Preview

Альтернативная энергетика и экология (ISJAEE)

Расширенный поиск
Доступ открыт Открытый доступ  Доступ закрыт Доступ платный или только для Подписчиков

ПРОТОННО-ОБМЕННЫЕ МЕМБРАНЫ НА ОСНОВЕ ГЕТЕРОПОЛИСОЕДИНЕНИЙ ДЛЯ НИЗКОТЕМПЕРАТУРНЫХ ТОПЛИВНЫХ ЭЛЕМЕНТОВ

https://doi.org/10.15518/isjaee.2015.04.02

Полный текст:

Аннотация

В обзоре проанализирована научная литература по использованию гетерополисоединений, твердых протонных проводников, полимерных протонно-обменных мембран для низкотемпературных топливных элементов. Кратко рассмотрены функции электролитов, выполняемые при работе в составе топливных элементов, и предъявляемые к ним требования, структура и транспортные свойства перфторированных протонно-обменных мембран – основных кандидатов на практическое применение в топливных элементах, – отмечены основные недостатки мембран, ограничивающие их использование. Отдельное внимание в обзоре уделено структуре и свойствам гетерополисоединений. Подробно рассмотрены свойства гетерополикислот (фосфор- и кремневольфрамовых), содержащих анионы со структурой Кеггина. В основной части обзора проанализированы методы получения композитных мембран на основе перфторированных и ароматических сульфосодержащих полимеров и гетерополисоединений и экспериментальные данные по влиянию природы и содержания гетерополисоединений на транспортные свойства полимерного электролита. Показано, что модифицирование гетерополисоединениями полимерных мембран является одним из перспективных методов улучшения их характеристик. Благодаря наличию собственной протонной проводимости и высокой гидрофильности, введение гетерополисоединений в полимерный электролит в ряде случаев позволяет существенно улучшить их протонную проводимость, особенно при повышенных температурах, а также уменьшить проницаемость по метанолу. В заключительной части обзора рассмотрены данные по использованию композитных полимерных электролитов, содержащих гетерополисоединения, в топливных элементах, проанализировано влияние гетерополисоединений на характеристики электрохимических устройств. Показано, что введение гетерополисоединений в мембрану позволяет существенно повысить рабочую температуру эксплуатации и характеристики топливного элемента.

Об авторах

Ю. А. Добровольский
Институт проблем химической физики Российской академии наук
Россия
доктор химических наук,  профессор, заведующий отделом ИПХФ РАН


А. И. Чикин
Институт проблем химической физики Российской академии наук
Россия
кандидат химических наук, младший научный сотрудник ИПХФ РАН


Е. А. Сангинов
Институт проблем химической физики Российской академии наук
Россия
кандидат химических наук, старший научный сотрудник ИПХФ РАН


А. В. Чуб
Институт проблем химической физики Российской академии наук
Россия
инженер ИПХФ РАН


Список литературы

1. Carrette L., Friedrich K.A., Stimming U. Fuel cells – fundamentals and applications // Fuel Cells. 2001. Vol. 1, No. 1. P. 5–39.

2. Aricò A.S., Srinivasan S., Antonucci V. DMFCs: from fundamental aspects to technology development // Fuel Cells. 2001. Vol. 1, No. 1. P. 133–161.

3. Jannasch P. Recent developments in high-temperature proton conducting polymer electrolyte membranes // Current Opinion in Colloid and Interface Science. 2003. Vol. 8, No. 1. P. 96–102.

4. Rikukawa M., Sanui K. Proton-conducting polymer electrolyte membranes based on hydrocarbon polymers // Prog. Polym. Sci. 2000. Vol. 25, No. 10. P. 1463–1502.

5. Rozi`ere J., Jones D.J. Non-fluorinated polymer materials for proton exchange membrane fuel cells // Annu. Rev. Mater. Res. 2003. Vol. 33. P. 503–555.

6. Li Q.F, He R.H., Jensen J.O., Bjerrum N.J. Ap-proaches and recent development of polymer electrolyte membranes for fuel cells operating above 100 °C // Chem. Mater. 2003. Vol. 15, No. 26. P. 4896–4915.

7. Hickner M.A., Ghassemi H., Kim Y.S., et al. Al-ternative polymer systems for proton exchange mem-branes (PEMs) // Chem. Rev. 2004. Vol. 104, No. 10. P. 4587–4612.

8. Добровольский Ю.А., Волков Е.В., Писарева А.В. и др. Протонообменные мембраны для водо-родно-воздушных топливных элементов // Рос. Хим. Ж. 2006. Т. L, № 6. С. 95–104.

9. Neburchilov V., Martin J., Wang H., Zhang J. A review of polymer electrolyte membranes for direct methanol fuel cells // J. Power Sources. 2007. Vol. 169. P. 221–238.

10. Добровольский Ю.А., Джаннаш П., Лаффит Б. и др. Успехи в области протонпроводящих полимерных электролитных мембран // Электрохимия. 2007. Т. 43, № 5. С. 515–527.

11. Добровольский Ю.А., Сангинов Е.А., Русанов А.Л. Протонообменные мембраны для низкотемпера-турных электрохимических устройств // Международ-ный научный журнал «Альтернативная энергетика и экология» (ISJAEE). 2009. Т. 76, № 8. С. 112–132.

12. Dobrovolsky Yu.A., Sanginov E.A., Rusanov A.L. Proton-exchange membranes for low temperature electrochemical devices // Fast proton-ion transport compounds, Ed.: Ubavka B. Mioč and Milorad Davidov-ić. Kerala, India: Transworld Research Network, 2010. P. 81–126.

13. Peighambardoust S.J., Rowshanzamir S., Amjadi M. Review of the proton exchange membranes for fuel cell applications // Int. J. Hydrogen Energy. 2010. Vol. 35, No. 17. P. 9349–9384.

14. Thiam H.S., Daud W.R.W., Kamarudin S.K., et al. Overview on nanostructured membrane in fuel cell appli-cations // Int. J. Hydrogen Energy. 2011. Vol. 36, No. 4. P. 3187–3205.

15. Ярославцев А.Б., Добровольский Ю.А., Шаг-лаева Н.С. и др. Наноструктурированные материалы для низкотемпературных топливных элементов // Успехи химии. 2012. Т. 81, № 3. С. 191–220.

16. Патент 3041317 США МКИЗ C08F28/00, C07C309/81. Fluorocarbon sulfonyl fluorides/Harper G.H., Norman G.R. // Chem. Abstracts. 1963. Vol. 58. P. 451a.

17. Патент 3282875 США МКИЗ C08F28/00, C07C309/82. Fluorocarbon vinyl ether polymers/ Con-nolly D.J., Gresham W.F. // Chem. Abstracts. 1966. Vol. 66. P. 11326.

18. Паншин Ю.А., Малкевич С.Г., Дунаевская Ц.С. Фторопласты. Л: Химия, 1978.

19. Souzy R., Ameduri B. Functional fluoropolymers for fuel cell membranes // Prog. Polym. Sci. 2005. Vol. 30, No. 6. P. 644–687.

20. Иванчев С.С., Мякин С.В. Полимерные мем-браны для топливных элементов: получение, струк-тура, модифицирование, свойства // Успехи Химии. 2010. Т. 79, № 2. С. 117–134.

21. Mauritz K.A., Moore R.B. State of understanding of Nafion // Chem. Rev. 2004. Vol. 104, No. 10. P. 4535–4585.

22. Yang Y., Siu A., Peckham T.J., Holdcrof S. Structural and morphological features of acid-bearing polymers for pem fuel cells // Adv. Polym. Sci. 2008. Vol. 215. P. 55–126.

23. Gierke T.D., Munn G.E., Wilson F.C. The mor-phology in Nafion perfluorinated membrane products, as determined by wide- and small- angle X-ray studies // J. of Polym. Sci.: Polym. Phys. Ed. 1981. Vol. 19. P. 1687–1704.

24. Hsu W.Y., Gierke T.D. Ion-transport and cluster-ing in Nafion perfluorinated membranes // J. Membrane Sci. 1983. Vol. 13, No. 3. P. 307–326.

25. Gebel G. Structural evolution of water swollen perfluorosulfonated ionomers from dry membrane to solution // Polymer. 2000. Vol. 41, No. 15. P. 5829–5838.

26. Kreuer K.D. On the development of proton con-ducting polymer membranes for hydrogen and methanol fuel cells // J. Membrane Sci. 2001. Vol. 185, No. 1. P. 29–39.

27. McLean R.S., Doyle M., Sauer B.B. High-resolution imaging of ionic domains and crystal mor-phology in ionomers using AFM techniques // Macro-molecules. 2000. Vol. 33, No. 17. P. 6541–6550.

28. Zawodzinski T.A., Neeman Jr.M., Sillerud L.O., Cottesfeld S. Determination of water dlffusion coeff icients in perfluorosulfonate ionomeric membranes // J. Phys. Chem. 1991. Vol. 95, No. 15. P. 6040–6044.

29. Meier-Haack J., Taeger A., Vogel C., et al. Membranes from sulfonated block copolymers for use in fuel cells // Sep. Purif. Technol. 2005. Vol. 41, No. 3. P. 207–220.

30. Higashihara T., Matsumoto K., Ueda M. Sul-fonated aromatic hydrocarbon polymers as proton ex-change membranes for fuel cells // Polymer. 2009. Vol. 50, No. 23. P. 5341–5357.

31. Gürsel S.A., Gubler L., Gupta B., Scherer G.G. Radiation grafted membranes // Adv. Polym. Sci. 2008. Vol. 215. P. 157–217.

32. Ярославцев А.Б. Композиционные материалы с ионной проводимостью — от неорганических ком-позитов до гибридных мембран // Успехи Химии. 2009. Т. 78, № 11. С. 1094–1112.

33. Ahmad H., Kamarudin S.K., Hasran U.A., Daud W.R.W. Overview of hybrid membranes for direct-methanol fuel-cell applications // Int. J. Hydrogen Energy. 2010. Vol. 35, No. 5. P. 2160–2175.

34. Никитина Е.А. Гетерополисоединения. М.: Госхимиздат, 1962. 422 с.

35. Keggin J.P. The Structure and Formula of 12-Phosphotungstic Acid // Proc. Roy. Soc. 1934. Vol. A144. P. 75–100.

36. Himeno S., Takamoto M., Ueda T. Synthesis, characterisation and voltammetric study of β-Keggin-type [PW12O40]3- complex // J. Electroanal. Chem. 1999. Vol. 465, No. 2. P. 129–135.

37. Коростелева E.A., Леонова Л.С., Укше E.A. Зависимость протонной проводимости гетерополисоединений от степени гидратации // Электрохимия. 1987. Т. 23. С. 1349–1353.

38. Mioc U.B., Todorovic M.R., Davidovic M. et al. Differential impedance analysis of solid oxide materials // Solid State Ionics. 2005. Vol. 176, No. 25–28. P. 2005–2009.

39. Vakulenko A., Dobrovolsky Yu., Leonova L. et al. Protonic conductivity of neutral and acidic silicotung-states // Solid State Ionics. 2000. V. 136–137. P. 285–290.

40. Chikin A.I., Chernyak A.V., Jin Zh. et al. Mobility of protons in 12-phosphotungstic acid and its acid and neutral salts // J. Solid State Electrochem. 2012. V. 16, No. 8. P. 2767–2775.

41. Mioc U., Davidovic M., Tjapkin N. et al. Equilib-rium of the protonic species in hydrates of some hetero-polyacids at elevated temperatures // Solid State Ionics. 1991. Vol. 46, No. 1–2. P. 103–109.

42. Патент 4024036 США МКИЗ H01M8/10, C25B13/04, H01M10/36. Proton permselective solid-state member and apparatus utilizing said permselective member / Nakamura O., Kodama T., Ogino I., Miyake Y. 1977.

43. Mikhailenko S.D., Kaliaguine S., Moffat J.B. Electrical impedance studies of the ammonium salt of 12-tungstophosphoric acid in the presence of liquid water // Solid State Ionics. 1997. Vol. 99, No. 3–4. P. 281–286.

44. Highfield J.G., Moffat J.B. Characterization of 12-tungstophosphoric acid and related salts using photo-acoustic spectroscopy in the infrared region: I. Thermal stability and interactions with ammonia // J. Catal. 1984. Vol. 88, No. 1. P. 177–187.

45. Moffat J.B. Implicit and explicit microporosity in heteropoly oxometalates // J. Catal. 1989. Vol. 52, No. 1. P. 169–191.

46. Dobrovolsky Yu., Leonova L., Vakulenko A. Thermodynamic equilibria and kinetic reversibility of the solid electrolyte/electron conductor/gas boundary at low temperature // Solid State Ionics. 1996. V. 86–88. P. 1017–1021.

47. Treglazov I., Leonova L., Dobrovolsky Yu. et al. Electrocatalytic effects in gas sensors based on low–temperature superprotonics // Sensors & Actuators B. 2005. V. 106, No. 1. P. 164–169.

48. Nakamura O., Adachi M., Kawai M. et al. Copper (I) oxide as oxygen electrode catalyst in a solid elec-trolyte, H3Mo12PO40•29H2O, fuel cell // Materials Research Bulletin. 1985. Vol. 20, No. 3. P. 293–297.

49. Патент 4554224 США МКИЗ H01M8/10, H01M4/90. Copper oxide as cathode catalyst/Nakamura O., Ogino I., Adachi M. 1985.

50. Giordano N., Staiti P., Hocevar S., Arico A.S. High performance fuel cell based on phosphotungstic acid as proton conducting electrolyte // Electrochim. Acta. 1996. Vol. 41, No. 3. P. 397–403.

51. Staiti P., Hocevar S., Giordano N. Fuel cells with H3PW12O40 29H2O as solid electrolyte // Int. J. Hydrogen Energy. 1997. Vol. 22, No. 8. P. 809–814.

52. Staiti P., Freni S., Hocevar S. Synthesis and char-acterization of proton-conducting materials containing dodecatungstophosphoric and dodecatungstosilic acid supported on silica // J. Power Sources. 1999. Vol. 79, No. 2. P. 250–255.

53. Malhotra S., Datta R. Membrane-supported non-volatile acidic electrolytes allow higher temperature op-eration of proton-exchange membrane fuel cells // J. Electrochem. Soc. 1997. Vol. 144. P. L23–L26.

54. Xu W., Lu T., Liu C., Xing W. Low methanol permeable composite Nafion/silica/PWA membranes for low temperature direct methanol fuel cells // Electrochim. Acta. 2005. Vol. 50, No. 16–17. P. 3280–3285.

55. Tazi B., Savadogo O. Parameters of PEM fuel-cells based on new membranes fabricated from Nafion®, sili-cotungstic acid and thiophene // Electrochim. Acta. 2000. Vol. 45, No. 25–26. P. 4329–4339.

56. Dimitrova P., Friedrich K.A., Stimming U., Vogt B. Modified Nafion®-based membranes for use in direct methanol fuel cells // Solid State Ionics. 2002. Vol. 150, No. 1–2. P. 115–122.

57. Ramani V., Kunz H., Fenton J. Stabilized hetero-polyacid/Nafion composite membranes for elevated temperature/low relative humidity PEFC operation // Electrochim. Acta. 2005. Vol. 50, No. 5. P. 1181–1187.

58. Staiti P., Arico A.S., Baglio V. et al. Hybrid Nafion–silica membranes doped with heteropolyacids for application in direct methanol fuel cells // Solid State Ionics. 2001. Vol. 145, No. 1–4. P. 101–107.

59. Arico A., Baglio V., Di Blasi A., et al. Influence of the acid–base characteristics of inorganic fillers on the high temperature performance of composite membranes in direct methanol fuel cells // Solid State Ionics. 2003. Vol. 161, No. 3–4. P. 251–265.

60. Kim H.-J., Shul Y.-G., Han H. Sulfonic-functionalized heteropolyacid–silica nanoparticles for high temperature operation of a direct methanol fuel cell // J. Power Sources. 2006. Vol. 158, No. 1. P. 137–142.

61. Ramani V., Kunz H.R., Fenton J.M. Metal dioxide supported heteropolyacid/Nafion® composite mem-branes for elevated temperature/low relative humidity PEFC operation // J. Membrane Sci. 2006. Vol. 279, No. 1–2. P. 506–512.

62. Mahreni A., Mohamad A.B., Kadhum A.A.H., et al. Nafion/silicon oxide/phosphotungstic acid nanocom-posite membrane with enhanced proton conductivity // J. Membrane Sci. 2009. Vol. 327, No. 1–2. P. 32–40.

63. Сафронова Е.Ю., Стенина И.А., Ярославцев А.Б. Синтез и исследование гибридных мембран МФ-4СК-SiO2, модифицированных фосфорно-вольфрамовой гетерополикислотой // Ж. неорган. химии. 2010. Т. 55, № 1. С. 16–20.

64. Wang, L. Yi B.L., Zhang H.M., Xing D.M. Cs2.5H0.5PWO40/SiO2 as addition self-humidifying com-posite membrane for proton exchange membrane fuel cells // Electrochim. Acta. 2007. Vol. 52, No. 17. P. 5479–5483.

65. Ramani V., Kunz H.R., Fenton J.M. Stabilized composite membranes and membrane electrode assem-blies for elevated temperature/low relative humidity PEFC operation // J. Power Sources. 2005. Vol. 152. P. 182–188.

66. Amirinejad M., Madaeni S.S., Navarra M.A., et al. Preparation and characterization of phosphotungstic acid-derived salt/Nafion nanocomposite membranes for proton exchange membrane fuel cells // J. Power Sources. 2011. Vol. 196, No. 3. P. 988–998.

67. Xiang Y., Yang M., Zhang J., et al. Phosphotung-stic acid (HPW) molecules anchored in the bulk of Nafion as methanol-blocking membrane for direct methanol fuel cells // J. Membrane Sci. 2011. Vol. 368, No. 1–2. P. 241–245.

68. Gerasimova E.V., Safronova E.Yu., Volodin A.A. et al. Electrocatalytic properties of the nanostructured elec-trodes and membranes in hydrogen-air fuel cells // Ca-talysis Today. 2012. V. 193. P. 81–86.

69. Ramani V., Kunz H.., Fenton J. Investigation of Nafion®/HPA composite membranes for high tempera-ture/low relative humidity PEMFC operation // J. Mem-brane Sci. 2004. Vol. 232, No. 1–2. P. 31–44.

70. Ramani V., Kunz H., Fenton J. Effect of particle size reduction on the conductivity of Nafi-on/phosphotungstic acid composite membranes // J. Membrane Sci. 2005. Vol. 266, No. 1–2. P. 110–114.

71. Sacca A., Carbone A., Pedicini R., et al. Phos-photungstic Acid Supported on a Nanopowdered ZrO2 as a Filler in Nafion-Based Membranes for Polymer Elec

72. Electrolyte Fuel Cells // Fuel Cells. 2008. Vol. 8, No. 3–4. P. 225–235.

73. Zaidi S.M., Mikhailenko S.D., Robertson G.P., et al. Proton conducting composite membranes from polyether ether ketone and heteropolyacids for fuel cell ap-plications // J. Membrane Sci. 2000. Vol. 173, No. 1. P. 17–34.

74. Ponce M., Prado L.A.S.A., Ruffmann B. et al. Reduction of methanol permeability in polyetherketone–heteropolyacid membranes // J. Membrane Sci. 2003. Vol. 217, No. 1–2. P. 5–15.

75. Ponce M., Prado L.A.S.A., Silva V., Nunes S.P. Membranes for direct methanol fuel cell based on modi-fied heteropolyacids // Desalination. 2004. Vol. 162. P. 383–391.

76. Prado L.A.S.A., Goerigk G., Ponce M. L., et al. Characterization of proton-conducting organic-inorganic polymeric materials by ASAXS // J. Polym. Sci., Part B: Polym. Phys. 2005. Vol. 43, No. 21. P. 2981–2992.

77. Prado L.A.S.A., Ponce M.L., Funari S.S., et al. SAXS/WAXS characterization of proton-conducting polymer membranes containing phosphomolybdic acid // J. Non-Crystalline Solids. 2005. Vol. 351, No. 27–29. P. 2194-2199.

78. Ahmad M.I., Zaidi S.M.J., Rahman S.U. Proton conductivity and characterization of novel composite membranes for medium-temperature fuel cells // Desali-nation. 2006. Vol. 193, No. 1–3. P. 387–397.

79. Prado L.A.S.A., Ponce M.L., Goerigk G., et al. Analysis of proton-conducting organic–inorganic hybrid materials based on sulphonated poly(ether ether ketone) and phosphotungstic acid via ASAXS and WAXS // J. Non-Crystalline Solids. 2009. Vol. 355, No. 1. P. 6–11.

80. Ismail A.F., Othman N.H., Mustafa A. Sulfonated polyether ether ketone composite membrane using tung-stosilicic acid supported on silica–aluminium oxide for direct methanol fuel cell (DMFC) // J. Membrane Sci. 2009. Vol. 329, No. 1–2. P. 18–29.

81. Celso F., Mikhailenko S.D., Kaliaguine S., et al. SPEEK based composite PEMs containing tungstophos-phoric acid and modified with benzimidazole derivatives // J. Membrane Sci. 2009. Vol. 336, No. 1–2. P. 118–127.

82. Colicchio I., Wen F., Keul H., et al. Sulfonated poly(ether ether ketone)–silica membranes doped with phosphotungstic acid. Morphology and proton conductivity // J. Membrane Sci. 2009. Vol. 326, No. 1. P. 45–57.

83. Fontananova E., Trotta F., Jansen J.C., Drioli E. Preparation and characterization of new non-fluorinated polymeric and composite membranes for PEMFCs // J. Membrane Sci. 2010. Vol. 348, No. 1–2. P. 326–336.

84. Dogan H., Inan T.Y., Unveren E., Kaya M. Effect of cesium salt of tungstophosphoric acid (Cs-TPA) on the properties of sulfonated polyether ether ketone (SPEEK) composite membranes for fuel cell applications // Int. J. Hydrogen Energy. 2010. Vol. 35, No. 15. P. 7784–7795.

85. Smitha B., Sridhar S., Khan A.A. Proton conduct-ing composite membranes from polysulfone and hetero-polyacid for fuel cell applications // J. Polym. Sci., Part B: Polym. Phys. 2005. Vol. 43, No. 12. P. 1538–1547.

86. Tan A.R., Magno de Carvalho L., de Souza Gomes A. Nanostructured Proton-Conducting Membranes for Fuel Cell Applications // Macromol. Symp. 2005. Vol. 229, No. 1. P. 168–178.

87. Kim Y.S., Wang F., Hickner M., et al. Fabrication and characterization of heteropolyacid (H3PW12O40)/directly polymerized sulfonated poly(arylene ether sulfone) copolymer composite mem-branes for higher temperature fuel cell applications // J. Membrane Sci. 2003. Vol. 212, No. 1–2. P. 263–282.

88. Zhang H., Pang J., Wang D., et al. Sulfonated poly(arylene ether nitrile ketone) and its composite with phosphotungstic acid as materials for proton exchange membranes // J. Membrane Sci. 2005. Vol. 264, No. 1–2. P. 56–64.

89. Zhang H., Zhu B., Xu Y. Composite membranes of sulfonated poly(phthalazinone ether ketone) doped with 12-phosphotungstic acid (H3PW12O40) for proton exchange membranes // Solid State Ionics. 2006. Vol. 177, No. 13–14. P. 1123–1128.

90. Wang Z., Ni H., Zhao C., et al. Investigation of sulfonated poly(ether ether ketone sul-fone)/heteropolyacid composite membranes for high temperature fuel cell applications // J. Polym. Sci., Part B: Polym. Phys. 2006. Vol. 44, No. 14. P. 1967–1978.

91. Tan A.R., de Carvalho L.M., de Ramos Filho F. G., de Souza Gomes A. Nanocomposite Membranes based on sulfonated poly(etheretherketone) structured with modified silica for direct ethanol fuel cell // Macromol. Symp. 2006. Vol. 245–246, No. 1. P. 470–475.

92. Xue S., Yin G., Cai K., Shao Y. Permeabilities of methanol, ethanol and dimethyl ether in new composite membranes: A comparison with Nafion membranes // J. Membrane Sci. 2007. Vol. 289, No. 1–2. P. 51–57.

93. Jang W., Choi S., Lee S., et al. Characterizations and stability of polyimide–phosphotungstic acid compo-site electrolyte membranes for fuel cell // Polym. Degrad. Stab. 2007. Vol. 92, No. 7. P. 1289–1296.

94. Yamada M., Honma I. Heteropolyacid-encapsulated self-assembled materials for anhydrous proton-conducting electrolytes. // J. Phys. Chem. B. 2006. Vol. 110, No. 41. P. 20486–20490.

95. Choi J.K., Lee D.K., Kim Y.W., et al. Composite polymer electrolyte membranes comprising triblock co-polymer and heteropolyacid for fuel cell applications // J. Polym. Sci., Part B: Polym. Phys. 2008. Vol. 46, No. 7. P. 691–701.

96. Gomez-Romero P., Asensio J., Borros S. Hybrid proton-conducting membranes for polymer electrolyte fuel cells phosphomolybdic acid doped poly(2,5-benzimidazole)—(ABPBI-H3PMo12O40) // Electrochim. Acta. 2005. Vol. 50, No. 24. P. 4715–4720.

97. Staiti P., Minutoli M. Influence of composition and acid treatment on proton conduction of composite polybenzimidazole membranes // J. Power Sources. 2001. Vol. 94, No. 1. P. 9–13.

98. He R., Li Q., Xiao G., Bjerrum N.J. Proton con-ductivity of phosphoric acid doped polybenzimidazole and its composites with inorganic proton conductors // J. Membrane Sci. 2003. Vol. 226, No. 1–2. P. 169–184

99. Staiti P. Proton conductive membranes based on silicotungstic acid/silica and polybenzimidazole // Mater. Lett. 2001. Vol. 47, No. 4–5. P. 241–246.

100. Staiti P., Minutoli M. Influence of composition and acid treatment on proton conduction of composite polybenzimidazole membranes // J. Power Sources. 2001. Vol. 94, No. 1. P. 9–13.

101. Honma I., Takeda Y., Bae J.M. Protonic con-ducting properties of sol-gel derived organic/inorganic nanocomposite membranes doped with acidic functional molecules // Solid State Ionics. 1999. Vol. 120, No. 1–4. P. 255–264.

102. Honma I., Nomura S., Nakajima H. Protonic conducting organic/inorganic nanocomposites for poly-mer electrolyte membrane // J. Membrane Sci. 2001. Vol. 185, No. 1. P. 83–94.

103. Lavrencic Stangar U., Groselj N., Orel B., et al. Proton-conducting sol–gel hybrids containing heteropoly acids // Solid State Ionics. 2001. Vol. 145, No. 1–4. P. 109–118.

104. Nakajima H., Nomura S., Sugimoto T., et al. High temperature proton conducting organic/inorganic nanohybrids for polymer electrolyte membrane // J. Elec-trochem. Soc. 2002. Vol. 149, No. 8. P. A953–A959.

105. Vernon D.R., Menga F., Dec S.F., et al. Syn-thesis, characterization, and conductivity measurements of hybrid membranes containing a mono-lacunary heter-opolyacid for PEM fuel cell applications // J. Power Sources. 2005. Vol. 139, No. 1–2. P. 141–151.

106. Mustarelli P., Carollo A., Grandi S., et al. Com-posite Proton-Conducting Membranes for PEMFCs // Fuel Cells. 2007. Vol. 7, No. 6. P. 441–446.

107. Gong J., Li X.-D., Shao C.-L., et al. Photochromic and thermal properties of poly(vinyl alcohol)/H6P2W18O62 hybrid membranes // Mater. Chem. Phys. 2003. Vol. 79, No. 1. P. 87–93.

108. Lin C.W., Thangamuthu R., Yang C.J. Proton-conducting membranes with high selectivity from phos-photungstic acid-doped poly(vinyl alcohol) for DMFC applications // J. Membrane Sci. 2005. Vol. 253, No. 1–2. P. 23–31.

109. Helen M., Viswanathan B., Murthy S.S. Fabri-cation and properties of hybrid membranes based on salts of heteropolyacid, zirconium phosphate and polyvi-nyl alcohol // J. Power Sources. 2006. Vol. 163, No. 1. P. 433–439.

110. Helen M., Viswanathan B., Murthy S. Synthesis and characterization of composite membranes based on α-zirconium phosphate and silicotungstic acid // J. Membrane Sci. 2007. Vol. 292, No. 1–2. P. 98–105

111. Lakshminarayana G., Nogami M. Synthesis and characterization of proton conducting inorganic-organic hybrid nanocomposite membranes based on mixed PWA-PMA-TEOS-GPTMS-H3PO4-APTES for H2/O2 fuel cells // J. Phys. Chem. C. 2009. Vol. 113, No. 32. P. 14540–14550.

112. Helen M., Viswanathan B., Murthy S.S. Poly(vinyl alcohol)–polyacrylamide blends with cesium salts of heteropolyacid as a polymer electrolyte for direct methanol fuel cell applications // J. Appl. Polym. Sci. 2010. Vol. 116, No. 6. P. 3437–3447.

113. Bhat S.D., Sahu A.K., Jalajakshi A., et al. PVA–SSA–HPA mixed-matrix-membrane electrolytes for DMFCs // J. Electrochem. Soc. 2010. Vol. 157, No. 10. P. B1403–B1412.

114. Honma I., Nakajima H., Nishikawa O., et al. Amphiphilic organic/inorganic nanohybrid macromole-cules for intermediate-temperature proton conducting electrolyte membranes // J. Electrochem. Soc. 2002. Vol. 149, No. 10. P. A1389–A1392.

115. Honma I., Nakajimaa H., Nishikawa O., et al. Organic/inorganic nano-composites for high temperature proton conducting polymer electrolytes // Solid State Ionics. 2003. Vol. 162–163. P. 237–245.

116. Cui Z., Liu Ch, Lu T., Xing W. Polyelectrolyte complexes of chitosan and phosphotungstic acid as pro-ton-conducting membranes for direct methanol fuel cells // J. Power Sources. 2007. Vol. 167, No. 1. P. 94–99.

117. Zukowska G., Stevens J.R., Jeffrey K.R. Anhy-drous gel electrolytes doped with silicotungstic acid // Electrochim. Acta. 2003. Vol. 48, No. 14–16. P. 2157–2164.

118. Патент 6465136 США МКИЗ C25B13/08, H01M4/88, H01M4/86, B05D5/12, H01M4/96, H01M8/10, C08J5/22, B01D69/12, H01M6/18, H01M4/92, B01D69/14, H01M8/02. Perfluorinated sulfonic acid polymers such as nafion.rtm. and other ion exchange materials incorporated into films to form composite membranes; optionally a noble metal is dispersed within the matrix/ Fenton J.M., Kunz H.R., Cutlip M.B., Lin J.C. // 2002.

119. Sauk J., Byun J., Kim H. Composite Nafi-on/polyphenylene oxide (PPO) membranes with phos-phomolybdic acid (PMA) for direct methanol fuel cells // J. Power Sources. 2005. Vol. 143. P.136–141.

120. Malers J.L., Sweikart M.A., Horan J.L., et al. Studies of heteropoly acid/polyvinylidenedifluoride–hexafluoroproylene composite membranes and implica-tion for the use of heteropoly acids as the proton con-ducting component in a fuel cell membrane // J. Power Sources. 2007. Vol. 172. P. 83–88.


Для цитирования:


Добровольский Ю.А., Чикин А.И., Сангинов Е.А., Чуб А.В. ПРОТОННО-ОБМЕННЫЕ МЕМБРАНЫ НА ОСНОВЕ ГЕТЕРОПОЛИСОЕДИНЕНИЙ ДЛЯ НИЗКОТЕМПЕРАТУРНЫХ ТОПЛИВНЫХ ЭЛЕМЕНТОВ. Альтернативная энергетика и экология (ISJAEE). 2015;(4):22-45. https://doi.org/10.15518/isjaee.2015.04.02

For citation:


Dobrovolsky Y.A., Chikin A.I., Sanginov E.A., Chub A.V. PROTON-EXCHANGE MEMBRANES BASED ON HETEROPOLY COMPOUNDS FOR LOW TEMPERATURE FUEL CELLS. Alternative Energy and Ecology (ISJAEE). 2015;(4):22-45. (In Russ.) (In Russ.) https://doi.org/10.15518/isjaee.2015.04.02

Просмотров: 1249


ISSN 1608-8298 (Print)