两步固相碳包覆法制备磷酸锰铁锂正极材料的研究

doi:10.19964/j.issn.1006-4990.2024-0607

Abstract

Abstract:

In order to further enhance the electrochemical performance of lithium iron manganese phosphate cathode materials and alleviate particle agglomeration，a two-step solid-phase carbon coating method was employed in this study.The experimental results indicated that this preparation technique did not alter the original olivine structure of the material.Compared with the samples synthesized via the conventional solid-phase method，the materials prepared using the two-step carbon coating approach exhibited smaller particle sizes and improved dispersion.Among the three modified samples，the LMFP/C-2 material demonstrated the highest crystallinity.The electrochemical tests conducted at a rate of 0.1C（1.0C=170 mA·h/g） reveal that the initial discharge capacities of LMFP/C-1，LMFP/C-2，and LMFP/C-3 were 147.4，151.2，and 142.5 mA·h/g，respectively.After 50 charge-discharge cycles，the corresponding capacity retention rates were 94.7%，95.3%，and 94.3%.In contrast，the conventional material exhibited an initial discharge capacity of only 137.6 mA·h/g and a capacity retention rate of 93.2% after 50 cycles.These results demonstrated that the LMFP/C-2 sample prepared via the two-step solid-phase carbon coating method achieved the best electrochemical performance.Specifically，the initial discharge capacity was increased from 137.6 mA·h/g to 151.2 mA·h/g，while the capacity retention rate was improved from 93.2% to 95.3%.It indicated that the LiMn_0.8Fe_0.2PO₄/C material synthesized using this method possessesed superior cycling stability and higher initial capacity.The sintering temperature and duration significantly influenced the crystallization of lithium iron manganese phosphate.Insufficient sintering conditions would result in incomplete crystal formation，thereby deteriorating electrochemical performance.Conversely，excessive temperatures or prolonged sintering times could lead to overgrowth of crystals and increased particle agglomeration，as observed under electron microscopy.The research indicated that the cathode materials synthesized through a two-stage sintering process exhibited optimal electrochemical performance， when the first-stage sintering process was conducted at 390 ℃ for 5 h， followed by a second-stage sintering process at 650 ℃ for 6 h.

Key words: LiMn_0.8Fe_0.2PO₄, two-step solid phase method, cathode, carbon-coated

CLC Number:

TQ131.11

MIAO Pu, LUO Xiaoqiang, HOU Cuihong, RUAN Haobo, XUE Lingwei. Study on preparation of lithium ferric manganese phosphate cathode materials by two-step carbon coating methods[J]. Inorganic Chemicals Industry, 2025, 57(11): 36-42.

Figures/Tables 10

Fig.1

Fig.2

Fig 3

Fig.4

Fig.5

Fig.6

Fig.7

Fig.8

Fig.9

Fig.10

References 18

[1]	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）：1188-1194.
[2]	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 on modification of dynamic Ferrous lithium phosphate cathode materials［J］.Inorganic Chemicals Industry，2023，55（6）：18-26.
[3]	李志军，王红英，汤伟杰，等.锂离子电池正极材料LiMnPO₄/C的固相法制备及性能研究［J］.人工晶体学报，2015，44（3）：773-778.
	LI Zhijun， WANG Hongying， TANG Weijie，et al.Study on synthesis and characterization of LiMnPO₄/C cathode materials for lithium ion batteries by solid state method［J］.Journal of Synthetic Crystals，2015，44（3）：773-778.
[4]	FU L J， LIU H， LI C，et al.Electrode materials for lithium secondary batteries prepared by sol-gel methods［J］.Progress in Materials Science，2005，50（7）：881-928.
[5]	ZHANG Ping， LIU Debo.Effect of organic carbon coating prepared by hydrothermal method on performance of lithium iron phosphate battery［J］.Alexandria Engineering Journal，2023，80：1-7.
[6]	GUO Ju， WU Fuyong.Preparation of nano-spherical iron phosphate by hydrothermal method and its application as the precursor of lithium iron phosphate［J］.Journal of Electrochemical Energy Conversion and Storage，2021，18：011014.
[7]	ZHANG Junxi， XU Mingyu， CAO Xiaowei，et al.A synthesis route for lithium iron phosphate prepared by improved coprecipitati-on［J］.Functional Materials Letters，2010，3（3）：177-180.
[8]	李晶，秦元斌，宁晓辉.改进高温固相法制备磷酸锰铁锂正极材料［J］.材料导报，2020，34（16）：16001-16005.
	LI Jing， QIN Yuanbin， NING Xiaohui.Preparation of lithium manganese iron phosphate cathode material by improved high-temperature solid-state method［J］.Materials Reports，2020，34（16）：16001-16005.
[9]	NATARAJAN S， ARAVINDAN V.Burgeoning prospects of spent lithium-ion batteries in multifarious applications［J］.Advanced Energy Materials，2018，8（33）：1802303.
[10]	张彬，张萍，向晓刚，等.不同钴含量对三元正极材料性能的影响研究［J］.无机盐工业，2021，53（11）：91-94.
	ZHANG Bin， ZHANG Ping， XIANG Xiaogang，et al.Study on effect of different cobalt content on properties of ternary cathode materials［J］.Inorganic Chemicals Industry，2021，53（11）：91-94.
[11]	吴兆国，曹骏，杨则恒.基于水热/溶剂热法制备不同形貌LiNi_0.8Co_0.1Mn_0.1O₂锂离子电池正极材料［J］.无机盐工业，2022，54（2）：72-77，105.
	WU Zhaoguo， CAO Jun， YANG Zeheng.Preparation of LiNi_0.8Co_0.1Mn_0.1O₂ cathode materials with different morphologies based on hydrothermal/solvothermal method［J］.Inorganic Chemicals Industry，2022，54（2）：72-77，105.
[12]	马镰仁，谢红艳.采用两步固相法配合表面活性剂制备LiMn_0.7Fe_0.3PO₄/C正极材料的研究［J］.无机盐工业，2024，56（11）：39-44.
	MA Lianren， XIE Hongyan.Study on preparation of LiMn_0.7Fe_0.3PO₄/C cathode materials by two-step solid-phase method with surfactant［J］.Inorganic Chemicals Industry，2024，56（11）：39-44.
[13]	杜柯，伍斌，胡国荣，等.两步固相法制备正极材料LiNi_0.8Co_0.2O₂ ［J］.电池，2011，41（5）：264-267.
	DU Ke， WU Bin， HU Guorong，et al.Synthesis of cathode material LiNi_0.8Co_0.2O₂ by two-step solid state method［J］.Battery Bimonthly，2011，41（5）：264-267.
[14]	佟健，石迪辉，曹雁冰，等.两步碳包覆工艺制备锂离子电池正极复合材料LiFePO₄/C［J］.湖南有色金属，2015，31（1）：44-50.
	TONG Jian， SHI Dihui， CAO Yanbing，et al.Synthesis of double carbon-coated LiFePO₄/C composite cathode material by two-step synthesis route［J］.Hunan Nonferrous Metals，2015，31（1）：44-50.
[15]	WI S， PARK J， LEE S，et al.Synchrotron-based X-ray absorption spectroscopy for the electronic structure of Li_x Mn_0.8Fe_0.2PO₄ mesocrystal in Li⁺ batteries［J］.Nano Energy，2017，31：495-503.
[16]	AN Liwei， LI Zhenfei， REN Xin，et al.Low-cost synthesis of LiMn_0.7Fe_0.3PO₄/C cathode materials with Fe₂O₃ and Mn₃O₄ via two-step solid-state reaction for lithium-ion battery［J］.Ionics，2019，25（7）：2997-3007.
[17]	赵炯，李专，邹凌峰，等.溶胶-凝胶法结合二步烧结制备陶瓷刚玉磨料的微结构控制及晶粒细化机理［J］.粉末冶金材料科学与工程，2022，27（3）：319-326.
	ZHAO Jiong， LI Zhuan， ZOU Lingfeng，et al.Microstructure control and grain refinement mechanism of ceramic corundum abrasives prepared by sol-gel combined with two step sintering process［J］.Materials Science and Engineering of Powder Metallurgy，2022，27（3）：319-326.
[18]	冷科，李统业，喻冲，等.两步烧结制备细晶核燃料的研究［J］.核动力工程，2019，40（S2）：171-176.
	LENG Ke， LI Tongye， YU Chong，et al.Study on preparation of fine-grained nuclear fuel by two-step sintering［J］.Nuclear Power Engineering，2019，40，40（S2）：171-176.

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Study on preparation of lithium ferric manganese phosphate cathode materials by two-step carbon coating methods

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 10

References 18

Related Articles 15

Metrics

Comments

Recommended 0

[1]	WANG Zehui, LI Enze, QIU Xunzhao, SHANG Wenxin, LI Shasha, FENG Guobin, SHI Caixia. Research progress on anode and cathode electrocatalysts for hydrogen production by directly seawater electrolysis [J]. Inorganic Chemicals Industry, 2025, 57(8): 1-11.
[2]	FU Tongtong, HE Ting, ZHOU Shiyu, GU Shuai. Study on self-driven leaching of spent lithium-ion batteries cathodes and anodes with galvanic cell structure [J]. Inorganic Chemicals Industry, 2025, 57(7): 35-43.
[3]	SHEN Qirongxin, AI Dengdeng, JIN Shengping, XI Ruheng, HOU Xiaoyi. Study on effect of lithium concent on electrochemical performance of LiNi_0.90Mn_0.07Al_0.03O₂ cathode materials [J]. Inorganic Chemicals Industry, 2025, 57(7): 50-56.
[4]	DANG Jianmeng, ZHANG Zhichao, CAO Zhongkai, LI Zixuan, SHEN Jixue. Research on improving electrochemical performance of Ni-rich cathode materials under fast-charging operation [J]. Inorganic Chemicals Industry, 2025, 57(7): 14-23.
[5]	ZHENG Tianxin, YANG Yu, HUO Dongxing. Research progress on recycling technology of cathode metal materials for used lithium-ion batteries [J]. Inorganic Chemicals Industry, 2025, 57(6): 1-8.
[6]	YANG Fu, XIE Yulong. Study on preparation and Na⁺ doping modification of ternary material LiNi_0.65Co_0.15Mn_0.2O₂ [J]. Inorganic Chemicals Industry, 2025, 57(3): 43-49.
[7]	SONG Jiaxi, JI Renfei, CHEN Jun, LIN Sen, YU Jianguo. Research on characteristics analysis and pretreatment on deeply deactivated power battery ternary cathode materials [J]. Inorganic Chemicals Industry, 2025, 57(2): 44-49.
[8]	ZHANG Shanshan, ZENG Yule, ZHANG Ting, LIN Sen, LIU Chenglin. Research progress of cathode pre-lithiation technology for lithium-ion batteries [J]. Inorganic Chemicals Industry, 2025, 57(1): 1-13.
[9]	TIAN Peng, ZHANG Haoran, XU Jingang, MOU Chenxi, XU Qianjin, NING Guiling. Study on aluminum sol modified anode and cathode materials for lithium ion batteries [J]. Inorganic Chemicals Industry, 2024, 56(9): 44-53.
[10]	CHEN Xue, OUYANG Quansheng, SHAO Jiaojing. Recent research progress of lithium-sulfur batteries based on solid-solid reaction mechanism [J]. Inorganic Chemicals Industry, 2024, 56(9): 12-23.
[11]	SU Baocai, ZHANG Qin, XIE Yuanjian, CAI Pingxiong, PAN Yuanfeng. Advances in synthesis methods and structural modification of LiMnFePO₄ materials [J]. Inorganic Chemicals Industry, 2024, 56(7): 28-36.
[12]	WANG Junting, MA Hang, ZHA Zuotong, WAN Banglong, ZHANG Zhenhuan. Research progress of iron phosphate industrial wastewater treatment process [J]. Inorganic Chemicals Industry, 2024, 56(6): 26-33.
[13]	ZHOU Haitao, WEN Chengqin, ZHENG Ling, SUN Jie. Research on boron nitride modified film for cathode interface of metallic lithium battery [J]. Inorganic Chemicals Industry, 2024, 56(4): 85-89.
[14]	LIU Jie, SHI Xueru, WEI Shubing, CAO Xinxin. Artificial interface layer construction and sodium storage performance of P2-type layered oxide cathode [J]. Inorganic Chemicals Industry, 2024, 56(3): 39-44.
[15]	LIU Dexin, MA Tengyue, AN Jinling, LIU Jinrong, HE Weiyan. Study on cathode material design and electrochemical properties of manganese-based sodium ion battery [J]. Inorganic Chemicals Industry, 2024, 56(3): 51-55.