Electrolitos Sólidos

Como se ha mencionado anteriormente, estos electrolitos cumplen la mayoría de requerimientos de operación, especialmente aquellos relacionados con la interfase electrodo/electrolito y con la seguridad, aunque las conductividades obtenidas no siempre superan la barrera de conductividad iónica cercada a 10-4 Scm-1. Además, muchos de ellos permiten un control de la nano-estructura, debido a sus excelentes propiedades mecánicas. Consideremos los principales tipos de electrolitos sólidos para baterías [4, 63]:

- Electrolitos Sólidos Poliméricos: Actúan como un separador de los electrodos y presentan una amplia flexibilidad en cuanto al diseño y procesamiento. Este tipo de electrodos puede mantener el contacto en la interfase electrodo/electrolito durante pequeños cambios en el volumen del electrodo en estado de carga. En este apartado destacan los óxidos de polietileno (PEO) que contienen en su estructura una sal de litio, (LiPF6, LiAsF6). También podemos encontrar polímeros basados en poliacrilonitrilo (PAN), polimetil-metacrilato (PMMA), fluoruros de poli-vinilideno (PVdF), fluoruros de poli-vinilideno – fluoruro hexafluoruro propileno (PVdF-HFP), poli(acrilonitrilo-metil metacrilato (P(AN- MMA), éteres de poliamida y polifosfacenos [4, 64-76].

- Electrolitos Sólidos inorgánicos: Estos materiales tienen conductividades cercanas a 10-4 Scm-1, además poseen una ventana de operación electroquímica amplia y cumplen los requerimientos de operación del electrolito en buena medida. No obstante no conserva fácilmente la interfase electrodo/electrolito durante el ciclado de la batería. Lo anterior conlleva a tener problemas de operación cuando se desarrollan las baterías a gran escala, debido a que los cambios de volumen de estas estructuras son significativos. Habitualmente se emplean estos electrolitos en baterías de lámina delgada [4].

- Electrolitos Sólidos Híbridos: Estos materiales están conformados por unión a nivel molecular entre compuestos de naturaleza netamente orgánica con compuestos de naturaleza inorgánica. El material final, generalmente amorfo,

- 61 -

contiene propiedades distintas a las propiedades de sus precursores [4]. Este campo de la ciencia ha tomado gran relevancia en investigación en los últimos años [77]. Muchos de estos electrolitos pueden ser fabricados a través de metodologías de química en disolución como el proceso sol-gel [77-80].

- 62 -

BIBLIOGRAFÍA

1. Wenkel, R. and C. Papale, Cambios de Rumbo en el Panorama Energético, in Deutsche Welle2012: Alemania.

2. Aifantis, K.E., S. Hackney, and R. Vasant Kumar, High Energy Density Lithium Batteries. 2010, Weinheim: WILEY-VCH Verlag GmbH & Co. KGaA.

3. Scrosati, B. and J. Garche, Lithium batteries: Status, prospects and future. Journal of Power Sources, 2010. 195: p. 2419-2430.

4. Goodenough, J.B. and Y. Kim, Challenges for Rechargeable Li Batteries. Chem. Mater., 2010. 22: p. 587-603.

5. Yamada, I., et al., Lithium-ion transfer on a LixCoO2 thin film electrode

prepared by pulsed laser deposition - Effect of orientation -. Journal of Power Sources, 2007. 172: p. 933-937.

6. OCDE/AIE, World Energy Outlook, Edición 2013, 2013, International Energy Agency: Paris.

7. Contestabile, M., et al., Battery electric vehicles, hydrgen fuel cells and biofuels. Which will be the winner? Energy & Environ. Sci., 2011.

8. Rueter, G. and E. Romero-Castillo, Hacia el Cambio del Modelo Energético, in Deutsche Welle2012: Alemania.

9. Ormazabal, J.M., Política Energética y Desarrollo, in Doc. 902011, Fundación Ciudadanía y Valores Madrid. p. 7.

10. Rieger, P.H., Electrochemistry. 2nd. Ed. 1994, New York: Chapman & Hall. 11. Kiehne, H.A., ed. Battery Technology Handbook. Second Edition. 2003, Marcel

Dekker, Inc: New York; Basel.

12. Tarascon, J.M., Key Challenges in Future Li-Battery Research. Phil. Trans. R. Soc. A, 2010. 368: p. 3227-3241.

13. Rueter, G. and R. Muñoz-Lima, Más Energía Solar para Alemania... y Más Rápido, in Deutsche Welle2012: Alemania.

14. Battery-University. Global Battery Markets. Consultada en noviembre de 2014;

Available from:

http://batteryuniversity.com/learn/article/global_battery_markets.

15. Nagamedianova, Z. and E.M. Sánchez Cervantes, Nuevos Materiales con Potencial Aplicación en Microbaterías de Litio. Ciencia UANL, 2007. X(4): p. 443-450.

16. Aguado-Monsonet, M.A. and L. Bontoux, Nuevas Tecnologías para Baterías: Desarrollos Prometedores. The IPTS Report, 1999. 36: p. 366-375.

17. Bruce, P.G., B. Scrosati, and J.M. Tarascon, Nanomaterials for Rechargeable Lithium Batteries. Angew. Chem. Int. Ed., , 2008. 47: p. 2930-2946.

18. Besenhard, J.O., ed. Handbook of battery materials. 1999, WILEY-VCH Verlag GmbH: Weinheim.

19. Quartarone, E. and P. Mustarelli, Electrolytes for solid-state lithium rechargeable batteries: Recent advances and perspectives. Chem. Soc. Rev., 2011. 40: p. 2525-2540.

20. Yoda, S. and K. Ishihara, The Advent of Battery-Based Societies and the Global Environment in the 21st Century. Journal of Power Sources, 1999. 81–82(0): p. 162-169.

21. Linden, D. and T.B. Reddy, eds. Handbook of Batteries. Third Edition. 2002, McGraw-Hill: New York.

- 63 -

22. Dell, R.M. and D.A.J. Rand, eds. Understanding Batteries. Second Edition. 2001, Royal Society of Chemistry: Cambridge.

23. Bagotsky, V.S., 19. Batteries (Electrochemical Power Sources), in Fundamentals of Electrochemistry. 2006, John Wiley & Sons, Inc.: Hoboken, New Jersey.

24. Lavela Cabello, P. and J.L. Tirado Coello, Baterías Avanzadas. 1999, Córdoba: Servicio de Publicaciones de la Universidad de Córdoba.

25. Wang, J., Analytical Electrochemistry. Second Edition. 2001, New York / Chichester / Weinheim / Brisbane / Singapore / Toronto: Wiley-VCH.

26. Tarascon, J.M. and M. Armand, Issues and Challenges Facing Rechargeable Lithium Batteries. Nature, 2001. 414: p. 359-367.

27. Dell, R.M., Batteries: Fifty Years of Materials Development. Solid State Ionics, 2000. 134(1–2): p. 139-158.

28. Julien, C. and G.A. Nazri, Solid State Batteries Materials Design and Optimization. 1994, Boston; Dordrecht; London: Kluwer Academic Publishers. 629.

29. Winter, M., et al., Insertion Electrode Materials for Rechargeable Lithium Batteries. Advanced Materials, 1998. 10(10): p. 725-763.

30. Brissot, C., et al., Dendritic Growth Mechanisms in Lithium/Polymer Cells. Journal of Power Sources, 1999. 81-82: p. 925-929.

31. Scrosati, B., History of Lithium Batteries. Journal of Solid State Electrochemistry, 2011. 15: p. 1623-1630.

32. Whittingham, M.S., Electrical Energy Storage and Intercalation Chemistry. Science, 1976. 192(4244): p. 1126-1127.

33. Guyomard, D. and J.-M. Tarascon, Rocking-Chair or Lithium-Ion Rechargeable Lithium Batteries. Advanced Materials, 1994. 6(5): p. 408-412.

34. Gómez-Cámer, J.L., Síntesis y Caracterización de Composites Basados en Silicio Nanométrico para su Uso Como Electrodos en Baterías de Ion-Litio, in Departamento de Química Inorgánica e Ingeniería Química2010, Universidad de Córdoba: Córdoba. p. 176.

35. Ritchie, A.G., Recent Developments and Likely Advances in Lithium Rechargeable Batteries. Journal of Power Sources, 2004. 136(2): p. 285-289. 36. Ellis, B.L., K.T. Lee, and L.F. Nazar, Positive Electrode Materials for Li-Ion

and Li-Batteries. Chem. Mater., 2010. 22(3): p. 691-714.

37. Wakihara, M., Recent Developments in lithium ion batteries. Materials Science and Engineering, 2001. R33: p. 109-134.

38. Dahlin, G.R. and K.E. Strom, eds. Lithium Batteries: Research, Technology and Applications. 2010, Nova Science Publishers, Inc.: New York.

39. Schöllhorn, R., Reversible Topotactic Redox Reactions of Solids by Electron/Ion Transfer. Angew. Chem. Int. Ed.,Engl., 1980. 19: p. 983-sss.

40. Steele, B.C.H. and A. Heinzel, Materials for Fuel-Cell Technologies. Nature, 2001. 414(6861): p. 345-352.

41. Schlapbach, L. and A. Zuttel, Hydrogen-storage Materials for Mobile Applications. Nature, 2001. 414(6861): p. 353-358.

42. Scrosati, B., et al., Investigation of New Types of Lithium-ion Battery Materials. Journal of Power Sources, 2002. 105(2): p. 161-168.

43. Nishi, Y., Lithium Ion Secondary Batteries; Past 10 Years and the Future. Journal of Power Sources, 2001. 100(1–2): p. 101-106.

44. Bates, J.B., et al., Rechargeable thin-film lithium batteries. Solid State Ionics, 1994. 70/71: p. 619-628.

- 64 -

45. Oudenhoven, J.F.M., B. L., and N.P.H. L., All-Solid State Lithium-Ion Microbatteries: A Review of various Three-Dimensional Concepts. Adv. Energy Mater., 2011. 1: p. 10-33.

46. Dokko, K., et al., Sol-Gel fabrication of lithium-ion microarray battery. Electrochemistry Communications, 2007. 9: p. 857-862.

47. García-Alvarado, F., Baterías Recargables de Litio: Fundamentos y Materiales. Bol. Soc. Esp. Cerám. Vidrio, 1996. 35(5): p. 327-336.

48. Shokoohi, F.K., et al., Low Temperature LiMn2 O 4 Spinel Films for Secondary

Lithium Batteries. Journal of The Electrochemical Society, 1992. 139(7): p. 1845-1849.

49. Liu, Y., J.Y. Lee, and L. Hong, Morphology, Crystallinity, and Electrochemical Properties of In Situ Formed Poly(ethylene oxide)/TiO2 Nanocomposite Polymer

Electrolytes. Journal of Applied Polymer Science, 2003. 89: p. 2815-2822. 50. Souza, F.L., et al., Sol-Gel nonhydrolytic synthesis of a hybrid organic-

inorganic electrolyte for application in lithium-ion devices. Solid State Ionics, 2004. 166: p. 83-88.

51. Tigelaar, D.M., M.A.B. Meador, and W.R. Bennett, Composite Electrolytes for Lithium Batteries: Ionic Liquids in APTES Cross-Linked Polymers. Macromolecules, 2007. 40: p. 4159-4164.

52. Newman, G.H., et al., Hazard Investigations of LiClO4 / Dioxolane Electrolyte.

Journal of The Electrochemical Society, 1980. 127(9): p. 2025-2027.

53. Salomon, M. and B. Scrosati, Lithium Batteries: Present Trends and Prospects. Gazzetta Chimica Italiana, 1996. 126(7): p. 415.

54. Nakajima, T. and H. Groult, Fluorinated Materials for Energy Conversion. 2005, Amsterdam: Elsevier Ltd.

55. Aravindan, V., et al., Lithium-Ion Conducting Electrolyte Salts for Lithium Batteries. Chem. Eur. J., 2011. 17: p. 14326-14346.

56. Tasaki, K., et al., Solubility of Lithium Salts Formed on the Lithium-Ion Battery Negative Electrode Surface in Organic Solvents. Journal of The Electochemical Society, 2009. 156(12): p. A1019-A1027.

57. Webber, A., Conductivity and Viscosity of Solutions of LiCF3 SO 3,

Li ( CF3SO2)2N, and Their Mixtures. Journal of The Electrochemical Society,

1991. 138(9): p. 2586-2590.

58. Dominey, L.A., V.R. Koch, and T.J. Blakley, Thermally Stable Lithium Salts for Polymer Electrolytes. Electrochimica Acta, 1992. 37(9): p. 1551-1554.

59. Verma, P., P. Maire, and P. Novák, A Review of the Features and Analyses of the Solid Electrolyte Interphase in Li-Ion Batteries. Electrochimica Acta, 2010.

55: p. 6332-6341.

60. Hayner, C.M., X. Zhao, and H.H. Kung, Materials for Rechargeable Lithium- Ion Batteries. Annu. Rev. Chem. Biomol. Eng., 2012. 3: p. 445-471.

61. Kim, T.H., et al., The Current Move of Lithium Ion Batteries Towards the Next Phase. Adv. Energy Mater., 2012. 2: p. 860-872.

62. Bruce, P.G., Energy Storage Beyond the Horizon: Rechargeable Lithium Batteries. Solid State Ionics, 2008. 179: p. 752-760.

63. Niitani, T., et al., Characteristics of new-type solid polymer electrolyte controlling nano-structure. Journal of Power Sources, 2005. 146: p. 386-390. 64. Tsutsumi, H., et al., Conductivity enhancement of polymer electrolytes by

addition of cascade nitriles and polarization behavior of ithium electrode in the electrolytes. Solid State Ionics, 2002. 147: p. 317-323.

- 65 -

65. Skaarup, S., et al., Towards solid state lithium batteries based on ORMOCER electrolytes. Electrochimica Acta, 1998. 43: p. 1589-1592.

66. Popall, M., et al., New polymer lithium secondary batteries based on ORMOCER(R) electrolytes inorganic-organic polymers. Electrochimica Acta, 2001. 46: p. 1499-1508.

67. Dahmouche, K., et al., New Li+ ion-conducting ormolytes. Solar Energy Materials and Solar Cells, 1998. 54: p. 1-8.

68. Dahmouche, K., et al., Investigation of new ion-conducting ORMOLYTES: Structure and properties. Journal of Sol-Gel Science and Technology, 1997. 8: p. 711-715.

69. Cheng, C.L., C.C. Wan, and Y.Y. Wang, Preparation of porous, chemically cross-linked, PVdF-based gel polymer electrolytes for rechargeable lithium batteries. Journal of Power Sources, 2004. 134: p. 202-210.

70. Pu, W., et al., Preparation of P(AN-MMA) microporous membrane for Li-ion batteries by phase inversion. Journal of Membrane Science, 2006. 280: p. 6-9. 71. Derrien, G., et al., Nanocomposite PEO-based polymer electrolyte using a

highly porous, super acid zirconia filler. Solid State Ionics, 2009. 180: p. 1267- 1271.

72. Benrabah, D., J.Y. Sanchez, and M. Armand, New polyamide ether electrolytes. Electrochimica Acta, 1992. 37(9): p. 1737-1741.

73. Paulsdorf, J., et al., Synthesis and Ionic Conductivity of Polymer Electrolytes Based on a Polyphosphazene with Short Side Groups. Chem. Mater., 2006. 18: p. 1281-1288.

74. Song, J.Y., Y.Y. Wang, and C.C. Wan, Review of gel-type polymer electrolytes for lithium-ion batteries. Journal of Power Sources, 1999. 77: p. 183-197.

75. Stephan, A.M. and K.S. Nahm, Review on composite polymer electrolytes for lithium batteries. Polymer, 2006. 47: p. 5952-5964.

76. Tigelaar, D.M., et al., New APTES Cross-Linked Polymers from Poly(ethylene oxide)s and Cyanuric Chloride for Lithium Batteries. Macromolecules, 2006.

39: p. 120-127.

77. Walcarius, A., Electrochemical applications of silica-based organic-inorganic hybrid materials. Chem. Mater., 2001. 13: p. 1589-1592.

78. Nishio, K., et al., Structural Analysis and Properties of Organic-Inorganic Hybrid Ionic Conductor Prepared by Sol-Gel Process. Journal of Sol-Gel Science and Technology, 2000. 19: p. 187-191.

79. Ogasawara, T., Sol-Gel Electrolytes in Lithium Batteries. Journal of Sol-Gel Science and Technology, 1994. 2: p. 611-613.

80. Sanchez, C., et al., Applications of hybrid organic-inorganic nanocomposites. J. of Mater. Chem., 2005. 15: p. 3559-3592.