全固态锂电池的固态电解质进展与专利分析

doi:10.19799/j.cnki.2095-4239.2020.0205

摘要/Abstract

摘要：

固态锂电池由于具有安全性高、能量密度高等优势，已成为未来锂电池发展的必经之路。其中，固态电解质作为固态电池区别于传统液态电池的核心部件，已逐渐受到各国重视。本文介绍了三类固态电解质：聚合物、氧化物和硫化物固态电解质，分析了目前最新研究进展和突出研究成果。其中，聚合物电解质具有黏弹性好、机械加工性能优、质量轻等特点。氧化物固态电解质研究时间较长，本文简要介绍了钙钛矿型、NASICON型、Garnet型电解质。而硫化物电解质因具有较高的离子电导率，近年来也广受关注。最后对固态电解质的专利申请进行分析，期于让读者了解不同地区固态电解质的研究水平与进展，倡议加大相关研究经费的投入，为相关企业、高校寻求合作提供选择与建议。

关键词: 固态电解质, 全固态锂电池, 专利分析

Abstract:

Solid-state lithium batteries have become the primary focus in the field of lithium batteries due to their high safety, high energy density, long cycle life, and wide operating temperature range. Using solid electrolyte as the core component of a solid battery is the primary difference from a traditional liquid battery. The solid electrolyte largely determines the performance parameters of the solid lithium battery, including the power density, cycle stability, safety performance, high and low temperature performance, and service life. Therefore, further study of solid electrolytes is ongoing in research institutions of various countries, large electronics companies, and automobile manufacturing companies. This article systematically introduces three types of solid electrolytes that are favored by the industry: Polymer, oxide, and sulfide, and analyzes the latest progress and reported results for each. Among these three types, polymer electrolytes demonstrate good viscoelasticity, excellent machining performance, are lightweight, and transmit lithium ions through the process of "complexation and decomplexation". Oxide solid electrolytes can be found in the crystal state or the glass state. NASICON, perovskite, garnet, and LISICON electrolytes are examples of crystal state electrolytes, while the LiPON electrolyte used in thin film batteries is a popular type of glass oxide electrolyte. Compared with oxide electrolytes, sulfide solid electrolytes exhibit higher ionic conductivity because sulfur ions have a large radius and strong polarization, and for this reason have attracted much attention in recent years. To analyze the development of these electrolytes, a search for solid-state electrolyte patent applications for all-solid-state lithium batteries was performed in the Derwent Innovations Index patent database (DII). After 2015, patent applications for solid electrolytes exhibited a stage of rapid growth. The number of patent applications from Japanese and Korean companies was exceptionally high, from companies such as Toyota, Fuji, and Samsung. These companies have mastered the advanced technology of solid-state lithium batteries. Tracking patent applications allows readers to understand the level and progress of solid electrolytes in different regions, and helps enterprises and universities to seek relevant cooperation and increase investment in related research fields. At present, mass production of solid electrolytes still faces many technical difficulties. It is our hope that in the future, research on solid electrolytes can overcome the technical bottlenecks, realize the industrialization of all-solid lithium batteries, and contribute to the clean and safe use of energy around the world.

Key words: solid electrolyte, all-solid lithium battery, patent analysis

中图分类号:

TM 911

李茜, 郁亚娟, 张之琦, 王磊, 黄凯. 全固态锂电池的固态电解质进展与专利分析[J]. 储能科学与技术, 2021, 10(1): 77-86.

Xi LI, Yajuan YU, Zhiqi ZHANG, Lei WANG, Kai HUANG. Advance and patent analysis of solid electrolyte in solid-state lithium batteries[J]. Energy Storage Science and Technology, 2021, 10(1): 77-86.

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参考文献 45

1	刘鲁静, 贾志军, 郭强等. 全固态锂离子电池技术进展及现状[J]. 过程工程学报, 2019, 19(5): 900-909.
2	CHEN R, QU W, GUO X, et al. The pursuit of solid-state electrolytes for lithium batteries: From comprehensive insight to emerging horizons[J]. Mater Horiz, 2016, 3: 487-516.
3	李杨, 丁飞, 桑林, 等. 全固态锂离子电池关键材料研究进展[J]. 储能科学与技术, 2016, 5(5): 615-626.
	LI Yang, DING Fei, SANG Lin, et al. A review of key materials for all-solid-state lithium ion batteries[J]. Energy Storage Science and Technology, 2016, 5(5): 615-626.
4	MAUGER A, JULIEN C, PAOLELLA A, et al. Building better batteries in the solid state: A review[J]. Materials, 2019, 12: doi: 10.3390/ma12233892.
5	JITTI K, BRUCE P. All-solid-state batteries and their remaining challenges[J]. Johnson Matthey Technology Review, 2018, 62(2): 177-180.
6	WAN J, XIE J, KONG X, et al. Ultrathin, flexible, solid polymer composite electrolyte enabled with aligned nano-porous host for lithium batteries[J]. Nature Nanotechnology, 2019, 14(7): 705-711.
7	COMMARIEU B, PAOLELLA A. Solid-to-liquid transition of polycarbonate solid electrolytes in Li-metal batteries[J]. Journal of Power Sources, 2019, 436: doi: 10.1016/j.jpowsour.2019.226852.
8	SHIM J, KIM L, KIM H, et al. All-solid-state lithium metal battery with solid polymer electrolytes based on polysiloxane crosslinked by modified natural gallic acid[J]. Polymer, 2017, 122: 222-231.
9	LIU K, ZHANG Q, THAPALIYA B, et al. In situ polymerized succinonitrile-based solid polymer electrolytes for lithium ion batteries[J]. Solid State Ionics, 2020, 345: doi: 10.1016/j.ssi.2019.115159.
10	DIRICAN M, YAN C, ZHU P, et al. Composite solid electrolytes for all-solid-state lithium batteries[J]. Materials Science and Engineering, 2018, 136: 27-46.
11	SUN C, LIU J, GONG Y, et al. Recent advances in all-solid-state rechargeable lithium batteries[J]. Nano Energy, 2017, 33: 363-386.
12	LEO C, SUBBA R, CHOWDARI B. Studies on plasticized PEO-lithium triflate-ceramic filler composite electrolyte system[J]. Solid State Ionics, 2002, 148(1/2): 159-171.
13	LIU W, LIU N, SUN J, et al. Ionic conductivity enhancement of polymer electrolytes with ceramic nanowire fillers[J]. Nano Letters, 2015, 15(4): 2740-2745.
14	CHEN S, WANG J, ZHANG Z, et al. In-situ preparation of poly(ethylene oxide)/Li₃PS₄ hybrid polymer electrolyte with good nanofiller distribution for rechargeable solid-state lithium batteries[J]. Journal of Power Sources, 2018, 387(31): 72-80.
15	马丹丹. 聚合物电解质的合成在锂离子电池中的应用研究[D]. 宁波: 中国科学院大学(中国科学院宁波材料技术与工程研究所), 2018.
16	YUE H, LI J, WANG Q, et al. Sandwich-like poly(propylene carbonate)-based electrolyte for ambient-temperature solid-state lithium ion batteries[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(1): 268-274.
17	刘明珠. 锂电池用新型聚硅氧烷基固体电解质的制备及其性能研究[D]. 杭州: 浙江大学, 2018.
18	LI J, LIN Y, YAO H, et al. Tuning thin-film electrolyte for lithium battery by grafting cyclic carbonate and combed poly(ethylene oxide) on polysiloxane[J]. ChemSusChem, 2014, 7(7): 1901-1908.
19	LIU M, JIN B, ZHANG Q, et al. High-performance solid polymer electrolytes for lithium ion batteries based on sulfobetaine zwitterion and poly (ethylene oxide) modified polysiloxane[J]. Journal of Alloys & Compounds, 2018, 742: 619-628.
20	LIU J, XU J, LIN Y, et al. All-solid-state lithium ion battery: research and industrial prospects[J]. Acta Chimica Sinica, 2013, 71(6): 869-878.
21	吕晓娟, 孟繁丽, 吴亚楠. 钙钛矿型固体锂离子电解质的研究进展[J]. 中国陶瓷, 2019, 55(4): 1-6.
22	LU J, LI Y, DING Y. Structure, stability, and ionic conductivity of perovskite Li₂x_-ySr_1-x_-yLayTiO₃ solid electrolytes[J]. Ceramics International, 2019, 46: 7741-7747.
23	HU Z, SHENG J, CHEN J, et al. Enhanced Li-ion conductivity in Ge-doped Li_0.33La_0.56TiO₃ perovskite solid electrolytes for all-solid-state Li-ion batteries[J]. New Journal of Chemistry, 2018, 42: 9074-9079.
24	WANG S, DING Y, ZHOU G, et al. Durability of the Li₁₊xTi_2-xAlx(PO₄)₃ solid electrolyte in lithium-sulfur batteries[J]. ACS Energy Letters, 2016, 1(6): 1080-1085.
25	LAI Y, SUN Z, JIANG L, et al. Rapid sintering of ceramic solid electrolytes LiZr₂(PO₄)₃ and Li_1.2Ca_0.1Zr_1.9(PO₄)₃ using a microwave sintering process at low temperatures[J]. Ceramics International, 2019, 45: 11068-11072.
26	TAN G, FENG W, LI L, et al. Magnetron sputtering preparation of nitrogen-incorporated lithium-aluminum-titanium phosphate based thin film electrolytes for all-solid-state lithium ion batteries[J]. Journal of Physical Chemistry C, 2012, 116(5): 3817-3826.
27	GAI J, ZHAO E, MA F, et al. Improving the Li-ion conductivity and air stability of cubic Li₇La₃Zr₂O₁₂ by the co-doping of Nb, Y on the Zr site[J]. Journal of the European Ceramic Society, 2018, 38(4): 1673-1678.
28	GIDEON A, INGO B, JULIAN S. One-pot synthesis of polymeric LiPON[J]. Polymer, 2020, 192: doi: 10.1016/j.polymer.2020.122300.
29	SUZUKI N, INABA T, SHIGA T. Electrochemical properties of LiPON films made from a mixed powder target of Li₃PO₄ and Li₂O[J]. Thin Solid Films, 2012, 520(6): 1821-1825.
30	CHEN S, XIE D, LIU G, et al. Sulfide solid electrolytes for all-solid-state lithium batteries: Structure, conductivity, stability and application[J]. Energy Storage Materials, 2018, 14: 58-74.
31	WU Z, XIE Z, YOSHIDA A, et al. Utmost limits of various solid electrolytes in all-solid-state lithium batteries: A critical review[J]. Renewable and Sustainable Energy Reviews, 2019, 109: 367-385.
32	HU P, ZHANG Y, CHI X, et al. Stabilizing the interface between sodium metal anode and sulfide-based solid-state electrolyte with an electron-blocking interlayer[J]. ACS Applied Materials & Interfaces, 2019, 11(10): 9672-9678.
33	CHEN S, WEN K, FAN J, et al. Progress and future prospects of high-voltage and high-safety electrolytes in advanced lithium batteries: From liquid to solid electrolytes[J]. Journal of Materials Chemistry A, 2018, 6(25): 11631-11663.
34	WU Z, XIE Z, YOSHIDA A, et al. Novel SeS₂ doped Li₂S-P₂S₅ solid electrolyte with high ionic conductivity for all-solid-state lithium sulfur batteries[J]. Chemical Engineering Journal, 2019, 380: 122-132.
35	CENGIZ M, OH H, LEE S. Lithium dendrite growth suppression and ionic conductivity of Li₂S-P₂S₅-P₂O₅ glass solid electrolytes prepared by mechanical milling[J]. Journal of the Electrochemical Society, 166(16): A3997-A4004.
36	LU P, DING F, XU Z, et al. Study on (100-x)(70Li₂S -30P₂S₅)-xLi₂ZrO₃ glass-ceramic electrolyte for all-solid-state lithium-ion batteries[J]. Journal of Power Sources, 2017, 356: 163-171.
37	UJIIE S, HAYASHI A, TATSUMISAGO M. Structure, ionic conductivity and electrochemical stability of Li₂S-P₂S₅-LiI glass and glass-ceramic electrolytes[J]. Solid State Ionics, 2012, 211: 42-45.
38	XU R, XIA X, WANG X, et al. Tailored Li₂S-P₂S₅ glass-ceramic electrolyte by MoS₂ doping, possessing high ionic conductivity for all-solid-state lithium-sulfur batteries[J]. Journal of Materials Chemistry A, 2017, 5(6): 2829-2834.
39	KAMAYA N, HOMMA K, YAMAKAWA Y, et al. A lithium superionic conductor[J]. Nature Materials, 2011, 10(9): 682-686.
40	ZHANG Q, HU J, CHU Y, et al. Electrochemical performance of sulfide solid electrolyte Li₁₀GeP₂S₁₂ synthesized by a new method[J]. Materials Letters, 2019, 248: 153-156.
41	SUN Y, YAN W, AN L, et al. A facile strategy to improve the electrochemical stability of a lithium ion conducting Li₁₀GeP₂S₁₂ solid electrolyte[J]. Solid State Ionics, 2017, 301: 59-63.
42	ZHANG Y, CHEN R, LIU T, et al. High capacity and superior cyclic performances of all-solid-state lithium batteries enabled by a glass-ceramics solo[J]. ACS Applied Materials & Interfaces, 2018, doi: 10.1021/acsami.7b18211.
43	张波, 崔光磊, 刘志宏, 等. 无机固态锂电池专利分析[J]. 储能科学与技术, 2017, 6(2): 307-315.
	ZHANG Bo, CUI Guanglei, LIU Zhihong, et al. Patentmetrics on lithium-ion battery based on inorganic solid electrolyte[J]. Energy Storage Science and Technology, 2017, 6(2): 307-315.
44	芮雯奕, 姜疆, 宋海燕, 等. 固态锂电池全球专利分析[J]. 电池, 2018, 48(6): 417-420.
	RUI Wenyi, JIANG Jiang, SONG Haiyan, et al. Global patent analysis on solid-state lithium battery[J]. Battery Bimonthly, 2018, 48(6): 417-420.
45	王琳, 陈万朋, 庄卫东, 等. 全固态锂电池专利申请现状及发展趋势分析[J]. 电源技术, 2018, 42(3): 455-458.
	WANG Lin, CHEN Wangpeng, ZHUANG Weidong, et al. Current status and development trends of patent application in all solid state lithium battery[J]. Chinese Journal of Power Sources, 2018, 42(3): 455-458.

排名	申请人	专利数量/件	占总数比例/%
1	TOYOTA JIDOSHA KK (丰田株式会社)	293	11.47
2	FUJI FILM CORP(富士胶片株式会社)	134	5.24
3	MURATA MFG CO LTD(村田株式会社)	82	3.21
4	IDEMITSU KOSAN CO LTD (出光兴产株式会社)	61	2.39
5	HITACHI ZOSEN CORP (日立造船株式会社)	47	1.84
6	NGK INSULATORS LTD(NGK绝缘子株式会社)	45	1.76
7	PANASONIC INTELLECTUAL PROPERTY MANAGEME (松下知识产权管理)	45	1.76
8	TOYOTA MOTOR CORP (日本丰田汽车公司)	45	1.76
9	TDK CORP (TDK株式会社)	40	1.57
10	SAMSUNG ELECTRONICS CO LTD (三星电子有限公司)	38	1.49

序号	IPC	技术领域	数量
1	H01M-010/0562	二次电解质，电解质为固体材料	1067
2	H01M-010/052	锂二次蓄电池	763
3	H01M-004/62	活性物质中非活性材料成分的选择，例如胶合剂、填料	579
4	H01M-010/0525	摇椅式电池，即两个电极插入或嵌入有锂的电池；锂离子电池	517
5	H01M-010/0585	只具有板条结构元件，即板条式正极、负极、隔离件的蓄电池	418
6	H01M-004/13	非水电解质蓄电池的电极；其制造方法	348
7	H01B-001/06	主要由其他非金属物质组成的导体或导电物体	311
8	H01M-010/058	非水电解质(H01M-010/39优先)构造或制造	283
9	H01M-004/36	作为活性物质、活性体、活性液体的材料选择	249
10	H01M-010/0565	高分子有机材料，例如凝胶或固体型的锂蓄电池	235

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