橄榄石型磷酸铁锂正极材料的合成及改性研究进展
收稿日期: 2024-05-20
网络出版日期: 2024-07-22
基金资助
国家自然青年科学基金资助项目(52104330)
Research progress on synthesis and modification of olivine type lithium iron phosphate cathode materials
Received date: 2024-05-20
Online published: 2024-07-22
橄榄石结构的磷酸铁锂（LiFePO4）作为一种性能优良的正极材料，具有成本低、容量大、环境友好等优点。但由于磷酸铁锂电池的电子电导率、离子扩散速率低等缺陷，制约了磷酸铁锂在动力电池行业的进一步发展。因此，需要有效的策略来改善磷酸铁锂的电池性能。基于此，系统阐述了高温固相法、水热/溶剂热及溶胶-凝胶法合成磷酸铁锂的具体过程及各个方法的优缺点，表明不同方法对LiFePO4的形貌及粒度影响不同。然后，分析了表面包覆、离子掺杂等改性方法对磷酸铁锂电化学性能的影响，结果表明，两种改性方法均有效改善了离子间电导率及锂离子扩散速率，显著提升其电化学性能。最后，对磷酸铁锂未来的研究方向进行展望，未来仍需深入研究LiFePO4的包覆掺杂技术，推动LiFePO4在锂离子电池行业的持续发展，提高其在高性能锂电池等领域的应用价值。
唐振强 , 蔡宗英 , 曹卫刚 , 郑珑 . 橄榄石型磷酸铁锂正极材料的合成及改性研究进展[J]. 无机盐工业, 2025 , 57(5) : 55 -63 . DOI: 10.19964/j.issn.1006-4990.2024-0281
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
| 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 LiFePO3.98F0.02/3DG/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. |
/
| 〈 |
|
〉 |
