球形LiMnPO4/C正极材料的喷雾干燥法制备及性能研究

doi:10.11962/1006-4990.2020-0101

Abstract

Abstract:

One-time spray-drying method was used to prepare spherical LiMnPO₄/C cathode materials with lithium hydroxide,manganese acetate,NH₄H₂PO₄ and polyethylene glycol as raw materials.The effect of calcination temperature on the morpho-logy,structure and electrochemical performance of spherical LiMnPO₄/C samples was studied.Its structure and morphology were characterized by X-ray diffraction（XRD）and field emission scanning electron microscopy（SEM）.The morphology and prechemical properties of LiMnPO₄/C obtained after calcination at different temperatures are quite different.The results showed that the spherical LiMnPO₄/C calcined at 700 ℃ had olivine-type crystal structure,and it showed a spherical shape composed of one-dimensional nano particles with a diameter of about 50 nm under SEM.The specific discharge capacity of this sample reached 148 mA·h/g for the first time at a rate of 0.1C at room temperature.After 80 cycles,the specific discharge capacity was still around 140 mA·h/g,and the capacity retention rate was 94.6%.

Key words: lithium-ion batteries, cathode material, LiMnPO₄, spray drying method

CLC Number:

TQ131.11

Zhang Kai,Jiang Ao. Preparation and properties of spherical LiMnPO₄/C cathode materials by spray drying method[J]. Inorganic Chemicals Industry, 2021, 53(1): 54-58.

Figures/Tables 8

References 20

[1]	Delacourt C, Laffont L, Bouchet R, et al. Toward understanding of electrical limitations(electronic,ionic) in LiMPO₄(M=Fe,Mn) el-ectrode materials[J]. Journal of the Electrochemical Society, 2005,152(5):A913-A921. doi: 10.1149/1.1884787
[2]	Padhi A K, Nanjundaswamy K S, Goodenough J B. Phospho-olivines as positive-electrode materials for rechargedeadle lithiu batteries[J]. Journal of the Electrochemical Society, 1997,144(4):1188-1194. doi: 10.1149/1.1837571
[3]	Yang C, Wang X, Liu G, et al. One-step hydrothermal synjournal of Ni-Co sulfide on Ni foam as a binder-free electrode for lithium-sulfur batteries[J]. Journal of Colloid and Interface Science, 2020,565(1):378-387. doi: 10.1016/j.jcis.2019.12.112
[4]	Padhi A K, Nanjundaswamy K S, Masquelier C, et al. Effect of struc-ture on the Fe²+/Fe³+ redox couple in iron phosphates[J]. Journal of the Electrochemical Society, 1997,144(5):1609-1613. doi: 10.1149/1.1837649
[5]	Yin S C, Grondey H, Strobel P, et al. Electrochemical property:St-ructure relationships in monoclinic Li_3-yV₂(PO₄)₃[J]. ChemInform, 2003,125(34):10402-10411.
[6]	Deng C, Zhang S, Ma L, et al. Effects of precipitator on the morpho-logical,structural and electrochemical characteristics of Li[Ni_1/3Co_1/3Mn_1/3]O₂ prepared via carbonate co-precipitation[J]. Jo-urnal of Alloys and Compounds, 2011,509(4):1322-1327.
[7]	Yang S Y, Wang X Y, Yang X K, et al. Influence of Li source on tap density and high rate cycling performance of spherical Li[Ni_1/3Co_1/3Mn_1/3]O₂ for advanced lithium-ion batteries[J]. Journal of Solid State Electrochemistry, 2012,16(3):1229-1237. doi: 10.1007/s10008-011-1513-6
[8]	Wang L, Zhang L, Lieberwirth I, et al. A Li₃V₂(PO₄)₃/C thin film with high rate capability as a cathode material for lithium-ion batteries[J]. Electrochemistry Communications, 2010,12(1):52-55. doi: 10.1016/j.elecom.2009.10.034
[9]	Malik R, Burch D, Bazant M, et al. Particle size dependence of the ionic diffusivity[J]. Nano Letters, 2010,10(10):4123-4127. pmid: 20795627
[10]	Kang B, Ceder G. Battery materials for ultrafast charging and disc-harging[J]. Nature, 2009,458(7235):190-193. doi: 10.1038/nature07853 pmid: 19279634
[11]	Wang L, He X, Sun W, et al. Crystal orientation tuning of LiFePO₄ nanoplates for high rate lithium battery cathode materials[J]. Nano Letters, 2012,12(11):5632-5636. doi: 10.1021/nl3027839 pmid: 23074971
[12]	Padhi A K, Archibald W B, Nanjundaswamy K S, et al. Ambient and high-pressure structures of LiMnVO₄ and its Mn³+/Mn²+ redox en-ergy[J]. Journal of Solid State Chemistry, 1997,128(2):267-272. doi: 10.1006/jssc.1996.7217
[13]	Wei Y J, Liang G C, Wang L, et al. Synjournal and electrochemical performance of LiFe_1-xMn_xPO₄/C cathode material[J]. Advanced Materials Research, 2011,347-353(1):3434-3438. doi: 10.4028/www.scientific.net/AMR.347-353
[14]	Jiang A, Wang X, Gao M, et al. Enhancement of electrochemical properties of niobium-doped LiFePO₄/C synthesized by sol-gel met-hod[J]. Journal of the Chinese Chemical Society, 2018,65(8):977-981. doi: 10.1002/jccs.2018.65.issue-8
[15]	Zhou F, Zhu P, Fu X, et al. Comparative study of LiMnPO₄ cathode materials synthesized by solvothermal methods using different manganese salts[J]. CrystEngComm, 2013,16(5):766-774. doi: 10.1039/C3CE41567H
[16]	Wang X, Zhao X, Wang J, et al. Electrospun Li₃V₂(PO₄)₃ nanobel-ts:synjournal and electrochemical properties as cathode materials of lithium-ion batteries[J]. Journal of the Chinese Chemical Socie-ty, 2017,64(5):97-104.
[17]	Hu P, Zhong K, Zhang C, et al. Spray drying synjournal and electro-chemical performance of lithium ion battery cathode materials LiNi_0.5Mn_1.5O₄[J]. Journal of Synthetic Crystals, 2015,44(8):2184-2190.
[18]	Wang Y, Wang X, Jiang A, et al. A versatile nitrogen-doped carbon coating strategy to improve the electrochemical performance of LiFePO₄ cathodes for lithium-ion batteries[J]. Journal of Alloys and Compounds, 2019,810(25):151889. doi: 10.1016/j.jallcom.2019.151889
[19]	Doan T N L, Bakenov Z, Taniguchi I. Preparation of carbon coated LiMnPO₄ powders by a combination of spray pyrolysis with dry ball-milling followed by heat treatment[J]. Advanced Powder Te-chnology, 2010,21(2):187-196.
[20]	Fan L, Wu L, Guan M, et al. Preparation of LiFe_(1-3y/2)Al_yPO₄ cathode material by precursor-doping combined room temperature reduc-tion via ball-milling[J]. The Chinese Journal of Nonferrous Metals, 2014,24(2):468-475.

样品	a/nm	b/nm	c/nm	晶胞体积/ nm³	D₁₃₁/nm
LMP-500	0.606 994	0.473 751	1.602 74	0.299 75	2.405 3
LMP-600	0.606 932	0.473 722	1.605 55	0.300 48	2.468 5
LMP-700	0.607 234	0.473 983	1.605 31	0.301 12	2.512 4
LMP-800	0.608 342	0.474 996	1.606 24	0.301 98	2.589 6
LMP-900	0.609 667	0.475 445	1.608 68	0.303 30	2.671 2

样品	R_e/Ω	R_ct/Ω	σ/ （Ω·s^-1/2）	D/ （cm²·s^-1）	i^o/ （mA·cm^-2）
LMP-600	7.025	308.52	79.44	1.82×10^-16	8.18×10^-5
LMP-700	3.480	82.548	135.6	1.04×10^-16	3.06×10^-4
LMP-800	4.658	98.206	78.21	1.85×10^-16	2.57×10^-4

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Preparation and properties of spherical LiMnPO₄/C cathode materials by spray drying method

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 8

References 20

Related Articles 15

Metrics

Comments

Recommended 0

[1]	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.
[2]	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.
[3]	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.
[4]	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.
[5]	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.
[6]	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.
[7]	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.
[8]	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.
[9]	LI Yaguang, HAN Dongzhan, QI Lijuan. Recent research on pretreatment of waste lithium-ion batteries and electrolyte recovery technology [J]. Inorganic Chemicals Industry, 2024, 56(2): 1-10.
[10]	ZHOU Huang, HU Xiaoping, REN Wen, CAO Xinxin. Preparation and sodium storage properties of sulfur-doped Na₃（VOPO₄）₂F cathode materials [J]. Inorganic Chemicals Industry, 2024, 56(2): 30-37.
[11]	GE Jianhua, XIE Minyan, OUYANG Quansheng, SHAO Jiaojing. Advances in regeneration processes of cathode materials for spent power batteries [J]. Inorganic Chemicals Industry, 2024, 56(12): 79-87.
[12]	ZHAO Runze, QIAN A′niu. Research progress of lithium recovery for spent lithium-ion batteries and preparation in battery-grade lithium carbonate [J]. Inorganic Chemicals Industry, 2024, 56(12): 70-78.
[13]	LIU Jiasheng, LUO Xiaoqiang, HOU Cuihong, XUE Lingwei. Effects of fluorine doping on electrochemical behavior of LiMn_0.8Fe_0.2PO₄/C cathode materials [J]. Inorganic Chemicals Industry, 2024, 56(11): 45-50.
[14]	LIU Juan, JIANG Qinglai, ZHANG Yueyi. Study on Al-Zn co-doping of 4.6 V high voltage lithium cobalt oxide cathode materials [J]. Inorganic Chemicals Industry, 2024, 56(11): 59-64.
[15]	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.

Preparation and properties of spherical LiMnPO4/C cathode materials by spray drying method