benefit to introduce microwave irradiation into the electrolytic cell. The experiments revealed that the nickel-based superalloy is not suitable for use as a cathode material; although it wets with molten aluminum, it causes severe reaction with molten aluminum. In the anode experiments, the chosen superalloy did not meet corrosion resistance requirements. A nicked based alloy without iron content could be further investigated.

Ionic liquid-nanoparticle hybrid electrolytes

KAUST Repository

Lu, Yingying

2012-01-01

We investigate physical and electrochemical properties of a family of organic-inorganic hybrid electrolytes based on the ionic liquid 1-methyl-3-propylimidazolium bis(trifluoromethanesulfone) imide covalently tethered to silica nanoparticles (SiO 2-IL-TFSI). The ionic conductivity exhibits a pronounced maximum versus LiTFSI composition, and in mixtures containing 13.4 wt% LiTFSI, the room-temperature ionic conductivity is enhanced by over 3 orders of magnitude relative to either of the mixture components, without compromising lithium transference number. The SiO 2-IL-TFSI/LiTFSI hybrid electrolytes are thermally stable up to 400°C and exhibit tunable mechanical properties and attractive (4.25V) electrochemical stability in the presence of metallic lithium. We explain these observations in terms of ionic coupling between counterion species in the mobile and immobile (particle-tethered) phases of the electrolytes. © 2012 The Royal Society of Chemistry.

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

Electrochemical Synthesis of Ammonia in Solid Electrolyte Cells

Energy Technology Data Exchange (ETDEWEB)

Garagounis, Ioannis; Kyriakou, Vasileios [Department of Chemical Engineering, Aristotle University of Thessaloniki, Thessaloniki (Greece); Chemical Processes and Energy Resources Institute, Center for Research and Technology Hellas, Thessaloniki (Greece); Skodra, Aglaia [Chemical Processes and Energy Resources Institute, Center for Research and Technology Hellas, Thessaloniki (Greece); Vasileiou, Eirini; Stoukides, Michael, E-mail: stoukidi@cperi.certh.gr [Department of Chemical Engineering, Aristotle University of Thessaloniki, Thessaloniki (Greece); Chemical Processes and Energy Resources Institute, Center for Research and Technology Hellas, Thessaloniki (Greece)

2014-01-17

Developed in the early 1900s, the “Haber–Bosch” synthesis is the dominant NH{sub 3} synthesis process. Parallel to catalyst optimization, current research efforts are also focused on the investigation of new methods for ammonia synthesis, including the electrochemical synthesis with the use of solid electrolyte cells. Since the first report on Solid State Ammonia Synthesis (SSAS), more than 30 solid electrolyte materials were tested and at least 15 catalysts were used as working electrodes. Thus far, the highest rate of ammonia formation reported is 1.13 × 10{sup -8} mol s{sup -1} cm{sup -2}, obtained at 80°C with a Nafion solid electrolyte and a mixed oxide, SmFe{sub 0.7}Cu{sub 0.1}Ni{sub 0.2}O{sub 3}, cathode. At high temperatures (>500°C), the maximum rate was 9.5 × 10{sup −9} mol s{sup -1} cm{sup -2} using Ce{sub 0.8}Y{sub 0.2}O{sub 2-δ}–[Ca{sub 3}(PO{sub 4}){sub 2}–K{sub 3}PO{sub 4}] as electrolyte and Ag–Pd as cathode. In this paper, the advantages and the disadvantages of SSAS vs. the conventional process and the requirements that must be met in order to promote the electrochemical process into an industrial level are discussed.

Interaction and dynamics of (alkylamide + electrolyte) deep eutectics: Dependence on alkyl chain-length, temperature, and anion identity

Energy Technology Data Exchange (ETDEWEB)

Guchhait, Biswajit; Das, Suman; Daschakraborty, Snehasis; Biswas, Ranjit, E-mail: ranjit@bose.res.in [Department of Chemical, Biological and Macromolecular Sciences, S. N. Bose National Centre for Basic Sciences, Block-JD, Sector-III, Salt Lake, Kolkata 700098 (India)

2014-03-14

Here we investigate the solute-medium interaction and solute-centered dynamics in (RCONH{sub 2} + LiX) deep eutectics (DEs) via carrying out time-resolved fluorescence measurements and all-atom molecular dynamics simulations at various temperatures. Alkylamides (RCONH{sub 2}) considered are acetamide (CH{sub 3}CONH{sub 2}), propionamide (CH{sub 3}CH{sub 2}CONH{sub 2}), and butyramide (CH{sub 3}CH{sub 2}CH{sub 2}CONH{sub 2}); the electrolytes (LiX) are lithium perchlorate (LiClO{sub 4}), lithium bromide (LiBr), and lithium nitrate (LiNO{sub 3}). Differential scanning calorimetric measurements reveal glass transition temperatures (T{sub g}) of these DEs are ∼195 K and show a very weak dependence on alkyl chain-length and electrolyte identity. Time-resolved and steady state fluorescence measurements with these DEs have been carried out at six-to-nine different temperatures that are ∼100–150 K above their individual T{sub g}s. Four different solute probes providing a good spread of fluorescence lifetimes have been employed in steady state measurements, revealing strong excitation wavelength dependence of probe fluorescence emission peak frequencies. Extent of this dependence, which shows sensitivity to anion identity, has been found to increase with increase of amide chain-length and decrease of probe lifetime. Time-resolved measurements reveal strong fractional power dependence of average rates for solute solvation and rotation with fraction power being relatively smaller (stronger viscosity decoupling) for DEs containing longer amide and larger (weaker decoupling) for DEs containing perchlorate anion. Representative all-atom molecular dynamics simulations of (CH{sub 3}CONH{sub 2} + LiX) DEs at different temperatures reveal strongly stretched exponential relaxation of wavevector dependent acetamide self dynamic structure factor with time constants dependent both on ion identity and temperature, providing justification for explaining the fluorescence results in

Intermediate Temperature Fuel Cell Using CsH₂PO₄/ZrO₂-Based Composite Electrolytes

DEFF Research Database (Denmark)

Jensen, Annemette Hindhede; Li, Qingfeng; Christensen, Erik

2014-01-01

Proton conductors operating at intermediate temperatures are receiving significant attention due to their advantages over conventionally used materials in proton exchange membrane fuel cells. CsH2PO4 has proven to be proton conducting above 230°C, however within a narrow temperature range of the ...... to 280°C under low atmospheric humidification. Higher open circuit voltage and stability in the extended temperature range were achieved with composite electrolytes with a CsH2PO4 to ZrO2 molar ratio of 2....

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.

Lithium ion batteries (NMC/graphite) cycling at 80 °C: Different electrolytes and related degradation mechanism

Science.gov (United States)

Genieser, R.; Ferrari, S.; Loveridge, M.; Beattie, S. D.; Beanland, R.; Amari, H.; West, G.; Bhagat, R.

2018-01-01

A comprehensive study on high temperature cycling (80 °C) of industrial manufactured Li-ion pouch cells (NMC-111/Graphite) filled with different electrolytes is introduced. Ageing processes such as capacity fade, resistance increase and gas generation are reduced by the choice of appropriate electrolyte formulations. However, even by using additive formulations designed for elevated temperatures a large resistance increase is observed after 200 cycles and more (which does not happen at 55 °C). Symmetrical EIS (Electrochemical Impedance Spectroscopy) shows that the cathodic charge transfer resistance is the main reason for this behaviour. Nonetheless most of the active Li is still available when cycling with suitable additives. No change of the cathode crystalline structure or a growth of the cathodic surface reconstruction layer is observed post cycling at 80 °C. Therefore a disintegration of NMC secondary particles is believed to be the main reason of the cell failure. A separation of single grains is leading to new decomposition and reconstruction layers between primary particles and an increased charge transfer resistance. Further approaches to improve the high temperature cycle stability of NMC based materials should therefore be aimed at the cathode particles morphology in combination with similar electrolyte formulations as used in this study.

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.

Reduced graphene oxide aerogel with high-rate supercapacitive performance in aqueous electrolytes

Science.gov (United States)

Si, Weijiang; Wu, Xiaozhong; Zhou, Jin; Guo, Feifei; Zhuo, Shuping; Cui, Hongyou; Xing, Wei

2013-05-01

Reduced graphene oxide aerogel (RGOA) is synthesized successfully through a simultaneous self-assembly and reduction process using hypophosphorous acid and I2 as reductant. Nitrogen sorption analysis shows that the Brunauer-Emmett-Teller surface area of RGOA could reach as high as 830 m2 g-1, which is the largest value ever reported for graphene-based aerogels obtained through the simultaneous self-assembly and reduction strategy. The as-prepared RGOA is characterized by a variety of means such as scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy. Electrochemical tests show that RGOA exhibits a high-rate supercapacitive performance in aqueous electrolytes. The specific capacitance of RGOA is calculated to be 211.8 and 278.6 F g-1 in KOH and H2SO4 electrolytes, respectively. The perfect supercapacitive performance of RGOA is ascribed to its three-dimensional structure and the existence of oxygen-containing groups.

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

Intermediate Temperature Proton Conductors – Why and How

OpenAIRE

Li, Qingfeng; Aili, David; Jensen, Jens Oluf; Cleemann, Lars Nilausen

2016-01-01

The current technologies of fuel cells and electrolzers are based on ionic conducting electrolyte materials exclusively operational either in the low (20 - 200ºC) or high (600 - 1000ºC) temperature ranges. The intermediate temperature window, especially between 200 and 400 ºC, is still only represented by early fundamental material research for ionic electrolytes. Such materials, most likely based on proton conductors, are expected to bring a new generation of the technologies: fuel cells by ...

NEW POLYMER ELECTROLYTE MEMBRANES FOR FUEL CELLS OPERATING ABOVE 100°C

DEFF Research Database (Denmark)

Li, Qingfeng; Jensen, Jens Oluf; He, Ronghuan

2003-01-01

The state-of-the-art of PEMFC technology is based on perfluorosulfonic acid (PFSA) polymer membranes operating at a typical temperature of 80°C. The newest development in the field is alternative polymer electrolytes for operation above 100°C. This paper is devoted to a review on the development......, which is classified into three groups: modified PFSA membranes, alternative sulfonated polymer and their inorganic composite membranes and acid-base complex membranes. High temperature PEMFC has been demonstrated with advanced features such as fast electrode kinetics, high CO tolerance, simple thermal...

In-situ Plasticized Cross-linked Polymer Composite Electrolyte Enhanced with Lithium-ion Conducting Nanofibers for Ambient All-Solid-State Lithium-ion Batteries