低温锂离子电池石墨负极材料的缺陷、改性策略与展望

doi:10.19964/j.issn.1006-4990.2024-0489

Abstract

Abstract:

In recent years，with the rapid rise of the new energy industry，the application of lithium-ion batteries in various fields has continued to surge.However，the high performance of commercial lithium-ion batteries with graphite anodes can only be realized above 0 ℃，which limits the application of the batteries in low-temperature cold regions.In order to meet the demand for low-temperature applications of lithium-ion batteries，the mechanism was explored by analyzing the limiting factors of graphite low-temperature environments，providing insights into the key factors contributing to the poor low-temperature performance of lithium-ion batteries.It was focused on the feasible strategies and solutions to improve the low-temperature performance，and the latest progress in the engineering of low-temperature anode materials was reviewed in terms of structural design，morphology control，surface and interface modification，and multiphase materials.Finally，the problems to be solved in the field of low-temperature graphite anode materials were discussed.It was aimed to provide valuable insights and guidance for the development of next-generation LIBs with excellent low-temperature electrochemical properties.

Key words: lithium-ion battery, graphite anode material, low temperature performance, modification

CLC Number:

TQ131.11

LI Shuli, CHEN Shipeng, ZHANG Lingli, SHI Fanian. Defects，modification strategies and prospects of graphite anode materials for low temperature lithium-ion batteries[J]. Inorganic Chemicals Industry, 2025, 57(9): 21-29.

Figures/Tables 5

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References 66

[1]	CHEN Qiu， LUO Pan， LIAO Li，et al.Regulating diffusion coefficient of Li⁺ by high binding energy anion towards ultra-low temperature lithium-ion batteries［J］.Batteries & Supercaps，2024，7（11）：e202400246.
[2]	SCHIED T， NICKOL A， HEUBNER C，et al.Determining the diffusion coefficient of lithium insertion cathodes from GITT measurements：Theoretical analysis for low temperatures［J］.Chem Phys Chem，2021，22（9）：885-893.
[3]	GAO Yue， YAN Liangyu， ZHAO Cai，et al.Accurate calculation of solid-state Li⁺ diffusion coefficient and kinetic activation energies for an artificial graphite anode［J］.Journal of the Electrochemical Society，2024，171（2）：020558.
[4]	PARK J H， YOON H， CHO Y，et al.Investigation of lithium ion diffusion of graphite anode by the galvanostatic intermittent titration technique［J］.Materials，2021，14（16）：4683.
[5]	GUO Zixuan， HAN Xiaoshuai， ZHANG Chunmei，et al.Activation of biomass-derived porous carbon for supercapacitors：A review［J］.Chinese Chemical Letters，2024，35（7）：109007.
[6]	THENUWARA A C， SHETTY P P， MCDOWELL M T.Distinct nanoscale interphases and morphology of lithium metal electrodes operating at low temperatures［J］.Nano Letters，2019，19（12）：8664-8672.
[7]	UITZ M，EPP V， BOTTKE P，et al.Ion dynamics in solid electrolytes for lithium batteries［J］.Journal of Electroceramics，2017，38（2）：142-156.
[8]	穆泊源，杨宗松，董伟，等.基于稻壳基无定形碳的负极材料对锂离子电池低温性能的影响［J］.功能材料，2024，55（4）：4019-4028，4050.
	MU Boyuan， YANG Zongsong， DONG Wei，et al.The low temperature performance of rice husk based amorphous carbon as anode material for lithium-ion batteries［J］.Journal of Functional Materials，2024，55（4）：4019-4028，4050.
[9]	DONG Liwei， YAN Huijuan， LIU Qingxiang，et al.Quantification of charge transport and mass deprivation in solid electrolyte interphase for kinetically-stable low-temperature lithium-ion batteri-es［J］.Angewandte Chemie International Edition，2024，63（43）：e202411029.
[10]	NICKOL A， SCHIED T， HEUBNER C，et al.GITT analysis of lithium insertion cathodes for determining the lithium diffusion coefficient at low temperature：Challenges and pitfalls［J］.Journal of the Electrochemical Society，2020，167（9）：090546.
[11]	LOVE C T， BATURINA O A， SWIDER-LYONS K E.Observation of lithium dendrites at ambient temperature and below［J］.ECS Electrochemistry Letters，2015，4（2）：A24-A27.
[12]	LU Xuekun， LAGNONI M， BERTEI A，et al.Multiscale dynamics of charging and plating in graphite electrodes coupling operando microscopy and phase-field modelling［J］.Nature Communications，2023，14：5127.
[13]	DRÜE M， SEYRING M， RETTENMAYR M.Phase formation and microstructure in lithium-carbon intercalation compounds during lithium uptake and release［J］.Journal of Power Sources，2017，353：58-66.
[14]	ZHANG Wenjun， XU Datong， WANG Fengjue，et al.Element-doped graphitic carbon nitride：Confirmation of doped elements and applications［J］.Nanoscale Advances，2021，3（15）：4370-4387.
[15]	IM U S， HWANG J U， YUN J H，et al.The effect of mild activation on the electrochemical performance of pitch-coated graphite for the lithium-ion battery anode material［J］.Materials Letters，2020，278：128421.
[16]	ZHOU Junhua， MA Keni， LIAN Xueyu，et al.Eliminating graphite exfoliation with an artificial solid electrolyte interphase for stable lithium-ion batteries［J］.Small，2022，18（15）：2107460.
[17]	SHENG Yeliang， YUE Xinyang， HAO Wei，et al.Balancing the ion/electron transport of graphite anodes by a La-doped TiNb₂O₇ functional coating for fast-charging Li-ion batteries［J］.Nano Letters，2024，24（12）：3694-3701.
[18]	MATSUNAGA T， TAKAGI S， SHIMODA K，et al.Comprehensive elucidation of crystal structures of lithium-intercalated grap- hite［J］.Carbon，2019，142：513-517.
[19]	MANKA D， IVERS-TIFFÉE E.Electro-optical measurements of lithium intercalation/de-intercalation at graphite anode surfac- es［J］.Electrochimica Acta，2015，186：642-653.
[20]	张丽津，彭大春，何月德，等.氧化微扩层处理对天然鳞片石墨结构及其电化学性能的影响研究［J］.炭素技术，2016，35（6）：17-22.
	ZHANG Lijin， PENG Dachun， HE Yuede，et al.Structure and electrochemical performance of flake graphite anode materials with mildly expanded interlayer by oxidation［J］.Carbon Techniques，2016，35（6）：17-22.
[21]	廖林，尹伟乐，叶昱昕.石墨化温度对人造石墨微观结构及电化学性能的影响［J］.炭素技术，2023，42（1）：46-50.
	LIAO Lin， YIN Weile， YE Yuxin.Influence of graphitization temperature on the microstructure and electrochemical properties of artificial graphite［J］.Carbon Techniques，2023，42（1）：46-50.
[22]	王晓亮，杨绍斌，汉贻玉，等.少层石墨及其复合材料制备和电化学性能研究［J］.非金属矿，2015，38（6）：15-18.
	WANG Xiaoliang， YANG Shaobin， HAN Yiyu，et al.Study on preparation and electrochemical property of few-layer graphite and its composite materials［J］.Non-Metallic Mines，2015，38（6）：15-18.
[23]	WALDMANN T， HOGG B I， KASPER M，et al.Interplay of operational parameters on lithium deposition in lithium-Ion cells：Systematic measurements with reconstructed3-Electrode pouch full cells［J］.Journal of The Electrochemical Society，2016，163（7）： A1232-A1238.
[24]	YADEGARI H， KORONFEL M A， WANG Kang，et al.Operando measurement of layer breathing modes in lithiated graphite［J］.ACS Energy Letters，2021：1633-1638.
[25]	SETHURAMAN V A， HARDWICK L J， SRINIVASAN V，et al.Surface structural disordering in graphite upon lithium intercalation/deintercalation［J］.Journal of Power Sources，2010，195（11）：3655-3660.
[26]	LI Tong， CAO Yun， SONG Qiuchen，et al.A slightly expanded graphite anode with high capacity enabled by stable lithium-ion/metal hybrid storage［J］.Small，2024，20（40）：2403057.
[27]	杜爱芳，张胜恩，路培中，等.高强度各向同性石墨材料的制备与研究［J］.炭素技术，2020，39（3）：41-44.
	DU Aifang， ZHANG Sheng’en， LU Peizhong，et al.Study on the preparation of high strength isotropic graphite［J］.Carbon Techniques，2020，39（3）：41-44.
[28]	胡孔明.焦原料类型对人造石墨负极性能的影响［J］.有色冶金设计与研究，2024，45（3）：15-20.
	HU Kongming.Influence of coke material types on the performance of artificial graphite negative electrode［J］.Nonferrous Metals Engineering & Research，2024，45（3）：15-20.
[29]	范青杰，宋岩，赖仕全，等.煤系针状焦原料在成焦过程中的XRD结构分析［J］.光谱学与光谱分析，2022，42（6）：1979-1984.
	FAN Qingjie， SONG Yan， LAI Shiquan，et al.XRD structural analysis of raw material used as coal-based needle coke in the coking process［J］.Spectroscopy and Spectral Analysis，2022，42（6）：1979-1984.
[30]	YUAN Guanming， JIN Zhao， ZUO Xiaohua，et al.Effect of carbonaceous precursors on the structure of mesophase pitches and their derived cokes［J］.Energy & Fuels，2018，32（8）：8329-8339.
[31]	SHEN Ke， HUANG Zhenghong， HU Kaixin，et al.Advantages of natural microcrystalline graphite filler over petroleum coke in isotropic graphite preparation［J］.Carbon，2015，90：197-206.
[32]	HE Zhao， SONG Jinliang， WANG Zheng，et al.Comparison of ultrafine-grain isotropic graphite prepared from microcrystalline graphite and pitch coke［J］.Fuel，2021，290：120055.
[33]	SOLTANI HOSSEINI M， CHARTRAND P.Thermodynamics and phase relationship of carbonaceous mesophase appearing during coal tar pitch carbonization［J］.Fuel，2020，275：117899.
[34]	WANG Haibin， NING Guoqing， HE Xing，et al.Carbon quantum dots derived by direct carbonization of carbonaceous microcrystals in mesophase pitch［J］.Nanoscale，2018，10（45）：21492-21498.
[35]	崔贝贝，王美君，常丽萍，等.炼焦煤成焦机理再认识：“衍构成焦机理”的提出［J］.煤炭学报，2024，49（6）：2826-2839.
	CUI Beibei， WANG Meijun， CHANG Liping，et al.A renew cognition of coking mechanism：Proposing the“Structure Derivation Coking Mechanism”［J］.Journal of China Coal Society，2024，49（6）：2826-2839.
[36]	HWANG J U， CHO J H， LEE J D，et al.Characteristics of an artificial graphite anode material for rapid charging：Manufactured with different coke particle sizes［J］.Journal of Materials Science：Materials in Electronics，2022，33（25）：20095-20105.
[37]	王英，阮威，唐仁衡，等.不同粒径纳米硅制备Si@C/石墨负极材料及其电化学性能［J］.材料导报，2019，33（18）：3021-3025.
	WANG Ying， RUAN Wei， TANG Renheng，et al.Preparation of Si@C/graphite anode materials with different particle size nanoscale-Si and their electrochemical properties［J］.Materials Reports，2019，33（18）：3021-3025.
[38]	丁晓博，黄倩晖，熊训辉.锂离子电池快充石墨负极研究与应用［J］.物理化学学报，2022，38（11）：95-110.
	DING Xiaobo， HUANG Qianhui， XIONG Xunhui.Research and application of fast-charging graphite anodes for lithium-ion batteries［J］.Acta Physico-Chimica Sinica，2022，38（11）：95- 110.
[39]	穆江涛，杨林，王英新，等.提高锂离子电池天然石墨负极倍率性能研究［J］.炭素，2020（2）：5-12.
	MU Jiangtao， YANG Lin， WANG Yingxin，et al.Investgation on improving the negative rate performance of natural graphite in lithium ion battery［J］.Carbon，2020（2）：5-12.
[40]	CHEN Zhongyi， LIU Yan， ZHANG Yanzong，et al.Ultrafine layered graphite as an anode material for lithium ion batteries［J］.Materials Letters，2018，229：134-137.
[41]	WANG Guanyi， MIJAILOVIC A， YANG Jian，et al.Particle size effect of graphite anodes on performance of fast charging Li-ion batteries［J］.Journal of Materials Chemistry A，2023，11（40）：21793-21805.
[42]	张鑫，雷维新，潘俊安，等.粒径级配对石墨基负极材料电化学性能的影响［J］.电源技术，2020，44（3）：318-321.
	ZHANG Xin， LEI Weixin， PAN Jun′an，et al.Effects of particle size grading on electrochemical properties of graphite anode materials［J］.Chinese Journal of Power Sources，2020，44（3）：318- 321.
[43]	闻文，王慧艳，周静红，等.石墨负极颗粒对锂离子电池容量衰减及SEI膜生长影响的模拟研究［J］.化工学报，2024，75（1）：366-376.
	WEN Wen， WANG Huiyan， ZHOU Jinghong，et al.Simulation study on the impact of graphite anode particles on lithium-ion battery capacity fading and SEI film growth［J］.CIESC Journal，2024，75（1）：366-376.
[44]	CHOI Y J， LEE Y S， KIM J H，et al.Optimization of pore characteristics of graphite-based anode for Li-ion batteries by control of the particle size distribution［J］.Materials，2023，16（21）：6896.
[45]	WANG Cong， GAI Guosheng， YANG Yufen.Shape modification and size classification of microcrystalline graphite powder as anode material for lithium-ion batteries［J］.JOM，2018，70（8）：1392-1397.
[46]	LI Fusheng， WU Y S， CHOU J，et al.A mechanically robust and highly ion-conductive polymer-blend coating for high-power and long-life lithium-ion battery anodes［J］.Advanced Materials，2015，27（1）：130-137.
[47]	ZHENG Xueying， SHI Qiang， WANG Yan，et al.The role of carbon bond types on the formation of solid electrolyte interphase on graphite surfaces［J］.Carbon，2019，148：105-114.
[48]	WU Xuan， YANG Xuelin， ZHANG Fei，et al.Carbon-coated isotropic natural graphite spheres as anode material for lithium-ion batteries［J］.Ceramics International，2017，43（12）：9458-9464.
[49]	MARIN-MONTIN J， ZURITA-GOTOR M，MONTERO-CHACÓN F.A numerical study of mechanical degradation of carbon-coated graphite active particles in Li-ion battery anodes［J］.Journal of the Electrochemical Society，2022，169（7）：070528.
[50]	GUO Jianqiang， LIU Shiqi， YANG Maoxia，et al.Outstanding low temperature performance of hollow carbon sphere@MnO₂ anode based on pseudo-capacitive storage mechanism［J］.Journal of Alloys and Compounds，2023，937：168325.
[51]	LIU Wenping， XU Huarui， QIN Haiqing，et al.Rapid coating of asphalt to prepare carbon-encapsulated composites of nano-silicon and graphite for lithium battery anodes［J］.Journal of Materials Science，2020，55（10）：4382-4394.
[52]	DONG Xiaoli， WANG Yonggang， XIA Yongyao.Promoting rechargeable batteries operated at low temperature［J］.Accounts of Chemical Research，2021，54（20）：3883-3894.
[53]	LUO Dan， LI Ming， ZHENG Yun，et al.Electrolyte design for lithium metal anode-based batteries toward extreme temperature application［J］.Advanced Science，2021，8（18）：2101051.
[54]	KIM D S， CHUNG D J，BAE J，et al.Surface engineering of graphite anode material with black TiO_2- _x for fast chargeable lithium ion battery［J］.Electrochimica Acta，2017，258：336-342.
[55]	LEE S， KIM J， MOON J，et al.A cooperative biphasic MoO _x -MoP _x promoter enables a fast-charging lithium-ion batte-ry［J］.Nature Communications，2021，12：39.
[56]	KIM D S， KIM Y E， KIM H.Improved fast charging capability of graphite anodes via amorphous Al₂O₃ coating for high power lithi-um ion batteries［J］.Journal of Power Sources，2019，422：18- 24.
[57]	GAO Yang， ZHANG Jialiang， CHEN Yongqiang，et al.Improvement of the electrochemical performance of spent graphite by asphalt coating［J］.Surfaces and Interfaces，2021，24：101089.
[58]	LUO Jing， WU Changen， SU Linya，et al.A proof-of-concept graphite anode with a lithium dendrite suppressing polymer coating［J］.Journal of Power Sources，2018，406：63-69.
[59]	WANG Ziqi， WANG Zijian， YANG Luyi，et al.Boosting interfacial Li⁺ transport with a MOF-based ionic conductor for solid-state batteries［J］.Nano Energy，2018，49：580-587.
[60]	TANG Shun， ZHANG Xiaokun， LI Yan，et al.A fast ionic conductor and stretchable solid electrolyte artificial interphase layer for Li metal protection in lithium batteries［J］.Journal of Alloys and Compounds，2020，843：155839.
[61]	WANG Chaonan， XIE Yuansen， HUANG Yingshan，et al.Li₃PO₄-enriched SEI on graphite anode boosts Li⁺ de-solvation enabling fast-charging and low-temperature lithium-ion batteries［J］.Angewandte Chemie International Edition，2024，63（21）：e202402301.
[62]	HUANG Yingshan， WANG Chaonan， LV Haifeng，et al.Bifunctional interphase promotes Li⁺ de-solvation and transportation enabling fast-charging graphite anode at low temperature［J］.Advanced Materials，2024，36（13）：2308675.
[63]	AN Juan， WANG Fan， YANG Jiayue，et al.An ion-pumping interphase on graphdiyne/graphite heterojunction for fast-charging lithium-ion batteries［J］.CCS Chemistry，2024，6（1）：110-124.
[64]	NA Ying， SUN Xiaohong， FAN Anran，et al.Methods for enhancing the capacity of electrode materials in low-temperature lithium-ion batteries［J］.Chinese Chemical Letters，2021，32（3）：973- 982.
[65]	FLEUTOT B， DAVOISNE C， GACHOT G，et al.New chemical approach to obtain dense layer phosphate-based ionic conductor coating on negative electrode material surface：Synthesis way，outgassing and improvement of C-rate capability［J］.Applied Surface Science，2017，400：139-147.
[66]	LIU Yangyang， SHI Haodong， WU Zhongshuai.Recent status，key strategies and challenging perspectives of fast-charging grap-hite anodes for lithium-ion batteries［J］.Energy & Environmental Science，2023，16（11）：4834-4871.

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Defects，modification strategies and prospects of graphite anode materials for low temperature lithium-ion batteries

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