橄榄石型磷酸铁锂正极材料的合成及改性研究进展

doi:10.19964/j.issn.1006-4990.2024-0281

Abstract

Abstract:

Lithium iron phosphate with olivine structure（LiFePO₄），as a high⁃performance cathode material，has the advantages of low cost，large capacity，and environmental friendliness.However，due to the low electronic conductivity and ion diffusion rate of lithium iron phosphate batteries，their further development in the power battery industry is restricted.Therefore，effective strategies are needed to improve the battery performance of lithium iron phosphate.The specific process of synthesizing LiFePO₄ by high⁃temperature solid phase method，hydrothermal method，solvothermal method and sol-gel method，as well as the advantages and disadvantages of each method were systematically described.It showed that different methods had different effects on the morphology and particle size of LiFePO₄.Afterwards，the influence of surface coating，ion doping and other modification methods on the electrochemical performance of lithium iron phosphate was analyzed.The analysis showed that both modification methods effectively improved the ion conductivity and lithium ion diffusion rate，significantly enhancing its electrochemical performance.Finally，the future research directions of lithium iron phosphate were prospected.In the future，it was still necessary to conduct in⁃depth research on the coating and doping technology of LiFePO₄，promote its sustainable development in the lithium⁃ion battery industry，and improve its application value in high⁃performance lithium batteries and other fields.

Key words: lithium iron phosphate, synthetic method, surface coating, ion doping

CLC Number:

TQ131.11

TANG Zhenqiang, CAI Zongying, CAO Weigang, ZHENG Long. Research progress on synthesis and modification of olivine type lithium iron phosphate cathode materials[J]. Inorganic Chemicals Industry, 2025, 57(5): 55-63.

Figures/Tables 7

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Table 1

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Table 2

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References 65

1	LIANG Qian， YUE Haifeng， WANG Shaofeng，et al.Recycling and crystal regeneration of commercial used LiFePO₄ cathode materi⁃ als［J］.Electrochimica Acta，2020，330：135323.
2	PADHI A K， NANJUNDASWAMY K S， GOODENOUGH J B.Phospho⁃olivines as positive⁃electrode materials for rechargeable lithium batteries［J］.Journal of the Electrochemical Society，1997，144（4）：1188.
3	AHSAN Z， DING Bo， CAI Zhenfei，et al.Recent progress in capacity enhancement of LiFePO₄ cathode for Li-ion batteries［J］.Journal of Electrochemical Energy Conversion and Storage，2021，18（1）：010801.
4	王延壮，程仁飞，杨金星，等.磷酸铁锂的高性能化研究进展［J］.现代技术陶瓷，2024，45（S1）：74-99.WANG Yanzhuang， CHENG Renfei， YANG Jinxing，et al.Research progress of high performance in ferrous lithium phospha⁃te［J］.Advanced Ceramics，2024，45（S1）：74-99.
5	SHAN Minghui， DANG Chenyang， MENG Kai，et al.Recycling of LiFePO₄ cathode materials：From laboratory scale to industrial production［J］.Materials Today，2024，73：130-150.
6	SYED M A， SALEHABADI M， OBROVAC M N.High energy density large particle LiFePO₄ ［J］.Chemistry of Materials，2024，36（2）：803-814.
7	LUO Nan， LIN Yong， CHAMAS M，et al.Cold isostatic sintering to enhance the ionic conductivity of LiFePO₄ ［J］.Ceramics International，2021，47（7）：9296-9302.
8	ZHENG Wei， LI Zhiqiang， HE Ming，et al.Enhanced electrical conductivity and lithium ion diffusion rate of LiFePO₄ by Fe site and P site doping［J］.AIP Advances，2023，13（7）：075306.
9	LIU Yuanyuan， LIU Hao， AN Liwei，et al.Blended spherical lithium iron phosphate cathodes for high energy density lithium⁃ion batteries［J］.Ionics，2019，25（1）：61-69.
10	SONG Lingjun， LIANG Tongyi， LU Languang，et al.Lithium⁃ion battery pack equalization based on charging voltage curves［J］.International Journal of Electrical Power & Energy Systems，2020，115：105516.
11	ZHANG Baofeng， XU Youlong， WANG Jie，et al.Electrochemical performance of LiFePO₄/graphene composites at low temperature affected by preparation technology［J］.Electrochimica Acta，2021，368：137575.
12	TÉLIZ E， MARTÍNEZ M， FACCIO R，et al.Electrochemical response of carbon doped LiFePO₄ olivine nanoparticles：Cobalt doping and temperature calcination effects［J］.Journal of Electroanalytical Chemistry，2020，878：114581.
13	ZHANG Huanhuan， ZOU Zhengguang， ZHANG Shuchao，et al.A review of the doping modification of LiFePO₄ as a cathode material for lithium ion batteries［J］.International Journal of Electrochemical Science，2020，15（12）：12041-12067.
14	HU Jiangtao， HUANG Weiyuan， YANG Luyi，et al.Structure and performance of the LiFePO₄ cathode material：From the bulk to the surface［J］.Nanoscale，2020，12（28）：15036-15044.
15	ZHENG Shuohang， WANG Xiaotong， GU Zhenyi，et al.Direct and rapid regeneration of spent LiFePO₄ cathodes via a high⁃temperature shock strategy［J］.Journal of Power Sources，2023，587：233697.
16	LI Shuping， XIONG Ruoyu， HAN Zhilong，et al.Unveiling low⁃tortuous effect on electrochemical performance toward ultrathick LiFePO₄ electrode with 100 mg cm^-2 area loading［J］.Journal of Power Sources，2021，515：230588.
17	KANAGARAJ A B， CHATURVEDI P， KIM H J，et al.Controllable synthesis of LiFePO₄ microrods and its superior electrochemical performance［J］.Materials Letters，2021，283：128737.
18	张婷，林森，于建国.磷酸铁锂正极材料的制备及性能强化研究进展［J］.无机盐工业，2021，53（6）：31-40.ZHANG Ting， LIN Sen， YU Jianguo.Research progress in synthesis and performance enhancement of LiFePO₄ cathode materi⁃als［J］.Inorganic Chemicals Industry，2021，53（6）：31-40.
19	DONG Y Z， ZHAO Y M， CHEN Y H，et al.Optimized carbon⁃coated LiFePO₄ cathode material for lithium⁃ion batteries［J］.Materials Chemistry and Physics，2009，115（1）：245-250.
20	GIM J， SONG Jinju， NGUYEN D，et al.A two⁃step solid state synthesis of LiFePO₄/C cathode with varying carbon contents for Li-ion batteries［J］.Ceramics International，2014，40（1）：1561-1567.
21	VERNARDOU D.Recent report on the hydrothermal growth of LiFePO₄ as a cathode material［J］.Coatings，2022，12（10）：1543.
22	LI Yin， WANG Li， ZHANG Keyu，et al.Optimized synthesis of LiFePO₄ cathode material and its reaction mechanism during solvothermal［J］.Advanced Powder Technology，2021，32（6）：2097-2105.
23	郭举，贾双珠.水热法一步合成磷酸铁锂及其性能研究［J］.无机盐工业，2020，52（6）：36-40.
	GUO Ju， JIA Shuangzhu.Study on the one⁃step hydrothermal synthesis of LiFePO₄ and its properties［J］.Inorganic Chemicals Industry，2020，52（6）：36-40.
24	HUANG Xiaopeng， ZHANG Keyu， LIANG Feng，et al.Optimized solvothermal synthesis of LiFePO₄ cathode material for enhanced high⁃rate and low temperature electrochemical performances［J］.Electrochimica Acta，2017，258：1149-1159.
25	LI Zongfeng， DONG Guixia， KANG Jingrui，et al.Preparation and electrochemical properties of nanoparticle structural LiFePO₄/C by sol-gel method as cathode material for lithium ion batteries［J］.Journal of Materials Science：Materials in Electronics，2019，30（7）：6593-6600.
26	PENG Wenxiu， JIAO Lifang， GAO Haiyan，et al.A novel sol-gel method based on FePO₄·2H₂O to synthesize submicrometer structured LiFePO₄/C cathode material［J］.Journal of Power Sour⁃ ces，2011，196（5）：2841-2847.
27	ALSAMET M A M M， BURGAZ E.Synthesis and characterization of nano⁃sized LiFePO₄ by using consecutive combination of sol-gel and hydrothermal methods［J］.Electrochimica Acta，2021，367：137530.
28	OMIDI A H， BABAEI A， ATAIE A.Low temperature synthesis of nanostructured LiFePO₄/C cathode material for lithium ion batteries［J］.Materials Research Bulletin，2020，125：110807.
29	RIGAMONTI M G， CHAVALLE M， LI He，et al.LiFePO₄ spray drying scale⁃up and carbon⁃cage for improved cyclability［J］.Journal of Power Sources，2020，462：228103.
30	ZHAO Qunfang， YU Yonghui， OUYANG Quansheng，et al.Surface modification of LiFePO₄ by coatings for improving of lithium⁃ion battery properties［J］.International Journal of Electrochemical Science，2022，17（11）：221142.
31	CAO Yue， FENG Wangjun， SU Wenxiao.The effect of different carbon sources on LiFePO₄ for electrochemical performance［J］.Integrated Ferroelectrics，2018，190（1）：13-19.
32	ZHU Shaoqing， HUANG Aoming， XU Ye.Improving methods for better performance of commercial LiFePO₄/C batteries［J］.International Journal of Electrochemical Science，2021，16（5）：210564.
33	ZHANG Yin， ALARCO J A， NERKAR J Y，et al.Observation of preferential cation doping on the surface of LiFePO₄ particles and its effect on properties［J］.ACS Applied Energy Materials，2020，3（9）：9158-9167.
34	ZHANG Dongxu， WANG Jie， DONG Kangze，et al.First principles investigation on the elastic and electronic properties of Mn，Co，Nb，Mo doped LiFePO₄ ［J］.Computational Materials Science，2018，155：410-415.
35	ZHANG Huanhuan， ZOU Zhengguang， ZHANG Shuchao，et al.A review of the doping modification of LiFePO₄ as a cathode material for lithium ion batteries［J］.International Journal of Electrochemical Science，2020，15（12）：12041-12067.
36	WANG Can， YUAN Xunlong， TAN Huiyun，et al.Three⁃dimensional carbon⁃coated LiFePO₄ cathode with improved Li-ion battery performance［J］.Coatings，2021，11（9）：1137.
37	王甲泰，赵段，马莲花，等.锂离子电池正极材料磷酸铁锂的研究进展［J］.无机盐工业，2020，52（4）：18-22.
	WANG Jiatai， ZHAO Duan， MA Lianhua，et al.Research progress of LiFePO₄ cathode materials for Li-ion battery［J］.Inorganic Chemicals Industry，2020，52（4）：18-22.
38	CAO He， WEN Lei， GUO Zhenqiang，et al.Application and prospects for using carbon materials to modify lithium iron phosphate materials used at low temperatures［J］.New Carbon Materials，2022，37（1）：46-58.
39	GENG Jing， ZHANG Shuchao， HU Xixi，et al.A review of graphene⁃decorated LiFePO₄ cathode materials for lithium⁃ion batteries［J］.Ionics，2022，28（11）：4899-4922.
40	IARCHUK A R， NIKITINA D V A， KARPUSHKIN D E A，et al.Influence of carbon coating on intercalation kinetics and transport properties of LiFePO₄ ［J］.ChemElectroChem，2019，6（19）：5090-5100.
41	KIM J K， JEONG S M.Physico⁃electrochemical properties of carbon coated LiFePO₄ nanoparticles prepared by different preparation method［J］.Applied Surface Science，2020，505：144630.
42	WANG Zhen， CHEN Da， GE Qisheng，et al.Synthesis of carbon⁃coated LiFePO₄ composites as a cathode material for improved electrochemical performance［J］.International Journal of Electrochemical Science，2019，14（5）：4611-4619.
43	JIANG Weiwei， WU Mengqiang， LIU Fei，et al.Variation of carbon coatings on the electrochemical performance of LiFePO₄ cathodes for lithium ionic batteries［J］.RSC Advances，2017，7（70）：44296-44302.
44	YI Dawei， CUI Xumei， LI Nali，et al.Enhancement of electrochemical performance of LiFePO₄@C by Ga coating［J］.ACS Omega，2020，5（17）：9752-9758.
45	CUI Xumei， YI Dawei， LI Nali，et al.Novel LaFeO₃ coating modification for a LiFePO₄ cathode［J］.Energy & Fuels，2020，34（6）：7600-7606.
46	TENG Tao， XIAO Li， SHEN Li，et al.Effect of Nb doping at Fe site on the cycling stability and rate capability of LiFePO₄ for lithium⁃ion batteries［J］.Vacuum，2022，203：111306.
47	吴星宇，阮丁山，毛林林，等.溶剂热法制备Mn掺杂LiFePO₄正极材料及其电化学性能［J］.无机化学学报，2021，37（8）：1399-1406.
	WU Xingyu， RUAN Dingshan， MAO Linlin，et al.Mn-doped LiFePO₄ cathode material：Solvothermal preparation and electrochemical performance［J］.Chinese Journal of Inorganic Chemistry，2021，37（8）：1399-1406.
48	LIU Huan， LUO Shaohua， YAN Shengxue，et al.A novel and low⁃cost iron source for synthesizing Cl-doped LiFePO₄/C cathode materials for lithium⁃ion batteries［J］.Journal of Electroanalytical Chemistry，2019，850：113434.
49	LI Xuetian， YU Lina， CUI Yonghui，et al.Enhanced properties of LiFePO₄/C cathode materials co⁃doped with V and F ions via high⁃temperature ball milling route［J］.International Journal of Hydrogen Energy，2019，44（50）：27204-27213.
50	潘晓晓，庄树新，孙雨晴，等.动力型磷酸铁锂正极材料改性的研究进展［J］.无机盐工业，2023，55（6）：18-26.
	PAN Xiaoxiao， ZHUANG Shuxin， SUN Yuqing，et al.Research progress of modified-LiFePO₄ as cathode materials for lithium ion batteries［J］.Inorganic Chemicals Industry，2023，55（6）：18- 26.
51	CONG Jun， LUO Shaohua， LI Kun，et al.High⁃performance Na-doped LiFePO₄ cathode material derived from acid⁃washed iron red for the simultaneous immobilization of multi⁃metals［J］.Ionics，2023，29（10）：3915-3926.
52	KULKA A， BRAUN A， HUANG T W，et al.Evidence for Al doping in lithium sublattice of LiFePO₄ ［J］.Solid State Ionics，2015，270：33-38.
53	LI Xuetian， SHAO Zhongbao， LIU Kuiren，et al.Enhancement of Nb-doping on the properties of LiFePO₄/C prepared via a high⁃temperature ball milling⁃based method［J］.Journal of Solid State Electrochemistry，2019，23（2）：465-473.
54	MADRAM A R， FARAJI M.Site⁃dependent electrochemical performance of Na and K co⁃doped LiFePO₄/C cathode material for lithium⁃ion batteries［J］.New Journal of Chemistry，2017，41（20）：12190-12197.
55	JIANG Shanshan， WANG Yuansheng.Synthesis and characterization of vanadium⁃doped LiFePO₄@C electrode with excellent rate capability for lithium⁃ion batteries［J］.Solid State Ionics，2019，335：97-102.
56	LIU Yuan， GU Yijing， DENG Jiali，et al.Effect of doped Mn on improving the electrochemical performance of LiFePO₄ ［J］.Journal of Materials Science：Materials in Electronics，2020，31（4）：2887-2894.
57	LIU H C， WANG Y M， HSIEH C C.Optimized synthesis of Cu-doped LiFePO₄/C cathode material by an ethylene glycol assisted co⁃precipitation method［J］.Ceramics International，2017，43（3）：3196-3201.
58	TU Jiguo， WU Kai， TANG Hui，et al.Mg-Ti co⁃doping behavior of porous LiFePO₄ microspheres for high⁃rate lithium⁃ion batteries［J］.Journal of Materials Chemistry A，2017，5（32）：17021-17028.
59	GAO Libin， XU Zhengrui， ZHANG Shu.The co⁃doping effects of Zr and Co on structure and electrochemical properties of LiFePO₄ cathode materials［J］.Journal of Alloys and Compounds，2018，739：529-535.
60	YANG Xujiao， HU Zhendong， LIANG Jun.Effects of sodium and vanadium co⁃doping on the structure and electrochemical performance of LiFePO₄/C cathode material for lithium⁃ion batteries［J］.Ceramics International，2015，41（2）：2863-2868.
61	MENG Yanshuang， LI Yuzhu， XIA Jun，et al.F-doped LiFePO₄@N/B/F-doped carbon as high performance cathode materials for Li-ion batteries［J］.Applied Surface Science，2019，476：761-768.
62	SUN C S， ZHANG Y， ZHANG X J，et al.Structural and electrochemical properties of Cl-doped LiFePO₄/C［J］.Journal of Power Sources，2010，195（11）：3680-3683.
63	WANG Xufeng， FENG Zhijun， HOU Xiaolong，et al.Fluorine doped carbon coating of LiFePO₄ as a cathode material for lithium⁃ion batteries［J］.Chemical Engineering Journal，2020，379：122371.
64	CHEN Chao， CHEN Quanqi， LI Yanwei，et al.Microspherical LiFePO_3.98F_0.02/3DG/C as an advanced cathode material for high⁃energy lithium⁃ion battery with a superior rate capability and long⁃term cyclability［J］.Ionics，2021，27（1）：1-11.
65	LI Chunlei， XIE Yingchun， ZHANG Ningshuang，et al.Optimization of LiFePO₄ cathode material based on phosphorus doped graphite network structure for lithium ion batteries［J］.Ionics，2019，25（3）：927-937.

制备方法	优点	缺点
高温固相法	原料选择广泛，成本较低；产物纯度高；工艺简单且易于控制，适合大规模生产	反应温度较高，能耗大，需要惰性气氛保护；产物粒径大，尺寸分布不均
水热法	反应条件温和，物相单一且结晶度高；产物粒径小，化学性质稳定	反应时间较长；反应条件不易控制；设备要求较高，不易于大规模生产
溶剂热法	溶剂选择灵活；物相单一且均匀性好；可使原料达到分子或原子级别的混合；产物粒径及形貌可控	成本较高；反应时间较长；溶剂回收困难，对环境不友好
溶胶-凝胶法	原料来源广泛；可实现纳米级别的均匀混合；产物粒度小，纯度高	耗时长；反应条件难以控制；不易工业化

掺杂元素	掺杂位点	电化学性能（放电比容量；容量保持率）
Na^［51］	Li_1-_x Na _x FePO₄/C	139.2 mA·h/g；98.9%
Al^［52］	Li_1-_x Al _x FePO₄	95.0 mA·h/g（0.2C）
Nb^［53］	Li_1-_x Nb _x FePO₄/C	164.9 mA·h/g；97.3%
Na&K^［54］	Li_1-_x_-_y Na _x K _y FePO₄/C	159.0 mA·h/g（0.1C）
V^［55］	LiFe_1-_x V _x PO₄/C	162.9 mA·h/g；96.0%
Mn^［56］	LiFe_1-_x Mn _x PO₄/C	156.0 mA·h/g；105.0%
Cu^［57］	LiFe_1-_x Cu _x PO₄/C	148.0 mA·h/g；99.9%
Mg&Ti^［58］	LiFe_1-_x_-_y Mg _x Ti _y PO₄	161.5 mA·h/g；99.6%
Zr&Co^［59］	Li_0.99Zr_{0.002 5}Fe_1-_x Co _x PO₄	139.9 mA·h/g；85.0%
Na&V^［60］	Li_1-_x Na _x Fe_1-_y V _y PO₄/C	156.5 mA·h/g；98.2%

掺杂元素	掺杂位点	电化学性能（放电比容量；容量保持率）
N&B&F^［61］	LiFePO_1-_x F _x	161.5 mA·h/g； 100.0%
Cl^［62］	LiFePO_1-_x Cl _x /C	162.0 mA·h/g （0.1C）
F^［63］	LiFePO_1-_x F _x	174.3 mA·h/g； 86.6%
F^［64］	LiFePO_1-_x F _x /3DG/C	158.7 mA·h/g； 98.9%
P^［65］	LiFePO₄/C-P	168.8 mA·h/g； 98.8%

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Research progress on synthesis and modification of olivine type lithium iron phosphate cathode materials

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