| 3,436 | 5 | 162 |
| 下载次数 | 被引频次 | 阅读次数 |
作为锂离子电池正极材料之一，磷酸锰铁锂具有能量密度大、安全性好、成本较低等优点，被认为是磷酸铁锂理想的升级品。但是，磷酸锰铁锂较低的电导率和Li+扩散系数限制了其商业化应用。介绍了磷酸锰铁锂材料性能，总结了高温固相法、共沉淀法、溶胶凝胶法、水热/溶剂热法等合成方法的优缺点，综述了碳包裹、纳米化及形貌控制、离子掺杂等改性策略，指出磷酸锰铁锂材料应具有一个合适的锰铁原子数量比；在总结前人研究成果的基础上，展望了未来磷酸锰铁锂正极材料的研究方向。
Abstract：As one of the cathode materials for lithium ion batteries, lithium manganese phosphate has the advantages of high energy density, good safety and low cost, and is considered as the ideal upgrade of lithium iron phosphate. However, the low conductivity and Li+ diffusion coefficient of lithium manganese phosphate limit its commercial application. The properties of lithium manganese phosphate material were introduced, and the advantages and disadvantages of synthesis method such as high temperature solid state method, coprecipitation method, sol-gel method and hydrothermal/solvothermal method were summarized. the modification strategies such as carbon coating, nanocrystallization, morphology control and ion doping were summarized. It was pointed out that lithium manganese phosphate materials should have a suitable atomic ratio of manganese and iron. On the basis of summarizing previous research achievements, the future research directions of lithium manganese phosphate cathode materials were prospected.
[1] BIBI S,KHAN A,KHAN S,et al.Synthesis of Cr doped LiMnPO4 cathode materials and investigation of their dielectric properties[J].International Journal of Energy Research,2021,46(2):810-821.
[2] CHEN X L,GONG Y D,LI X,et al.Perspective on low-temperature electrolytes for LiFePO4-based lithium-ion batteries[J].International Journal of Minerals,Metallurgy and Materials,2022,30(1):1-13.
[3] WAND X F,FENG Z J,HOU X L,et al.Fluorine doped carbon coating of LiFePO4 as a cathode material for lithiu-mion batteries[J].Chemical Engineering Journal,2020,379:122371.
[4] RAO N B,NARSIMULU D,SATYANARAYANA N,et al.Effect of Mg doping on the electrical,dielectric and relaxation properties of LiMnPO4 nanoparticles[J].Indian Journal of Physics,2021,96(4):1-7.
[5] HAN J,YANG J,LU H C,et al.Effffect of synthesis processes on the microstructure and electrochemical properties of LiMnPO4 cathode material[J].Industrial & Engineering Chemistry Research,2022,61:7451-7463.
[6] YANG H,FU C M,SUN Y J,et al.Fe-doped LiMnPO4@C nanofifibers with high Li-ion diffusion coeffificient[J].Carbon,2020,158:102-109.
[7] LUO C,JIANG Y,ZHANG X X,et al.Misfit strains inducing voltage decay in LiMnyFe1-yPO4/C[J].Journal of Energy Chemistry,2022,68:206-212.
[8] YANG L,DENG W,XU W,et al.Olivine LiMnxFe1-xPO4 cathode materials for lithium ion batteries:restricted factors of rate performances[J].Journal of Materials Chemistry A,2021,9(25):14214-14232.
[9] WANG L,LI Y,WU J,et al.Synthesis mechanism and cha-racterization of LiMn0.5Fe0.5PO4/C composite cathode material for lithium-ion batteries[J].Journal of Alloys and Compounds,2020,839:1-7.
[10] WANG L,ZHANG H Q,LI Y,et al.Improving the rate performance of LiMn0.5Fe0.5PO4/C materials by the precursor method[J].Journal of Materials Research and Technology,2022,20:4018-4025.
[11] BEZZA I,AZIAM H,SAADOUNE I,et al.On the LiFe1-xMnxPO4 (x=0,0.4,0.6,0.65,1) olivine-type cathode materials for lithium ion batteries[J].Materials Today:Proceedings,2022,51:1913-1917.
[12] TRINH D V,NGUYEN M T T,Dang H T M,et al.Hydrothermally synthesized nanostructured LiMnxFe1-xPO4 (x=0-0.3) cathode materials with enhanced properties for lithium-ion batteries[J].Scientifc Reports,2021,11(1):12280.
[13] LUO T,ZENG T T,CHEN S L,et al.Structure,perfor-mance,morphology and component transformation mechanism of LiMn0.8Fe0.2PO4/C nanocrystal with excellent stability[J].Journal of Alloys and Compounds,2020,834:155143.
[14] ZHANG X,HOU M Y,TAMIRATE A G,et al.Carbon coated nano-sized LiMn0.8Fe0.2PO4 porous microsphere cathode material for Li-ion batteries[J].Journal of Power Sources,2019,448:227438.
[15] FREDJ E B,ROUSSELOT S,DANIS L,et al.Synthesis and characterization of LiFe1-xMnxPO4 (x=0.25,0.50,0.75) lithium ion battery cathode synthesized via a melting process[J].Journal of Energy Storage,2020,27:101116.
[16] LI Y C,XU G R,FAN S M,et al.Synthesis of carbon-coated LiMn0.8Fe0.2PO4 materials via an aqueous rheological phase-assisted solid-state method[J].Journal of Solid State Electrochemistry,2020,24(4):821-828.
[17] LI Z F,REN X,ZHENG Y,et al.Double-layer carbon-coating method for simultaneous improvement of conducti-vity and tap density of LiMn0.65Fe0.35PO4/C/KB cathode materials[J].ACS Applied Energy Materials,2020,3(9):8573-8582.
[18] LI Z F,REN X,TIAN W C,et al.LiMn0.6Fe0.4PO4/CA cathode materials with carbon aerogel as additive synthesized by wet ball-milling combined with spray drying[J].Journal of The Electrochemical Society,2020,167(9):1-9.
[19] XIE X M,ZHANG B C,HU G R,et al.A new route for green synthesis of LiFe0.25Mn0.75PO4/C@rGO material for lithium ion batteries[J].Journal of Alloys & Compounds,2021,853:157106.
[20] LI J L,WANG Y,WU J H,et al.CNT-embedded LiMn0.8Fe0.2PO4/C microsphere cathode with high rate capability and cycling stability for lithium ion batteries[J].Journal of Alloys and Compounds,2018,731:864-872.
[21] ZHANG B C,MENG W,GONG Y F,et al.[001]-oriented LiMn0.6Fe0.4PO4/C nanorod-microspheres contributing high-rate performance to olivine-structured cathode for lithium-ion battery[J].Materials Today Energy,2022,30:101162.
[22] WU K P,YIN S,WANG S,et al.Construction of submicron-sized LiFe0.4Mn0.6PO4/C enwrapped into graphene framework for advanced Li-storage[J].Carbon,2020,169:55-64.
[23] TIAN W C,ZHENG Y,ZHANG K C,et al.Facile synthesis and excellent electrochemical performance of LiMn0.6-Fe0.4PO4/C with 3D conductive network[J].Ionics,2020,26(12):5981-5989.
[24] WANG L,LI Y,WANG Y K,et al.Effect of vacuum assistance on the morphology and electrochemical properties of LiMn0.2Fe0.8PO4/C composites prepared by solid-phase method[J].Electrochimica Acta,2020,36:137675.
[25] 赵露，宁国庆，李兴洵.掺硫碳纳米管作导电添加剂改进磷酸锰铁锂电化学性能[J].化工学报，2021,72(12):6388-6398.ZHAO L,NING G Q,LI X X.S-doped carbon nanotubes used as conductive additives to improve the electrochemical performance of LMFP[J].CIESC Journal,2021,72(12):6388-6398.
[26] FAN R Z,FAN C L,HU Z,et al.Construction of high performance N-doped carbon coated LiMn0.8Fe0.2PO4 nanocrystal cathode for lithium-ion batteries[J].Journal of Alloys and Compounds,2021,876:160090.
[27] CUI X L,TUO K Y,DONG H,et al.Modification of phosphorus-doped carbon coating enhances the electrochemical performance of LiFe0.8Mn0.2PO4 cathode material[J].Journal of Alloys and Compounds,2021,885:160946.
[28] YU M,LI J,NING X H.Improving electrochemical perfor-mance of LiMn0.5Fe0.5PO4 cathode by hybrid coating of Li3VO4 and carbon[J].Electrochimica Acta,2021,368:137597.
[29] CHANG H,LI Y,FANG Z K,et al.Construction of carbon-coated LiMn0.5Fe0.5PO4@ Li0.33La0.56TiO3 nanorod composites for high-performance Li-ion batteries[J].ACS Applied Materials & Interfaces 2021,13(28):33102-33111.
[30] 张凯成.磷酸锰铁锂正极材料的合成与改性研究[D].天津：河北工业大学，2022.ZHANG K C.Study on synthesis and modification of lithium manganese iron phosphate cathode materials[D].Tianjin:Hebei University of Technology,2022.
[31] 汪志华.高比能磷酸锰铁锂正极材料的结构设计及电化学改性研究[D].武汉：武汉工程大学，2022.WANG Z H.Study on structural design and electrochemical modification of lithium manganese phosphate cathode material with high specific energy[D].Wuhan:Wuhan Institute of Technology,2022.
[32] LIU S J,ZHENG J G,ZHANG B,et al.Engineering manganese-rich phospho-olivine cathode materials with exposed crystal {010} facets for practical Li-ion batteries[J].Chemical Engineering Journal,2023,454(1):139986.
[33] ZHANG K C,CAO J R,TIAN S Y,et al.The prepared and electrochemical property of Mgdoped LiMn0.6Fe0.4PO4/C as cathode materials for lithiumion batteries[J].Ionics,2021,27(11):4629-4637.
[34] TIAN S Y,ZHANG K C,CAO J R,et al.Spherical Ni-doped LiMn0.6Fe0.4PO4/C composites with high-rate performance[J].Ionics,2021,27(7):1-11.
[35] HUANG Z G,LI J T,WANG K,et al.Synthesis of LiFe0.4Mn0.4Co0.2PO4/C cathode material of lithium ion battery with enhanced electrochemical performance[J].Journal of Alloys and Compounds,2018,782:413-420.
[36] JIN H B,ZHANG J H,QIN L,et al.Dual modification of olivine LiFe0.5Mn0.5PO4 cathodes with accelerated kinetics for high-rate lithium-ion batteries[J].Industrial & Engineering Chemistry Research,2023,62:1029-1034.
[37] JENSEN K,CHRISTENSEN M,TYRSTED C,et al.Real-time synchrotron powder X-ray diffraction study of the antisite defect formation during sub- and supercritical synthesis of LiFePO4 and LiFe1-xMnxPO4 nanoparticles[J].Journal of Applied Crystallography,2011,44(2):287-294.
[38] 王杰.非化学计量磷酸锰铁锂的制备与电化学性能研究[D].广州：华南理工大学，2021.WANG J.Study on the synthesis and electrochemical performance of non-stoichiometric lithium ferromanganese phosphate[D].Guangzhou:South China University of Technology,2021.
[39] GONG S M,BAI X,LIU R,et al.Study on discharge voltage and discharge capacity of LiFe1-xMnxPO4 with high Mn content[J].Journal of Materials Science.Materials in Electronics,2020,31(10):7742-7752.
[40] LI S Q,MENG X Y,YI Q,et al.Structural and electrochemical properties of LiMn0.6Fe0.4PO4 as a cathode material for flexible lithium-ion batteries and self-charging power pack[J].Nano Energy,2018,52:510-516.
[41] XIAO P F,DING B,LAI M O,et al.High performance LiMn1-xFexPO4(0≤x≤1) synthesized via a facile polymer-assisted mechanical activation[J].Journal of The Electrochemical Society,2013,160(6):A918-A926.
[42] WANG L,LI Y,DAI Y N,et al.Effect of Mn content on electrochemical performance and energy density of LiFe1-xMnxPO4/C[J].Vacuum,2022,196:110730.
[43] FANG K B,ZHU J H,XIE Q,et al.Synthesis of Fe2+ substituted high-performance LiMn1-xFexPO4/C (x=0,0.1,0.2,0.3,0.4) cathode materials for lithium-ion batteries via sol-gel processes[J].Molecules,2021,26(24):7641.
基本信息:
DOI：10.16283/j.cnki.hgkwyjg.2024.04.004
中图分类号:TM912;TQ131.11
引用信息:
[1]刘帅杰,孙妍,邓子昭.磷酸锰铁锂正极材料研究进展[J].化工矿物与加工,2024,53(04):24-32.DOI:10.16283/j.cnki.hgkwyjg.2024.04.004.
2023-06-09
2023-06-09
2023-06-09