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

摘要/Abstract

摘要：

以氢氧化锂、乙酸锰、磷酸二氢铵和聚乙二醇为原料,采用一次喷雾干燥法制备了球形LiMnPO₄/C正极材料,并研究了煅烧温度对球形LiMnPO₄/C样品形貌、结构和电化学性能的影响。通过X射线衍射（XRD）和场发射扫描电镜（SEM）对其进行了结构和形貌的表征。结果表明,经700 ℃焙烧的LiMnPO₄/C为橄榄石型结构,在SEM下呈规则的球形,由粒径约为50 nm的一维纳米颗粒堆积而成。该样品在室温0.1C倍率下首次放电比容量可达148 mA·h/g,循环80圈后的放电比容量依然在140 mA·h/g左右,容量保持率为94.6%。

关键词: 锂离子电池, 正极材料, LiMnPO₄, 喷雾干燥法

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

中图分类号:

TQ131.11

张凯,江奥. 球形LiMnPO₄/C正极材料的喷雾干燥法制备及性能研究[J]. 无机盐工业, 2021, 53(1): 54-58.

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.

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参考文献 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.
[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.
[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.
[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.
[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.
[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.
[9]	Malik R, Burch D, Bazant M, et al. Particle size dependence of the ionic diffusivity[J]. Nano Letters, 2010,10(10):4123-4127.
[10]	Kang B, Ceder G. Battery materials for ultrafast charging and disc-harging[J]. Nature, 2009,458(7235):190-193.
[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.
[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.
[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.
[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.
[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.
[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.
[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

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球形LiMnPO₄/C正极材料的喷雾干燥法制备及性能研究

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

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