高能量密度的锂离子混合型电容器

doi:10.13208/j.electrochem.170346

摘要/Abstract

摘要：

锂离子混合型电容器兼有锂离子电池和超级电容器的优点，在电化学储能领域具有广泛的应用前景. 但其产业化仍存在一系列的基础及工艺方面的问题，具体包括器件结构设计、电极材料筛选、预嵌锂工艺和电解液与电极的界面等. 本文结合作者课题组的研究工作介绍了近年来高能量密度的锂离子混合型电容器的研究进展，内容涉及锂离子电容器正/负极材料的筛选、预嵌锂工艺的优化、内并联结构的锂离子电池型超级电容器复合正极组成材料的调控、隔膜的选择、电解液的组成、以及器件的高/低温性能，分析了锂离子电容器的容量衰减机制，探讨了锂离子电池型超级电容器的储能机制，提出了未来对高能量密度的锂离子混合型电容器研究的展望.

关键词: 锂离子电容器, 锂离子电池型超级电容器, 预嵌锂工艺, 储能机制, 容量衰减行为, 高/低温性能

Abstract:

Lithium ion hybrid capacitors are electrochemical energy storage devices combining the advantages of both Li-ion battery and electrochemical capacitor. They can be extensively used in many fields. However, the commercialization of lithium ion hybrid capacitor has been encountered several problems, e.g., the device structure design, the screening of materials, the pre-lithiation process, and the interface between electrolyte and electrode, etc. This review summarizes the recent research advances in lithium ion hybrid capacitor with high energy density, including the selection of the active materials in cathode/anode and the separator, the pre-lithiation method using the three-electrode structure, the high- and low-temperature performances, the capacity fading behaviors, the charge storage mechanisms and the device fabrication of lithium ion hybrid capacitor (including lithium ion capacitor and lithium battery-type supercapacitor). Finally, the perspectives and future developments of lithium ion hybrid capacitor are highlighted.

Key words: Lithium Ion Capacitor, Lithium Ion Battery-type Supercapacitor, Pre-lithiation Process, Energy Storage Mechanism, Capacity Fading Behavior, High- and Low-Temperature Performances.

中图分类号:

TM911

孙现众, 张熊, 王凯, 马衍伟. 高能量密度的锂离子混合型电容器[J]. 电化学（中英文）, 2017, 23(5): 586-603.

SUN Xian-zhong, ZHANG Xiong, WANG Kai, MA Yan-wei. Lithium Ion Hybrid Capacitor with High Energy Density[J]. Journal of Electrochemistry, 2017, 23(5): 586-603.

参考文献

[1] Simon P, Gogotsi Y, Materials for electrochemical capacitors. [J]. Nature Materials 7 (2008) 845-854.

[2] Zhang X, Zhang H, Li C, et al., Recent advances in porous graphene materials for supercapacitor applications. [J]. RSC Advances 4 (2014) 45862-45884.

[3] Hu C-C, Important parameters of electrode materials in constructing supercapacitors of the asymmetric type, in: International Conference on Advanced Capacitors, Osaka, Japan, 2013.

[4] Cericola D, Kötz R, Hybridization of rechargeable batteries and electrochemical capacitors: Principles and limits. [J]. Electrochimica Acta 72 (2012) 1-17.

[5] Matsui K, Takahata R, Hato Y, et al. Lithium Ion Capacitor. Japan, CN1954397A. [P] 2007.04.25

[6] Nansaka K, Taguchi M. Lithium Ion Capacitor. Japan, CN103201803A. [P] 2013.07.10

[7] ZHENG J-P. High energy density electrochemical capacitors. USA, CN 102971889A. [P] 2013.03.13

[8] Cao W J, Zheng J P, Li-ion capacitors with carbon cathode and hard carbon/stabilized lithium metal powder anode electrodes. [J]. Journal of Power Sources 213 (2012) 180-185.

[9] Asanuma H, Inoue H, Maekawa Y, et al. Nonaqueous secondary battery having multiple-layered negative electrode. Japan, CN1177417A. [P] 1998.03.25

[10] You C (游从辉), Xu Y (徐延杰), Cao F (曹福彪), et al. Lithium Ion Battery and the Li-rich Anode. China (中国专利), 103490041A. [P] 2014.01.01

[11] Utsunomiya T. Method of manufacturing lithium ion storage device. 日本, CN 102738515A. [P] 2012.10.17

[12] Ando N, Kojima K. Electric Storage Device. Japan, CN101350432A. [P] 2009.01.21

[13] Wu F (吴锋), Su Y (苏岳锋), Chen S (陈实), et al. A method to pre-lithiate for lithium ion supercapacitor. China (中国专利), CN101252043A. [P] 2008.08.27

[14] Park M S, Lim Y G, Kim J H, et al., A novel lithium-doping approach for an advanced lithium ion capacitor. [J]. Advanced Energy Materials 1 (2011) 1002-1006.

[15] Zhang S S, Eliminating pre-lithiation step for making high energy density hybrid Li-ion capacitor. [J]. Journal of Power Sources 343 (2017) 322-328.

[16] Han X, Han P, Yao J, et al., Nitrogen-doped carbonized polyimide microsphere as a novel anode material for high performance lithium ion capacitors. [J]. Electrochimica Acta 196 (2016) 603-610.

[17] Zhang J, Wu H, Wang J, et al., Pre-lithiation design and lithium ion intercalation plateaus utilization of mesocarbon microbeads anode for lithium-ion capacitors. [J]. Electrochimica Acta 182 (2015) 156–164.

[18] Shan X-Y, Wang Y, Wang D-W, et al., A smart self-regenerative lithium ion supercapacitor with a real-time safety monitor. [J]. Energy Storage Materials 1 (2015) 146-151.

[19] Sun X, Zhang X, Zhang H, et al., High performance lithium-ion hybrid capacitors with pre-lithiated hard carbon anodes and bifunctional cathode electrodes. [J]. Journal of Power Sources 270 (2014) 318-325.

[20] Yuan M, Liu W, Zhu Y, et al., Electrochemical performance of pre-lithiated graphite as negative electrode in lithium-ion capacitors. [J]. Russian Journal of Electrochemistry 50 (2014) 1050-1057.

[21] Sun X (孙现众), Ma Y (马衍伟), Zhang X (张熊), et al. The pre-lithiation method for Li-ion capacitor. China (中国专利), CN105097293A. [P] 2015.11.25

[22] Sun X (孙现众), Ma Y (马衍伟), Zhang X (张熊), et al. The method to prepare Li-ion hybrid capacitor and the Li-ion hybrid capacitor China (中国专利), CN104008893A. [P] 2014.08.27

[23] Ping L N, Zheng J M, Shi Z Q, et al., Electrochemical performance of lithium ion capacitors using Li⁺-intercalated mesocarbon microbeads as the negative electrode. [J]. Acta Physico-Chimica Sinica 28 (2012) 1733-1738.

[24] Zhang J, Shi Z, Wang C, Effect of pre-lithiation degrees of mesocarbon microbeads anode on the electrochemical performance of lithium-ion capacitors. [J]. Electrochimica Acta 125 (2014) 22-28.

[25] Ping L N, Zheng J M, Shi Z Q, et al., Electrochemical performance of MCMB/(AC+LiFePO₄) lithium-ion capacitors. [J]. Chinese Science Bulletin 58 (2013) 689-695.

[26] Zhang S, Zhang X, Sun X, et al., Effect of the pre-lithiation capacity of mesocarbon microbeads anode on the performances of a flexible package lithium ion capacitors. [J]. Energy Storage Science and Technology 5 (2016) 834-840.

[27] Amatucci G G, Badway F, Du Pasquier A, et al., An asymmetric hybrid nonaqueous energy storage cell. [J]. Journal of the Electrochemical Society 148 (2001) A930-A939.

[28] Yang B (杨斌), Fu G (傅冠生), Chen Z (陈照荣), et al., Preparaton and performance of Li₄Ti₅O₁₂/AC hybrid capacitor. [J]. Battery monthly (电池) 45 (2015) 149-152.

[29] Dsoke S, Fuchs B, Gucciardi E, et al., The importance of the electrode mass ratio in a Li-ion capacitor based on activated carbon and Li₄Ti₅O₁₂. [J]. Journal of Power Sources 282 (2015) 385-393.

[30] Dong S, Wang X, Shen L, et al., Trivalent Ti self-doped Li₄Ti₅O₁₂: A high performance anode material for lithium-ion capacitors. [J]. Journal of Electroanalytical Chemistry 757 (2015) 1-7.

[31] Leng K, Zhang F, Zhang L, et al., Graphene-based Li-ion hybrid supercapacitors with ultrahigh performance. [J]. Nano Research 6 (2013) 581-592.

[32] Xu N, Sun X, Zhang X, et al., A Two-step Method for Preparing Li₄Ti₅O₁₂-graphene as an Anode Material for Lithium-ion Hybrid Capacitors. [J]. RSC Advances 5 (2015) 94361-94368.

[33] Xu N, Sun X, Zhao F, et al., The Role of Pre-Lithiation in Activated Carbon/Li₄Ti₅O₁₂ Asymmetric Capacitors. [J]. Electrochimica Acta 236 (2017) 443-450.

[34] Sivakkumar S R, Pandolfo A G, Evaluation of lithium-ion capacitors assembled with pre-lithiated graphite anode and activated carbon cathode. [J]. Electrochimica Acta 65 (2012) 280-287.

[35] Cao W J, Zheng J P, The effect of cathode and anode potentials on the cycling performance of Li-ion capacitors. [J]. Journal of the Electrochemical Society 160 (2013) A1572-A1576.

[36] Sun X, Zhang X, Liu W, et al., Electrochemical performances and capacity fading behaviors of activated carbon/hard carbon lithium ion capacitor. [J]. Electrochimica Acta 235 (2017) 158-166.

[37] Li C, Zhang X, Wang K, et al., Scalable Self-Propagating High-Temperature Synthesis of Graphene for Supercapacitors with Superior Power Density and Cyclic Stability. [J]. Advanced Materials 29 (2017) 1604690.

[38] Graphene-based Li-ion capacitor developed by QIBEBT, CAS. [J]. Zhejiang chemical industry (浙江化工) 47 (2016) 54-54.

[39] An Z (安仲勋), Yan L (颜亮亮), Xia H (夏恒恒), et al., Reaearch progress and pilot application of lithium-ion capacitor. [J]. Materials chian (中国材料进展) 35 (2016) 528-536.

[40] Sun X, Zhang X, Wang K, et al., Temperature effect on electrochemical performances of Li-ion hybrid capacitors. [J]. Journal of Solid State Electrochemistry 19 (2015) 2501-2506.

[41] Wang B, Wang Q M, Xu B H, et al., The synergy effect on Li storage of LiFePO₄ with activated carbon modifications. [J]. RSC Advances 3 (2013) 20024-20033.

[42] Hu X B, Deng Z H, Suo J S, et al., A high rate, high capacity and long life (LiMn₂O₄ + AC)/Li₄Ti₅O₁₂ hybrid battery-supercapacitor. [J]. Journal of Power Sources 187 (2009) 635-639.

[43] Chen S L, Hu H C, Wang C Q, et al., (LiFePO₄-AC)/Li₄Ti₅O₁₂ hybrid supercapacitor: The effect of LiFePO₄ content on its performance. [J]. Journal of Renewable and Sustainable Energy 4 (2012) 033114.

[44] Ruan D, Huang Y, Li L, et al., A Li₄Ti₅O₁₂+AC/LiMn₂O₄+AC hybrid battery capacitor with good cycle performance. [J]. Journal of Alloys and Compounds 695 (2017) 1685-1690.

[45] Sun X Z, Zhang X, Huang B, et al., (LiNi_0.5Co_0.2Mn_0.3O₂ + AC)/graphite hybrid energy storage device with high specific energy and high rate capability. [J]. Journal of Power Sources 243 (2013) 361-368.

[46] Sun X, Zhang X, Huang B, et al., Effects of separators on electrochemical performances of electrical double layer capacitor and hybrid battery-supercapacitor [J]. Acta Physico-Chimica Sinica 30 (2014) 485-491.

[47] Aravindan V, Chuiling W, Madhavi S, High power lithium-ion hybrid electrochemical capacitors using spinel LiCrTiO₄ as insertion electrode. [J]. Journal of Materials Chemistry 22 (2012) 16026-16031.

[48] Naoi K, Ishimoto S, Isobe Y, et al., High-rate nano-crystalline Li₄Ti₅O₁₂ attached on carbon nano-fibers for hybrid supercapacitors. [J]. Journal of Power Sources 195 (2010) 6250-6254.

[49] Naoi K, Ishimoto S, Miyamoto J-i, et al., Second generation ‘nanohybrid supercapacitor’: evolution of capacitive energy storage devices. [J]. Energy & Environmental Science 5 (2012) 9363-9373.

[50] Zhang S, Li C, Zhang X, et al., High Performance Lithium-Ion Hybrid Capacitors Employing Fe₃O₄-Graphene Composite Anode and Activated Carbon Cathode [J]. ACS Applied Materials & Interfaces, (2017), DOI: 10.1021/acsami.7b03452.

[51] Naoi K, Kisu K, Iwama E, et al., Ultrafast Cathode Characteristics of Nanocrystalline-Li₃V₂(PO₄)₃/Carbon Nanofiber Composites. [J]. Journal of the Electrochemical Society 162 (2015) A827-A833.

[52] Naoi K, Evolution of Energy Storage on the Platform of Supercapacitors. [J]. Electrochemistry 81 (2013) 775-776.

[53] Kisu K, Iwama E, Onishi W, et al., Ultrafast nano-spherical single-crystalline LiMn_0.792Fe_0.198Mg_0.010PO₄ solid-solution confined among unbundled interstices of SGCNTs. [J]. Journal of Materials Chemistry A 2 (2014) 20789-20798.

[54] Kisu K, Iwama E, Naoi W, et al., Electrochemical kinetics of nanostructure LiFePO₄/graphitic carbon electrodes. [J]. Electrochemistry Communications 72 (2016) 10-14.

[55] Naoi K, Kisu K, Iwama E, et al., Ultrafast charge-discharge characteristics of a nanosized core-shell structured LiFePO₄ material for hybrid supercapacitor applications. [J]. Energy & Environmental Science 9 (2016) 2143-2151.

[56] Naoi K, Kurita T, Abe M, et al., Ultrafast Nanocrystalline-TiO₂(B)/Carbon Nanotube Hyperdispersion Prepared via Combined Ultracentrifugation and Hydrothermal Treatments for Hybrid Supercapacitors. [J]. Advanced Materials 28 (2016) 6751.

[57] Iwama E, Kawabata N, Nishio N, et al., Enhanced Electrochemical Performance of Ultracentrifugation-Derived nc-Li₃VO₄/MWCNT Composites for Hybrid Supercapacitors. [J]. ACS Nano 10 (2016) 5398-5404.

[58] Liu M, Zhang L, Han P, et al., Controllable Formation of Niobium Nitride/Nitrogen-Doped Graphene Nanocomposites as Anode Materials for Lithium-Ion Capacitors. [J]. Particle & Particle Systems Characterization 32 (2015) 1006-1011.

[59] Wang R, Liu P, Lang J, et al., Coupling effect between ultra-small Mn₃O₄ nanoparticles and porous carbon microrods for hybrid supercapacitors. [J]. Energy Storage Materials 6 (2017) 53-60.

[60] Wang R, Lang J, Zhang P, et al., Fast and Large Lithium Storage in 3D Porous VN Nanowires-Graphene Composite as a Superior Anode Toward High-Performance Hybrid Supercapacitors. [J]. Advanced Functional Materials 25 (2015) 2270-2278.

[61] Gu H, Zhu Y-E, Yang J, et al., Nanomaterials and Technologies for Lithium-Ion Hybrid Supercapacitors. [J]. ChemNanoMat 2 (2016) 578-587.

[62] Yang M, Zhong Y, Ren J, et al., Fabrication of High-Power Li-Ion Hybrid Supercapacitors by Enhancing the Exterior Surface Charge Storage. [J]. Advanced Energy Materials 5 (2015) 1500550

[63] Liu S Q, Liu S Q, Huang K L, et al., A novel Et₄NBF₄ and LiPF₆ blend salts electrolyte for supercapacitor battery. [J]. Journal of Solid State Electrochemistry 16 (2012) 1631-1634.

[64] Schroeder M, Winter M, Passerini S, et al., On the use of soft carbon and propylene carbonate-based electrolytes in Lithium-ion capacitors. [J]. Journal of the Electrochemical Society 159 (2012) A1240-A1245.

[65] Qian Y, Niehoff P, Börner M, et al., Influence of electrolyte additives on the cathode electrolyte interphase (CEI) formation on LiNi_1/3Mn_1/3Co_1/3O₂ in half cells with Li metal counter electrode. [J]. Journal of Power Sources 329 (2016) 31-40.

[66] Deng B, Wang H, Ge W, et al., Investigating the influence of high temperatures on the cycling stability of a LiNi_0.6Co_0.2Mn_0.2O₂ cathode using an innovative electrolyte additive. [J]. Electrochimica Acta 236 (2017) 61-71.

[67] Cao W J, Shih J, Zheng J P, et al., Development and Characterization of Li-ion Capacitor Pouch Cells. [J]. Journal of Power Sources 257 (2014) 388-393.

[68] Zhang J, Liu X, Wang J, et al., Different types of pre-lithiated hard carbon as negative electrode material for lithium-ion capacitors. [J]. Electrochimica Acta 187 (2016) 134-142.

[69] Yu X, Deng J, Zhan C, et al., A high-power lithium-ion hybrid electrochemical capacitor based on citrate-derived electrodes. [J]. Electrochimica Acta (2017).

[70] Zhao Hengbing, Burke Andrew, Fuel cell powered vehicles using supercapaciotrs: Device characteristics, control strategies, and simulation results, in: University of California, Davis, 2010.