高比能量锂离子电池硅基负极材料研究进展

doi:10.15541/jim20180347

摘要/Abstract

摘要：

硅的理论嵌锂比容量是石墨材料比容量的十倍以上, 脱锂电位低, 资源丰富, 倍率特性较好, 故高比能量的硅基材料成为了电动汽车?可再生能源储能系统等领域的研究热点?但由于其在脱嵌锂过程中巨大的体积膨胀效应会导致硅电极材料粉化和结构崩塌, 并且在电解液中硅表面重复形成的固相电解质层(SEI)使极化增大?库伦效率降低, 最终导致电化学性能的恶化?为了解决上述问题, 加快实现硅基电极的商业化应用, 本文系统总结了通过硅基材料的选择和结构设计来解决充放电过程中体积效应的工作, 并深入分析和讨论了具有代表性的硅基复合材料的制备方法?电化学性能和相应机理, 重点介绍了硅碳复合材料和SiO_x(0<x≤2)基复合材料?最后对硅基负极材料存在的问题进行了分析, 并展望了其研究前景?

关键词: 硅基材料, 负极材料, 锂离子电池, 综述

Abstract:

Silicon has the highest theoretical lithium insertion specific capacity, more than ten times the theoretical specific capacity of graphite electrode material, and low delithiation potential, with abundant resources and good rate characteristics, high-energy-density lithium-ion battery silicon-based materials have become hot spots in application fields such as electric vehicles and renewable energy storage systems. However, it will cause powdering and structural collapse of the silicon electrode material due to its large volume expansion effect in the process of delithiation and lithium insertion. In addition, the solid electrolyte interface (SEI) layer on the surface of silicon is repeatedly formed in the electrolyte, which increases the polarization and reduces the coulomb efficiency, eventually leading to deterioration of electrochemical performance. In order to solve the above problems and realize the commercial application of silicon electrodes. This paper systematically summarizes the work to solve the volume effect in charge and discharge process through the selection and structural design of silicon-based materials, and deeply analyzes and discusses the preparation methods, electrochemical properties and corresponding mechanisms of representative silicon-based composite materials, focusing on silicon-carbon composites and SiO_x (0<x≤2) based anode materials. Finally, the problems of silicon-based anode materials are analyzed and their prospects are prospected.

Key words: silicon-based material, anode materials, lithium-ion batteries, review

中图分类号:

TM912

谭毅, 王凯. 高比能量锂离子电池硅基负极材料研究进展[J]. 无机材料学报, 2019, 34(4): 349-357.

Yi TAN, Kai WANG. Silicon-based Anode Materials Applied in High Specific Energy Lithium-ion Batteries: a Review[J]. Journal of Inorganic Materials, 2019, 34(4): 349-357.

图/表 14

图1 几种负极材料性能对比

Fig. 1 Performance comparison of common anode materials

图2 充电和放电期间硅体积膨胀示意图[9]

Fig. 2 Illustration of Si volume expansion during charge and discharge[9]

图3 硅的失效机制示意图[13]

Fig. 3 Schematic of the failure mechanism of silicon[13]

图4 CNT@mp-Si和中孔多孔Si纳米管的合成示意图[20]

Fig. 4 The composite map of synthesis of CNT@mp-Si and meso-porous Si nanotube [20]

图5 石榴状纳米硅碳材料设计示意图[25]

Fig. 5 Schematic of the pomegranate-inspired design[25](a) Three dimensional view and (b) simplified two-dimensional cross-section view

图6 (a)新型实心核壳Si@C@void@C的形成过程示意图, (b)原料Si、(c)Si@SiO2@C、(d) Si@void@C、(e) Si@C、(f) Si@C@SiO2@C和(g) Si@C@void@C的TEM照片[26]

Fig. 6 (a) Schematic diagram of the novel core-shell Si@C@void@C, TEM images of (b) raw Si, (c) Si@SiO2@C, (d) Si@void@C, (e) Si@C, (f) Si@C@SiO2@C, and (g) Si@C@void@C[26]

图7 (a)硅表面沉积银颗粒和(b, c)金属诱导刻蚀硅的扫描电镜照片[28]

Fig. 7 Scanning diagrams of (a) Ag-deposited on Si and (b, c) metal induced etching Si[28]

图8 从Al-Si合金到Si/C复合材料的制备过程示意图[30]

Fig. 8 Schematic illustration of the preparation process from Al-Si alloy to the Si/C composite[30]

表1 硅/碳锂离子电池负极材料的电化学性能

Table 1 Electrochemical performance of some silicon/carbon composite anodes for lithium-ion batteries

Composite type	Si source	Carbon source	Electrochemical performance	Method	Ref.
Si/Porous-C	Nano-silicon powder	Pitch	723.8 mAh/g (1st)600 mAh/g (100 mA/g, 100 )^a	Spray drying + High-temperature pyrolysis	[35]
Si@C@RGO	Silicon powder (80 nm)	Sucrose	1599 mAh/g (1st)1517 mAh/g (100 mA/g, 100 )	Spray drying + High-temperature pyrolysis	[36]
Si/C/G	Silicon powder (325 mesh)	Phenol-formaldehyde resin (PFR)	700 mAh/g (1st)550 mAh/g (100 mA/g, 40 )	High-temperature pyrolysis	[37]
Silicon-sponge	Si wafer (>20 μm)	Acetylene	790 mAh/g (1st)726 mAh/g (100 mA/g, 300 )	Electrochemical etching+ High-temperature pyrolysis	[38]
PS@C	Si powder (5 μm)	Propylene	1980 mAh/g (1st)1287 mAh/g (100 mA/g, 100)	Chemical etching + CVD	[39]
Si/C	Al-Si alloy (2-10 μm)	Polyacrylonitrile (PAN)	952 mAh/g (1st)826.3 mAh/g (200 mA/g, 300)	Chemical etching + High-temperature pyrolysis	[30]

图9 SiOx材料的基本电化学机理示意图[46]

Fig. 9 Schematic diagram of the basic electrochemical mechanism of SiOx-based materials[46]

图10 卷绕电池的金属箔电路短路预锂化处理的示意图[50]

Fig. 10 Schematic diagram of short-circuit prelithiation treatment of metal foil circuit of batteries[50]

图11 复合材料SiOx/Si/C的制备示意图[54]

Fig. 11 Schematic diagram of preparation of the SiOx/Si/C[54]

图12 (a)初始SiO@C原料与中空SiO@void@C材料的表面((b)二次电子相, (c)背散射相)及(d)截面SEM照片[59]

Fig. 12 SEM images of (a) initial SiO@C, surface ((b) secondary electron phase, (c) back scattered) and (d) cross-section of hollow SiO@void@C material[59]

图13 几种典型硅基负极材料性能对比[25,30, 35-39,47,53-54,59-62]

Fig. 13 Performance comparisons of common Si-based anode materials[25, 30, 35-39, 47, 53-54, 59-62]

参考文献 62

[1]	GOODENOUGH J B, PARK K S . The Li-ion rechargeable battery: a perspective.[J]. Am. Chem. Soc., 2013,135(4):1167-1176.
[2]	TAN Y, XUE B . Research progress on lithium titanate as anode material in lithium-ion battery.[J]. Inorg. Mater., 2018,33(5):475-482.
[3]	LUO W, CHEN X, XIA Y , et al. Surface and interface engineering of silicon-based anode materials for lithium-ion batteries. Adv. Energy Mater., 2017, 7(24): 1701083-1-28.
[4]	XIAO Q Z, FAN Y, WANG X H , et al. A multilayer Si/CNT coaxial nano fiber LiB anode with a high areal capacity. Energy Environ. Sci., 2014,7(2):655-661.
[5]	HUANG S, FAN F, LI J , et al. Stress generation during lithiation of high-capacity electrode particles in lithium ion batteries. Acta Mater., 2013,61(12):4354-4364.
[6]	LI J, DAHN J R . An in situ X-ray diffraction study of the reaction of Li with crystalline Si.[J]. Electrochem. Soc., 2007,154(3):A156-A161.
[7]	WANG F, WU L J, KEY B , et al. Electrochemical reaction of lithium with nanostructure silicon anodes: a study by in-situ synchrotron X-ray diffraction and electron energy-loss spectroscopy. Adv. Energy Mater., 2013,3(10):1324-1331.
[8]	OBROVAC M N, KRAUSE L J . Reversible cycling of crystalline silicon powder.[J]. Electrochem. Soc., 2007,154(2):A103-A108.
[9]	DING N, XU J, YAO Y X , et al. Improvement of cyclability of Si as anode for Li-ion batteries.[J]. Power Sources, 2009,192(2):644-651.
[10]	SETHURAMAN V A, CHON M J, SHIMSHAK M , et al. In situ, measurements of stress evolution in silicon thin films during electrochemical lithiation and delithiation.[J]. Power Sources, 2012,195(15):5062-5066.
[11]	NADIMPALLI S P V, SETHURAMAN V A, BUCCI G , et al. On plastic deformation and fracture in Si films during electrochemical lithiation/delithiation cycling.[J]. Electrochem. Soc., 2013,160(10):A1885-A1893.
[12]	GHASSEMI H, MING A, CHEN N , et al. In situ electrochemical lithiation/delithiation observation of individual amorphous Si nanorods. ACS Nano, 2011,5(10):7805-7811.
[13]	LIANG B, LIU Y, XU Y . Silicon-based materials as high capacity anodes for next generation lithium ion batteries.[J]. Power Sources, 2014,267:469-490.
[14]	WEN Z S, WANG K, XIE J Y . Interface formed on high capacity silicon anode for lithium ion batteries.[J]. Inorg. Mater., 2007,22(3):437-441.
[15]	CHAN C K, RUFFO R, HONG S , et al. Surface chemistry and morphology of the solid electrolyte interphase on silicon nanowire lithium-ion battery anodes.[J]. Power Sources, 2009,189(2):1132-1140.
[16]	KEY B, BHATTACHARYYA R, MORCRETTE M , et al. Real-time NMR investigations of structural changes in silicon electrodes for lithium-ion batteries.[J]. Am. Chem. Soc., 2009,131(26):9239-9249.
[17]	JI H R, KIM J W, SUNG Y E , et al. Failure modes of silicon powder negative electrode in lithium secondary batteries. Electrochem. Solid-State Lett., 2004,7(10):A306-A309.
[18]	HONG L, HUANG X, CHEN L , et al. The crystal structural evolution of nano-Si anode caused by lithium insertion and extraction at room temperature. Solid State Ionics, 2000,135(1):181-191.
[19]	LIANG J W, LI X N, ZHU Y C , et al. Hydrothermal synthesis of nano-silicon from a silica sol and its use in lithium ion batteries. Nano Res., 2015,8(5):1497-1504.
[20]	KIM W S, CHOI J, HONG S H . Meso-porous silicon-coated carbon nanotube as an anode for lithium-ion battery. Nano Lett., 2016,9(7):2174-2181.
[21]	ZHOU Y N, XUE M Z, FU Z W . Nanostructured thin film electrodes for lithium storage and all-solid-state thin-film lithium batteries.[J]. Power Sources, 2013,234(21):310-332.
[22]	DATTA M K, MARANCHI J, CHUNG S J , et al. Amorphous silicon- carbon based nano-scale thin film anode materials for lithium ion batteries. Electrochim. Acta, 2011,56(13):4717-4723.
[23]	CHENG H, XIAO R, BIAN H , et al. Periodic porous silicon thin films with interconnected channels as durable anode materials for lithium ion batteries. Mater. Chem. Phys., 2014,144(1/2):25-30.
[24]	TONG Y, XU Z, LIU C , et al. Magnetic sputtered amorphous Si/C multilayer thin films as anode materials for lithium ion batteries.[J]. Power Sources, 2014,247(2):78-83.
[25]	LIU N, LU Z, ZHAO J , et al. A pomegranate-inspired nanoscale design for large-volume-change lithium battery anodes. Nat. Nanotechnol., 2014,9(3):187-192.
[26]	XIE J, TONG L, SU L , et al. Core-shell yolk-shell Si@C@Void@C nanohybrids as advanced lithium ion battery anodes with good electronic conductivity and corrosion resistance.[J]. Power Sources, 2017,342:529-536.
[27]	BANG B M, LEE J I, KIM H , et al. High-performance macro porous bulk silicon anodes synthesized by template-free chemical etching. Adv. Energy Mater., 2012,2(7):878-883.
[28]	GE M, LU Y, ERCIUS P , et al. Large-scale fabrication, 3D tomography, and lithium-ion battery application of porous silicon. Nano Lett., 2014,14(1):261-268.
[29]	GE M, RONG J, FANG X , et al. Scalable preparation of porous silicon nanoparticles and their application for lithium-ion battery anodes. Nano Res., 2013,6:174-181.
[30]	TIAN H, TAN X, XIN F , et al. Micro-sized nano-porous Si/C anodes for lithium ion batteries. Nano Energy, 2015,11:490-499.
[31]	LIU N, WU H, MCDOWELL M T , et al. A yolk-shell design for stabilized and scalable Li-ion battery alloy anodes. Nano Lett., 2012,12(6):3315-3321.
[32]	KIM H, HAN B, CHOO J , et al. Three-dimensional porous silicon particles for use in high-performance lithium secondary batteries. Angew. Chem. Int. Ed., 2008,47(52):10151-10154.
[33]	JIANG H, ZHOU X, LIU G , et al. Free-standing Si/graphene paper using Si nanoparticles synthesized by acid-etching Al-Si alloy powder for high-stability Li-ion battery anodes. Electrochim. Acta, 2016,188:777-784.
[34]	WRODNIGG G H, WRODNIGG T M, BESENHARD J O , et al. Propylene sulfite as film-forming electrolyte additive in lithium ion batteries. Electrochem. Commun., 1999,1(3/4):148-150.
[35]	LI M, HOU X, SHA Y , et al. Facile spray-drying/pyrolysis synjournal of core-shell structure graphite/silicon-porous carbon composite as a superior anode for Li-ion batteries.[J]. Power Sources, 2014,248(2):721-728.
[36]	PAN Q, ZUO P, LOU S , et al. Micro-sized spherical silicon@carbon@graphene prepared by spray drying as anode material for lithium-ion batteries.[J]. Alloys Compd., 2017,723:434-440.
[37]	ZUO P, YIN G, MA Y , et al. Electrochemical stability of silicon/ carbon composite anode for lithium ion batteries. Electrochim. Acta, 2007,52(15):4878-4883.
[38]	LI X, GU M, HU S , et al. Mesoporous silicon sponge as an anti- pulverization structure for high-performance lithium-ion battery anodes. Nature Commun., 2014, 5(5): 4105-1-7.
[39]	KIM J S, HALIM M, BYUN D , et al. Amorphous carbon-coated prickle-like silicon of micro and nano hybrid anode materials for lithium-ion batteries. Solid State Ionics, 2014,260:36-42.
[40]	MIN K K, BO Y J, JIN S L , et al. Microstructures and electrochemical performances of nano-sized SiO_x (1.18≤ x ≤1.83) as an anode material for a lithium(Li)-ion battery.[J]. Power Sources, 2013,244:115-121.
[41]	TAKEZAWA H, IWAMOTO K, ITO S , et al. Electrochemical behaviors of nonstoichiometric silicon suboxides (SiO_x) film prepared by reactive evaporation for lithium rechargeable batteries.[J]. Power Sources, 2013,244:149-157.
[42]	SCHULMEISTER K, MADER W . TEM investigation on the structure of amorphous silicon monoxide. J. Non-Cryst. Solids, 2003,320(1):143-150.
[43]	HOHL A, WIEDER T, AKEN P A V , et al. An interface clusters mixture model for the structure of amorphous silicon monoxide (SiO). J. Non-Cryst. Solids, 2003,320(1):255-280.
[44]	LÜ P P, ZHAO H L, WANG J , et al. Facile preparation and electrochemical properties of amorphous SiO₂/C composite as anode material for lithium ion batteries.[J]. Power Sources, 2013,237(259):291-294.
[45]	LIU X, ZHAO H L, JIE J Y , et al. SiO_x(0<x≤2) based anode materials for lithium-ion batteries. Prog. Chem., 2015,27(4):336-348.
[46]	PHILIPPE B, DEDRYVÈRE R, ALLOUCHE J , et al. Nanosilicon electrodes for lithium-ion batteries: interfacial mechanisms studied by hard and soft X-ray photoelectron spectroscopy. Chem. Mater., 2017,24(24):1107-1115.
[47]	PARK C M, CHOI W, HWA Y , et al. Characterizations and electrochemical behaviors of disproportionate SiO and its composite for rechargeable Li-ion batteries.[J]. Mater. Chem., 2010,20(23):4854-4860.
[48]	MORITA T, TAKAMI N . Nano Si cluster-SiO_x-C composite material as high-capacity anode material for rechargeable lithium batteries.[J]. Electrochem. Soc., 2006,153(2):A425-A430.
[49]	YANG X L, ZHANG P C, WEN Z Y , et al. High performance silicon/carbon composite prepared by in situ carbon-thermal reduction for lithium ion batteries.[J]. Alloys Compd., 2010,496(1):403-406.
[50]	SEONG I W, KIM K T, YOON W Y , et al. Electrochemical behavior of a lithium-pre-doped carbon-coated silicon monoxide anode cell.[J]. Power Sources, 2009,189(1):511-514.
[51]	KIM H J, CHOI S, LEE S J , et al. Controlled prelithiation of silicon monoxide for high performance lithium-ion rechargeable full cells. Nano Lett., 2016,16(1):282-288.
[52]	XING A, ZHANG J, BAO Z , et al. A magnesiothermic reaction process for the scalable production of mesoporous silicon for rechargeable lithium batteries. Chem. Commun., 2013,49(60):6743-6745.
[53]	YU B C, HWA Y, KIM J H , et al. A new approach to synthesis of porous SiO_x, anode for Li-ion batteries via chemical etching of Si crystallites. Electrochim. Acta, 2014,117(4):426-430.
[54]	FENG X J, YANG J, LU Q W , et al. Facile approach to SiO_x/Si/C composite anode material from bulk SiO for lithium ion batteries. Phys. Chem. Chem. Phys., 2013,15(34):14420-144206.
[55]	YANG T, XIAO L I, TIAN X D , et al. Preparation and electrochemical performance of Si@C/SiO_x as anode material for lithium-ion batteries.[J]. Inorg. Mater., 2017,32(7):699-704.
[56]	LIU Y H, OKANO M, MUKAI T , et al. Improvement of thermal stability and safety of lithium ion battery using SiO anode material.[J]. Power Sources, 2016,304:9-14.
[57]	MIYUKI T, OKUYAMA Y, SAKAMOTO T , et al. Characterization of heat treated SiO powder and development of a LiFePO₄/ SiO lithium ion battery with high-rate capability and thermo stability. Electrochemistry, 2012,80(6):401-404.
[58]	MASAYUKI Y, KAZUTAKA U, ATSUSHI U . Performance of the “SiO”-carbon composite-negative electrodes for high-capacity lithium-ion batteries; prototype 14500 batteries.[J]. Power Sources, 2013,225:221-225.
[59]	LIU X . Facile synthesis and electrochemical performance of hollow SiO@void@C composite as anode material for lithium-ion batteries. Chin. Batt. Indust., 2017,21(6):3-9.
[60]	LIU W R, YEN Y C, WU H C , et al. Nano-porous SiO/carbon composite anode for lithium-ion batteries.[J]. Appl. Electrochem., 2009,39(9):1643-1649.
[61]	CHOI I, MIN J L, OH S M , et al. Fading mechanisms of carbon- coated and disproportionated Si/SiO_x negative electrode (Si/SiO_x/C) in Li-ion secondary batteries: dynamics and component analysis by TEM. Electrochim. Acta, 2012,85(1):369-376.
[62]	SHI C C, YAN X L, ZHANG L L , et al. High-performance SiO/C/G composite anode for lithium ion batteries.[J]. Inorg. Mater., 2013,28(9):943-948.