高性能钠离子电池黏合剂的研究进展

doi:10.16085/j.issn.1000-6613.2019-0079

摘要/Abstract

摘要：

为了实现钠离子电池优异的电化学性能，除了从电极材料的搭配方面入手，作为维持电极结构稳定性的关键材料，黏合剂的选择也至关重要。本文对黏合剂的主要作用与性能要求进行了讨论，系统综述了近年来高性能钠离子电池黏合剂的研究进展，分别阐述了聚偏氟乙烯、羧甲基纤维素、海藻酸钠、聚丙烯酸以及交联聚合物等5类黏合剂的特性：聚偏氟乙烯的化学稳定性良好，黏合效果较好，但存在溶胀率较大的问题；羧甲基纤维素具有良好的分散性，机械强度较大，由于脆性较大而需与丁苯橡胶搭配使用；海藻酸钠环保且廉价，保形性好，但稳定性较差；聚丙烯酸拥有较高的弹性模量和抗拉强度，但是力学性能较差；交联聚合物的机械强度大，弹性较好，可能存在网络缺陷。结合已有的研究报道，探讨了这些黏合剂在钠离子电池系统中的应用，展望了今后黏合剂在拓宽来源领域、匹配适合的电极材料以及消除水性黏合剂对电池性能的负面影响等方面的发展方向。

关键词: 黏合剂, 聚偏氟乙烯, 羧甲基纤维素, 海藻酸钠, 聚丙烯酸, 交联聚合物

Abstract:

In order to achieve the excellent electrochemical performance of sodium-ion battery, apart from the improvement on the combination of electrode materials, as a key material to maintain the stability of the electrode structure, the choice of binder is also crucial. In this paper, the main effects and performance requirements of binder are discussed. The research progress of binder for the high performance sodium-ion battery in recent years is systematically reviewed. The properties of five kinds of binder, such as polyvinylidene fluoride, carboxymethyl cellulose, sodium alginate, polyacrylic acid, crosslinked polymer, are described respectively: polyvinylidene fluoride has good chemical stability and adhesion, but has a problem of large swelling ratio; carboxymethyl cellulose has good dispersibility and mechanical strength, because of the large brittleness, it needs to be used together with polymerized styrene butadiene rubber; sodium alginate is environmentally friendly and cheap, with good shape retention, but poor stability; polyacrylic acid has high elasticity modulus and tensile strength, but poor mechanical properties; the mechanical strength and elasticity of crosslinked polymer are high, and there may be network defects. Combined with the existing research reports, the application of these binders in sodium-ion battery system is discussed. It is expected that the binder will broaden the source field, match the suitable electrode materials and eliminate the negative impact of the water-based binder on battery performance.

Key words: binder, polyvinylidene fluoride, carboxymethyl cellulose, sodium alginate, polyacrylic acid, crosslinked polymer

中图分类号:

TM911

朱子翼,黎永泰,董鹏,曾晓苑,许斌,郝涛,李雪,张英杰. 高性能钠离子电池黏合剂的研究进展[J]. 化工进展, 2019, 38(10): 4693-4704.

Ziyi ZHU,Yongtai LI,Peng DONG,Xiaoyuan ZENG,Bin XU,Tao HAO,Xue LI,Yingjie ZHANG. Research progress of binder for high performance sodium-ion battery[J]. Chemical Industry and Engineering Progress, 2019, 38(10): 4693-4704.

图/表 2

参考文献 51

52	KWON T W , YOU K J , LEE I, et al . Systematic molecular-level design of binders incorporating meldrum’s acid for silicon anodes in lithium rechargeable batteries[J]. Advanced Materials, 2014, 26(47): 7979-7985.
53	WEI H , XIA Z , XIA D . One step synthesis of uniform SnO₂ electrode by UV curing technology toward enhanced lithium-ion storage[J]. ACS Applied Materials & Interfaces, 2017, 9(8): 7169-7176.
54	SONG J , YU Z , GORDIN M L , et al . Advanced sodium ion battery anode constructed via chemical bonding between phosphorus, carbon nanotube, and cross-linked polymer binder[J]. ACS Nano, 2015, 9(12): 11933-11941.
55	GAO H , ZHOU W , JANG J , et al . Cross-linked chitosan as a polymer network binder for an antimony anode in sodium-ion batteries[J]. Advanced Energy Materials, 2016, 6(6): 1502130.
1	NISHI Y . Lithium ion secondary batteries; past 10 years and the future[J]. Journal of Power Sources, 2001, 100(1/2): 101-106.
2	张英杰, 朱子翼, 董鹏, 等 . LiFePO₄电化学反应机理、制备及改性研究新进展[J]. 物理化学学报, 2017, 33(6): 1085-1107.
	ZHANG Y J , ZHU Z Y , DONG P , et al . New research progress of the electrochemical reaction mechanism,preparation and modification for LiFePO₄ [J]. Acta Physico-Chimica Sinica, 2017, 33(6): 1085-1107.
3	HWANG J Y , MYUNG S T , YOON C S , et al . Novel cathode materials for Na-ion batteries composed of spoke-like nanorods of Na[Ni_0.61Co_0.12Mn_0.27]O₂ assembled in spherical secondary particles[J]. Advanced Functional Materials, 2016, 26(44): 8083-8093.
4	ZHU Z , LIANG F , ZHOU Z , et al . Expanded biomass-derived hard carbon with ultra-stable performance in sodium-ion batteries[J]. Journal of Materials Chemistry A, 2018, 6: 1513-1522.
5	张英杰, 朱子翼, 董鹏, 等 . 钠离子电池碳基负极材料的研究进展[J]. 化工进展, 2017, 36(11): 4106-4115.
	ZHANG Y J , ZHU Z Y , DONG P , et al . Research progress of carbon-based anode materials for sodium ion batteries[J]. Chemical Industry and Engineering Progress, 2017, 36(11): 4106-4115.
6	PONROUCH A , MARCHANTE E , COURTY M , et al . In search of an optimized electrolyte for Na-ion batteries[J]. Energy & Environmental Science, 2012, 5(9): 8572-8583.
7	VIGNAROOBAN K , KUSHAGRA R , ELANGO A , et al . Current trends and future challenges of electrolytes for sodium-ion batteries[J]. International Journal of Hydrogen Energy, 2016, 41(4): 2829-2846.
8	HWANG J Y , MYUNG S T , SUN Y K . Sodium-ion batteries: present and future[J]. Chemical Society Reviews, 2017, 46(12): 3529-3614.
9	BOMMIER C , JI X . Electrolytes, SEI formation, and binders: a review of nonelectrode factors for sodium-ion battery anodes[J]. Small, 2018, 14(16): 1703576.
10	SHI Y , ZHOU X , YU G . Material and structural design of novel binder systems for high-energy, high-power lithium-ion batteries[J]. Accounts of Chemical Research, 2017, 50(11): 2642-2652.
11	曾涛 . 聚丙烯酸粘结剂在锂离子电池正极中的应用研究[D]. 长沙：中南大学, 2013.
	ZENG T . Study on polyacrylic acid as binder of cathode in lithium ion battery[D]. Changsha: Central South University, 2013.
12	LIU G , XUN S , VUKMIROVIC N , et al . Polymers with tailored electronic structure for high capacity lithium battery electrodes[J]. Advanced Materials, 2011, 23(40): 4679-4683．
13	王晕 . PVDF粘结剂在锂离子电池中的应用研究[D]. 上海：复旦大学, 2013.
	WANG Y . The application of PVDF binder in lithium-ion battery[D]. Shanghai: Fudan University, 2013.
14	ZHANG L , LIU Z , CUI G , et al . Biomass-derived materials for electrochemical energy storages[J]. Progress in Polymer Science, 2015, 43(1): 136-164.
15	柴丽莉, 张力, 曲群婷, 等 . 锂离子电池电极粘结剂的研究进展[J]. 化学通报, 2013, 76(4): 299-306.
	CHAI L L , ZHANG L , QU Q T , et al . Progress of electrode binder in lithium ion batteries[J]. Chemistry Bulletin, 2013, 76(4): 299-306.
16	武兆辉, 杨娟玉, 闫坤, 等 . 锂离子电池硅基负极用聚合物粘结剂的研究进展[J]. 稀有金属, 2016, 40(8): 838-849.
	WU Z H , YANG J Y , YAN K , et al . Advances in polymeric binder for silicon based anode of lithium-ion batteries[J]. Chinese Journal of Rare Metals, 2016, 40(8): 838-849.
17	HONG K , LONG Q , ZENG R , et al . Biomass derived hard carbon used as a high performance anode material for sodium ion batteries[J]. Journal of Materials Chemistry A, 2014, 2(32): 12733-12738.
18	LIU H , JIA M , CAO B , et al . Nitrogen-doped carbon/graphene hybrid anode material for sodium-ion batteries with excellent rate capability[J]. Journal of Power Sources, 2016, 319: 195-201.
56	WEI Y , WANG Z , YE H , et al . A stable cross-linked binder network for SnO₂ anode with enhanced sodium-ion storage performance[J]. Chemistry Select, 2017, 2(35): 11365-11369.
19	熊鹏 . 高粘度羧甲基纤维素钠合成工艺及其在硅负极中应用研究[D]. 武汉：湖北工业大学, 2017.
	XIONG P . Preparation of high viscosity sodium carboxymethyl cellulose and its application on silicon cathode[D]. Wuhan: Hubei University of Technology, 2017.
20	刘欣, 赵海雷, 解晶莹, 等 . 锂离子电池高比容量负极用粘结剂[J]. 化学进展, 2013, 25(8): 1401-1410.
	LIU X , ZHAO H L , XIE J Y , et al . Polymer binders for high capacity electrode of lithium-ion battery[J]. Progress in Chemistry, 2013, 25(8): 1401-1410.
21	HOCHGATTERER N S , SCHWEIGER M R , KOLLER S , et al . Silicon/graphite composite electrodes for high-capacity anodes: influence of binder chemistry on cycling stability[J]. Electrochemical and Solid-State Letters, 2008, 11: A76-A80.
22	MAZOUZI D , LESTRIEZ B , ROUE L , et al . Silicon composite electrode with high capacity and long cycle life[J]. Electrochemical and Solid-State Letters, 2009 12(11): A215-218.
23	BRIDEL J S , AZAIS T , MORCRETTE M , et al . Key parameters governing the reversibility of Si/carbon/CMC electrodes for Li-ion batteries[J]. Chemistry of Materials, 2010, 22(3): 1229-1241.
24	MUNAO D , ERVEN J W M V , VALVO M , et al . Role of the binder on the failure mechanism of Si nano-composite electrodes for Li-ion batteries[J]. Journal of Power Sources, 2011, 196(16): 6695-6702.
25	PANG Y , ZHANG S , LIU L , et al . Few-layer MoS₂ anchored at nitrogen-doped carbon ribbons for sodium-ion battery anode with high rate performance[J]. Journal of Materials Chemistry A, 2017, 5(34): 17963-17972.
26	QIAN J , CHEN Y , WU L , et al . High capacity Na-storage and superior cyclability of nanocomposite Sb/C anode for Na-ion batteries[J]. Chemical Communications, 2012, 48(56): 7070-7072.
27	ZHAO J , YANG X , YAO Y , et al . Moving to aqueous binder: a valid approach to achieving high-rate capability and long-term durability for sodium-ion battery[J]. Advanced Science, 2018, 5(4): 1700768.
28	DAHBI M , NAKANO T , YABUUCHI N , et al . Sodium carboxymethyl cellulose as a potential binder for hard-carbon negative electrodes in sodium-ion batteries[J]. Electrochemistry Communications, 2014, 44(7): 66-69.
29	ZHANG W , DAHBI M , KOMABA S . Polymer binder: a key component in negative electrodes for high-energy Na-ion batteries[J]. Current Opinion in Chemical Engineering, 2016, 13: 36-44.
30	FAN M , YU H , CHEN Y . High-capacity sodium ion battery anodes based on CuO nanosheets and carboxymethyl cellulose binder[J]. Materials Technology, 2017, 32 (10): 598-605.
31	KOVALENKO I , ZDYRKO B , MAGASINSKI A , et al . A major constituent of brown algae for use in high-capacity Li-ion batteries[J]. Science, 2011, 334(6052): 75-79.
32	岳丽萍, 韩鹏献, 姚建华, 等 . 锂离子电池硅基负极粘结剂研究进展[J]. 电池工业, 2017, 21(1): 31-44.
	YUE L P , HAN P X , YAO J H , et al . Advances of binder for silicone-based anode in lithium ion batteries[J]. Chinese Battery Industry, 2017, 21(1): 31-44.
33	LI Y , HU Y , TITIRICI M , et al . Hard carbon microtubes made from renewable cotton as high-performance anode material for sodium-ion batteries[J]. Advanced Energy Materials, 2016, 6(18): 1600659.
34	FENG J , WANG L , LI D , et al . Enhanced electrochemical stability of carbon-coated antimony nanoparticles with sodium alginate binder for sodium-ion batteries[J]. Progress in Natural Science Materials International, 2018, 28(2): 205-211.
35	MITRA S , VELURI P S , CHAKRABORTHY A , et al . Electrochemical properties of spinel cobalt ferrite nanoparticles with sodium alginate as interactive binder[J]. ChemElectroChem, 2014, 1(6): 1068-1074.
36	LING L , BAI Y , WANG Z , et al . Remarkable effect of sodium alginate aqueous binder on anatase TiO₂ as high-performance anode in sodium ion batteries[J]. ACS Applied Materials & Interfaces, 2018, 10(6): 5560-5568.
37	KOMABA S , SHIMOMURA K , YABUUCHI N , et al . Study on polymer binders for high-capacity SiO negative electrode of Li-ion batteries[J]. Journal of Physical Chemistry C, 2011, 115(27): 13487-13495.
38	WU H , CHAN G , CHOI J W , et al . Stable cycling of double-walled silicon nanotube battery anodes through solid-electrolyte interphase control[J]. Nature Nanotechnology, 2012, 7(5): 310-315.
39	ZHAO F , XU P , GE H , et al . Na-Doped Li₄Ti₅O₁₂ as an anode material for sodium-ion battery with superior rate and cycling performance[J]. Journal of the Electrochemical Society, 2016, 163(5): A690-695.
40	FAN X , MAO J , ZHU Y , et al . Superior stable self-healing SnP₃ anode for sodium-ion batteries[J]. Advanced Energy Materials, 2015, 5(18): 2314-2316.
41	NGUYEN C C , YOON T , SEO D M, et al . Systematic investigation of binders for silicon anodes: interactions of binder with silicon particles and electrolytes and effects of binders on solid electrolyte interphase formation[J]. ACS Applied Materials & Interfaces, 2016, 8(19): 12211-12220.
42	LUO C , FAN X , MA Z , et al . Self-healing chemistry between organic material and binder for stable sodium-ion batteries[J]. Chem, 2017, 3(6): 1050-1062.
43	MAGASINSKI A , ZDYRKO B , KOVALENKO I , et al . Toward efficient binders for Li-ion battery Si-based anodes: polyacrylic acid[J]. ACS Applied Materials & Interfaces, 2010, 2(11): 3004-3010.
44	MAZOUZI D , KARKAR Z , HEMANDEZ C R , et al . Critical roles of binders and formulation at multiscales of silicon-based composite electrodes[J]. Journal of Power Sources, 2015, 280: 533-549.
45	CAI Z P , LIANG Y , LI W S , et al . Preparation and performances of LiFePO₄ cathode in aqueous solvent with polyacrylic acid as a binder[J]. Journal of Power Sources, 2009, 189(1): 547-551．
46	MING J , MING H , KWAK W J , et al . The binder effect on an oxide-based anode in lithium and sodium-ion battery applications: the fastest way to ultrahigh performance[J]. Chemical Communications, 2014, 50(87): 13307-13310.
47	YUI Y, HAYASHI M , HAYASHI K , et al . Electrochemical properties of Sn-Co electrode with various kinds of binder materials for sodium ion batteries[J]. Solid State Ionics, 2016, 288: 219-223.
48	LI W J , CHOU S L , WANG J Z , et al . A new, cheap, and productive FeP anode material for sodium-ion batteries[J]. Chemical Communications, 2015, 46(19): 3682-3685.
49	KIM Y , KIM Y , CHOI A , et al . Tin phosphide as a promising anode material for Na-ion batteries[J]. Advanced Materials, 2014,26（24）: 4139-4144.
50	LIM S, LEE K, SHIN I , et al . Physically cross-linked polymer binder based on poly(acrylic acid) and ion-conducting poly(ethylene glycol-co-benzimidazole) for silicon anodes[J]. Journal of Power Sources, 2017, 360: 585-592.
51	KOO B, KIM H , CHO Y, et al . A highly cross-linked polymeric binder for high-performance silicon negative electrodes in lithium ion batteries[J]. Angewandte Chemie: International Edition, 2012, 124(35): 8892-8897.

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