锂离子电池玻璃态电解质导电机理的研究进展

doi:10.3724/SP.J.1077.2013.13108

无机材料学报 ›› 2013, Vol. 28 ›› Issue (11): 1172-1180.DOI: 10.3724/SP.J.1077.2013.13108 CSTR: 32189.14.SP.J.1077.2013.13108

锂离子电池玻璃态电解质导电机理的研究进展

郑玥雷¹, 陈人杰^1,2, 吴锋^1,2, 李丽^1,2

(1. 北京理工大学化工与环境学院环境科学与工程北京市重点实验室, 北京100081; 2. 国家高技术绿色材料发展中心, 北京100081)

收稿日期:2013-03-07 修回日期:2013-04-23 出版日期:2013-11-20 网络出版日期:2013-10-18
作者简介:郑玥雷(1985–), 女, 博士研究生. E-mail:zyl_sky_1@sina.com
基金资助:
科技部国际合作项目(2010DFB63370); 国家高技术研究发展计划(2011AA11A256); 国家自然科学基金(21373 028); 教育部新世纪优秀人才支持计划(NCET-12-0050); 北京市科技新星计划 (2010B018)

Progress of Research on the Conductive Mechanism of the Glassy Electrolytes in Lithium Ion Batteries

ZHENG Yue-Lei¹, CHEN Ren-Jie^1,2, WU Feng^1,2, LI Li^1,2

(1. Beijing Key Laboratory of Environmental Science and Engineering, School of Chemical Engineering and the Environment, Beijing Institute of Technology, Beijing 100081, China; 2. National Development Center of High Technology Green Materials, Beijing 100081, China)

Received:2013-03-07 Revised:2013-04-23 Published:2013-11-20 Online:2013-10-18
About author:ZHENG Yue-Lei. E-mail:zyl_sky_1@sina.com
Supported by:
International S & T Cooperation Program of China (2010DFB63370); National 863 Program (2011AA11A256); National Natural Science Foundation of China (21373028); New Contury Educational Talents Plan of Chinese Eduation Ministry (NCET-12-0050); Beijing Novel Program (2010B018)

摘要/Abstract

摘要： 锂离子电池玻璃态电解质同晶体型电解质相比较具有导电性各向同性、锂离子电导率高等诸多优点, 开发在室温下具有较高的离子电导率及良好的化学、电化学稳定性的玻璃态电解质材料已经成为锂离子电池领域的重要研究方向之一。本文介绍了各种玻璃态电解质体系的导电特性及导电机理, 并重点分析与讨论混合网络形成体效应在一些典型玻璃态电解质体系中的微观作用机理。本文还总结了混合网络形成体效应在玻璃态电解质中发生的前提条件, 并指出深入研究玻璃态电解质的导电机理对开发出具有优异电化学性能的无机非晶固态电解质体系具有重要的指导意义。

关键词: 锂离子电池, 玻璃态电解质, 混合网络形成体效应, 相分离, 综述

Abstract: Glassy electrolytes have broad prospects for the application in all solid-state lithium ion batteries since they have isotropic conductivity and higher lithium ionic conductivity compared with ceramic electrolytes. In recent years, numerous groups have attempted to improve the lithium ionic conductivity, chemical and electrochemical stability of glassy electrolytes through nitrogen-incorporation by radio-frequency magnetron sputtering, preparing mixed former glasses and glass-ceramics by special technologies. In present review, conductive characteristics and mechanism in various glassy electrolytes are introduced. The micro-mechanisms of mixed former effect in several typical glassy electrolytes are discussed emphatically. The mixed former effect produces the non-bridge oxygen providing lithium-ion with the vacant place to move into or out, as well as expanding the lithium-ion conduction pathway to enhance ionic mobility in the network. The effect is brought about by the phase separation in micro structure of glassy electrolytes, which can be described as the isolation of continuous Li-rich phase with high ionic conductivity and isolated Li-poor phase with low ionic conductivity in micro structure. Finally, the premise conditions of mixed former effect occurring to a ternary glassy are summarized. Further study on conductive mechanisms of glassy electrolytes has important guiding significance for theory in developing glassy electrolytes with good chemical and electrochemical performances.

Key words: lithium ion batteries, glassy electrolytes, mixed former effect, phase separation, review

中图分类号:

TM911

郑玥雷, 陈人杰,吴锋,李丽. 锂离子电池玻璃态电解质导电机理的研究进展[J]. 无机材料学报, 2013, 28(11): 1172-1180.

ZHENG Yue-Lei, CHEN Ren-Jie, WU Feng, LI Li. Progress of Research on the Conductive Mechanism of the Glassy Electrolytes in Lithium Ion Batteries[J]. Journal of Inorganic Materials, 2013, 28(11): 1172-1180.

参考文献

[1] Tarascon J M, Armand M. Issues and challenges facing rechargeable lithium batteries. Nature, 2001, 414(15): 359-367.

[2] Knauth P. Inorganic solid Li ion conductors: an overview. Solid State Ion., 2009, 180(14/15/16): 911-916.

[3] XU Xiao-Xiong, WEN Zhao-Yin. Glass and glass-ceramics solid electrolytes for Lithium-ion battery. Journal of Inorganic Materials, 2005, 20(1): 21-26.

[4] 郑洪河, 曲群婷, 刘云伟, 等(ZHENG Hong-He, et al). 无机固体电解质用于锂及锂离子电池研究进展.电源技术(Chinese Journal of Power Sources), 2007 , 131(5): 1015-1020.

[5] 吴锋, 杨汉西. 绿色二次电池: 新体系与研究方法. 北京: 科学出版社, 2009: 80-81.

[6] 吴宇平, 万春荣, 姜长印. 锂离子二次电池. 北京: 化学工业出版社, 2002: 214-215.

[7] Rodrigues A C M, Keding R, Russel C. Mixed former effect between TeO2 and SiO2 in the Li2O-TeO2-SiO2 system. J. Non-Cryst. Solids, 2000, 273(1/2/3): 53-58.

[8] Kim C E, Hwang H C, Yoon M Y, et al. Fabrication of a high lithium ion conducting lithium borosilicate glass. J. Non-Cryst. Solids, 2011, 357(15): 2863-2867.

[9] Lee C H, Joo K H, Kim J H, et al. Characterizations of a new lithium ion conducting Li2O-SeO2-B2O3 glass electrolyte. Solid State Ion., 2002, 149(1/2): 59-65.

[10] Lee Y I, Lee J H, Hong S H, et al. Li-ion conductivity in Li2O-B2O3-V2O5 glass system. Solid State Ion., 2004, 175(1-4): 687-690.

[11] Pradel A, Rau C, Bittencourt D, et al. Mixed glass former effect in the system 0.3Li2S-0.7[(1-x) SiS2-xGeS2]: a structural explanation. Chem. Mater., 1998, 10(8): 2162-2166.

[12] Tatsumisago M, Mizuno F, Hayashi A. All-solid-state lithium secondary batteries using sulfide-based glass–ceramic electrolytes. J. Power Sources, 2006, 159(1): 193-199.

[13] Kamaya N, Homma K, Yamakawa Y, et al. A lithium superionic conductor. Nat. Mater., 2011, 10(9): 682-686.

[14] Yamashita M, Yamanaka H. Formation and ionic conductivity of Li2S-GeS2-Ga2S3 glasses and thin films. Solid State Ion., 2003, 158(1/2): 151-156.

[15] Minami K, Hayashi A, Tatsumisago M. Preparation and characterization of lithium ion conducting Li2S-P2S5-GeS2 glasses and glass-ceramics.-J.---------------Non-Cryst.--Solids,--2010,---356(44-49): 2666- 2669.

[16] Liu Z Q, Huang F Q, Yang J H, et al. Preparation of new lithium ion composite electrolyte 3Li4SiS4-0.5La2S3 by mechanical milling. Solid State Sci., 2008, 10(10): 1429-1433.

[17] Tan G Q, Wu F, Chen R J, et al. Magnetron sputtering preparation of nitrogen-incorporated lithium-aluminum-titanium phosphate based thin film electrolytes for all-solid-state lithium ion batteries. J. Phys. Chem. C, 2012, 116(5): 3817-3826.

[18] Wu F, Liu Y D, Chen R J, et al. Preparation and performance of novel Li-Ti-Si-P-O-N thin-film electrolyte for thin-film lithium batteries. J. Power Sources, 2009, 189(1): 467–470.

[19] Cho K I, Lee S H, Cho K H, et al. Li2O-B2O3-P2O5 solid electrolyte for thin film batteries. J. Power Sources, 2006, 163(1): 223-228.

[20] Cho K I, Lee S H, Shin D W, et al. Relationship between glass network structure and conductivity of Li2O-B2O3-P2O5 solid electrolyte. Electrochim. Acta, 2006, 52(4): 1576-1581.

[21] Faizal A F A, Majid S R, Subban R H Y. Conductivity studies of Li2O-TiO2-P2O5 system. Mater. Res. Innov., 2009, 13(3): 229-231.

[22] Okada T, Honma T, Komatsu T. Synthesis and Li+ ion conductivity of Li2O-Nb2O5-P2O5 glasses and glass–ceramics. Mater. Res. Bull., 2010, 45(10): 1443-1448.

[23] Mascaraque N, Durán A, Mu-oz F. Effect of alumina on the structure and properties of Li2O–B2O3–P2O5 glasses. J. Non-Cryst. Solids, 2011, 357(16/17): 3212-3220.

[24] Lee S H, Cho K I, Choi J B, et al. Phase separation and electrical conductivity of lithium borosilicate glasses for potential thin film solid electrolytes. J. Power Sources, 2006, 162(2): 1341-1345.

[25] Morimoto S. Phase separation and crystallization in the system SiO2-Al2O3-P2O5-B2O3-Na2O glasses. J. Non-Cryst. Solids, 2006, 352(8): 756-760.

[26] 吴锋, 刘亚栋, 陈人杰, 等(WU Feng, et al). LiBPON薄膜电解质的制备及电化学性能研究. 电化学(Electrochemistry), 2009, 15(1): 17-21.

[27] Raskar D, Rinke M T, Eckert H. The mixed network former effect in phosphate glasses: NMR and XPS studies of the connectivity distribution in the glass system (NaPO3)1-x(B2O3)x. J. Phys. Chem. C, 2008, 112(32): 12530-12539.

[28] Jin Y, Chen X, Huang X. Raman studies of lithium borophosphate glasses. J. Non-Cryst. Solids, 1989, 112(1/2/3): 147-150.

[29] Doweida H, El-Shahawi M S, Reicha F M, et al. Phase separation and physical properties of sodium borosilicate glasses with intermediate silica content. J. Phys. D: Appl. Phys., 1990, 23(11): 1441-1446.

[30] Maia L F, Rodrigues A C M. Electrical conductivity and relaxation frequency of lithium borosilicate glasses. Solid State Ion., 2004, 168(1/2): 87-92.

[31] El-Egili K. Infrared studies of Na2O-B2O3-SiO2 and Al2O3-Na2O-B2O3-SiO2 glasses. Phys. B, 2003, 325: 340-348.

[32] Kluva-nek P, Klement R, Karacon M. Investigation of the conductivity of the lithium borosilicate glass system. J. Non-Cryst. Solids, 2007, 353(18-21): 2004-2007.

[33] Lee C H, Sohn H J, Kim M G. XAS study on lithium ion conducting Li2O-SeO2-B2O3 glass electrolyte. Solid State Ion., 2005, 176(13/14): 1237-1241.

[34] Sharma M V N V D, Sarma A V, Rao R B. Electrical conductivity, relaxation, and scaling analysis studies of lithium alumino phosphate glasses and glass ceramics. J. Mater. Sci., 2009, 44(22): 5557-5562.

[35] Reddy C V K, Rao R B, Mouli K C, et al. Electrical conductivity, electrical modulus, and scaling studies of Li2O-Ga2O3-P2O5 glass electrolyte doped with selenium. Ions. Ion., 2012, 18(1/2): 65-73.

[36] Gedam R S, Deshpande V K. An anomalous enhancement in the electrical conductivity of Li2O: B2O3: Al2O3 glasses. Solid State Ion., 2006, 177(26-32): 2589-2592.

[37] Gedam R S, Deshpande V K. Enhancement in electrical conductivity of Li2O:B2O3:V2O5 glasses. Bull. Mater. Sci., 2009, 32(1): 83-87.

[38] Christensen R, Byer J, Olson G, et al. The glass transition temperature of mixed glass former 0.35Na2O+0.65[xB2O3+ (1-x)P2O5] glasses. J. Non-Cryst. Solids, 2012, 358(4): 826-831.

[39] Christensen R, Byer J, Olson G, et al. The densities of mixed glass former 0.35Na2O+0.65[xB2O3+ (1-x)P2O5] glasses related to the atomic fractions and volumes of short range structures. J. Non-Cryst. Solids, 2012, 358(4): 583-589.

[40] Seino Y, Takada K, Kim B C, et al. Synthesis of phosphorous sulfide solid electrolyte and all-solid-state lithium batteries with graphite electrode. Solid State Ion., 2005, 176(31-34): 2389-2393.

[41] Yamamoto H, Machida N, Shigematsu T. A mixed-former effect on lithium-ion conductivities of the Li2S-GeS2-P2S5 amorphous materials prepared by a high-energy ball-milling process. Solid State Ion., 2004, 175(1-4): 707-711.

[42] Kanno R, Murayama M. Lithium ionic conductor thio-LISICON the Li2S-GeS2-P2S5 system. J. Electrochem. Soc., 2001, 148(7): A742-A746.

[43] Matsumura T, Nakano K, Kanno R, et al. Nickel sulfides as a cathode for all-solid-state ceramic lithium batteries. J. Power Sources, 2007, 174(2): 632-636.

[44] Kobayashi T, Yamada A, Kanno R. Interfacial reactions at electrode/ electrolyte boundary in all solid-state lithium battery using inorganic solid electrolyte, thio-LISICON. Electrochim. Acta, 2008, 53(15): 5045-5050.

[45] Trevey J E, Jung Y S, Lee S H. High lithium ion conducting Li2S-GeS2-P2S5 glass-ceramic solid electrolyte with sulfur additive for all solid-state lithium secondary batteries. Electrochim. Acta, 2011, 56(11): 4243-4247.

[46] Trevey J E, Jung Y S, Lee S H. Preparation of Li2S-GeS2-P2S5 electrolytes by a single step ball milling for all-solid-state lLithium secondary batteries. J. Power Sources, 2010, 195(15): 4984-4989.

[47] El-All S A, Ezz-Eldin F M. Electrical conductivity of gamma-irradiated V2O5 doped lithium disilicate glasses doped and their glass-ceramics derivatives. Nucl. Instrum. Meth. Phys. Res. B, 2010, 268(1): 49-56.

[48] Mekki A, Khattak G D, Holland D, et al. Structure and magnetic properties of vanadium-sodium silicate glasses. J. Non-Cryst. Solids, 2003, 318(1/2): 193-201.

[49] Garbarczyk J E, Wasiucionek M, Józwiak P, et al. Studies of Li2O-V2O5-P2O5 glasses by DSC, EPR and impedance spectroscopy. Solid State Ion., 2002, 154-155: 367-373.

[50] Garbarczyk J E, Jozwiak P, Wasiucionek M, et al. Enhancement of electrical conductivity in lithium vanadate glasses by nanocrystallization. Solid State Ion., 2004, 175(1-4): 691-694.

编辑推荐 0

Metrics

阅读次数

全文

2157

HTML			PDF

最新录用	在线预览	正式出版	最新录用	在线预览	正式出版
0	0	1	0	0	2156

来源	本网站	其他网站

次数	988	1169
比例	46%	54%

摘要

1358

最新录用	在线预览	正式出版

0	0	1358

来源	本网站	其他网站

次数	197	1161
比例	15%	85%

锂离子电池玻璃态电解质导电机理的研究进展

Progress of Research on the Conductive Mechanism of the Glassy Electrolytes in Lithium Ion Batteries

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐 0

Metrics

本文评价

[1]	魏相霞, 张晓飞, 徐凯龙, 陈张伟. 增材制造柔性压电材料的现状与展望[J]. 无机材料学报, 2024, 39(9): 965-978.
[2]	杨鑫, 韩春秋, 曹玥晗, 贺桢, 周莹. 金属氧化物电催化硝酸盐还原合成氨研究进展[J]. 无机材料学报, 2024, 39(9): 979-991.
[3]	刘鹏东, 王桢, 刘永锋, 温广武. 硅泥在锂离子电池中的应用研究进展[J]. 无机材料学报, 2024, 39(9): 992-1004.
[4]	黄洁, 汪刘应, 王滨, 刘顾, 王伟超, 葛超群. 基于微纳结构设计的电磁性能调控研究进展[J]. 无机材料学报, 2024, 39(8): 853-870.
[5]	陈乾, 苏海军, 姜浩, 申仲琳, 余明辉, 张卓. 超高温氧化物陶瓷激光增材制造及组织性能调控研究进展[J]. 无机材料学报, 2024, 39(7): 741-753.
[6]	王伟明, 王为得, 粟毅, 马青松, 姚冬旭, 曾宇平. 以非氧化物为烧结助剂制备高导热氮化硅陶瓷的研究进展[J]. 无机材料学报, 2024, 39(6): 634-646.
[7]	蔡飞燕, 倪德伟, 董绍明. 高熵碳化物超高温陶瓷的研究进展[J]. 无机材料学报, 2024, 39(6): 591-608.
[8]	吴晓晨, 郑瑞晓, 李露, 马浩林, 赵培航, 马朝利. SiC_f/SiC陶瓷基复合材料高温环境损伤原位监测研究进展[J]. 无机材料学报, 2024, 39(6): 609-622.
[9]	赵日达, 汤素芳. 多孔碳陶瓷化改进反应熔渗法制备陶瓷基复合材料研究进展[J]. 无机材料学报, 2024, 39(6): 623-633.
[10]	方光武, 谢浩元, 张华军, 高希光, 宋迎东. CMC-EBC损伤耦合机理及一体化设计研究进展[J]. 无机材料学报, 2024, 39(6): 647-661.
[11]	张幸红, 王义铭, 程源, 董顺, 胡平. 超高温陶瓷复合材料研究进展[J]. 无机材料学报, 2024, 39(6): 571-590.
[12]	张慧, 许志鹏, 朱从潭, 郭学益, 杨英. 大面积有机-无机杂化钙钛矿薄膜及其光伏应用研究进展[J]. 无机材料学报, 2024, 39(5): 457-466.
[13]	李宗晓, 胡令祥, 王敬蕊, 诸葛飞. 氧化物神经元器件及其神经网络应用[J]. 无机材料学报, 2024, 39(4): 345-358.
[14]	程节, 周月, 罗薪涛, 高美婷, 骆思妃, 蔡丹敏, 吴雪垠, 朱立才, 袁中直. 蛋黄壳结构FeF₃·0.33H₂O@N掺杂碳纳米笼正极材料的构筑及其电化学性能[J]. 无机材料学报, 2024, 39(3): 299-305.
[15]	鲍可, 李西军. 化学气相沉积法制备智能窗用热致变色VO₂薄膜的研究进展[J]. 无机材料学报, 2024, 39(3): 233-258.