硼酸锂包覆改性尖晶石锰酸锂的研究

doi:10.19964/j.issn.1006-4990.2021-0738

摘要/Abstract

摘要：

尖晶石型锰酸锂由于具有优异的安全性能且成本低廉，成为锂离子电池正极材料的研究热点。然而，由于锰溶解所导致的循环性能衰退是锰酸锂发展的主要障碍。随着温度的升高，锰溶解加剧，因而电池在高温条件下衰退更加严重。将硼酸锂包覆于锰酸锂表面，可以抑制锰的溶解。通过高能球磨的方法可将硼酸锂均匀地包覆于锰酸锂表面。X射线衍射与电化学阻抗表征结果表明，硼酸锂不会引起锰酸锂结构的变化和电池阻抗的增加。通过对界面转移电阻的研究发现，硼酸锂包覆量超过2%（质量分数）时电池的极化会增加，因此将硼酸锂的最佳包覆量控制在2%。相比于未经包覆的锰酸锂，经包覆的锰酸锂不论是对锂半电池还是对石墨全电池均表现出优异的循环性能，尤其是在60 ℃下的循环性能大大改善。软包全电池体积能量密度达到308 W·h/L，1C循环200次后容量保持率可达到94.7%。通过硼酸锂包覆可有效抑制锰酸锂的锰溶解，改善其循环性能。

关键词: 硼酸锂, 锰酸锂, 锂离子电池, 包覆

Abstract:

Spinel lithium manganate is a research hotspot of cathode materials for lithium?ion batteries because of its excellent safety performance and low cost.However，the degradation of cycle performance caused by manganese dissolution is the main obstacle to the development of lithium manganite.With the increase of temperature，the dissolution of manganese intensifies，so the deterioration of the battery is more serious under high temperature conditions.Coating lithium borate on the surface of lithium manganate can inhibit the dissolution of manganese.Lithium borate can be uniformly coated on the surface of lithium manganate by high?energy ball milling.X-ray diffraction and electrochemical impedance spectroscopy showed that lithium borate would not cause the change of lithium manganate structure and the increase of battery impedance.Through the study of interface transfer resistance，it was found that the polarization of the battery would increase when the coating amount of lithium borate exceeded 2%（mass fraction），so the optimal coating amount of lithium borate was controlled at 2%.Compared with uncoated lithium manganate，coated lithium manganate showed excellent cycle performance for both lithium half battery and graphite full battery.especially at 60 ℃，the cycle performance was greatly improved.The volume energy density of soft packed full battery reached 308 W·h/L，and the capacity retention rate could reach 94.7% after 200 cycles at 1C.The coating of lithium borate could effectively inhibit the dissolution of manganese in lithium manganate and improve its cycle performance.

Key words: Li₃BO₃, LiMn₂O₄, lithium?ion battery, coating

中图分类号:

O646.542

刘卓钦,周晓崇,莫梁君. 硼酸锂包覆改性尖晶石锰酸锂的研究[J]. 无机盐工业, 2022, 54(9): 90-95.

LIU Zhuoqin,ZHOU Xiaochong,MO Liangjun. Study on modification of spinel lithium manganate coated with lithium borate[J]. Inorganic Chemicals Industry, 2022, 54(9): 90-95.

图/表 9

图1

图2

图3

表1

图4

图5

图6

图7

图8

参考文献 18

[1]	ARMAND M， TARASCON J M.Building better batteries[J].Nature，2008，451（7179）:652-657.
[2]	XU Kang.Electrolytes and interphases in Li-ion batteries and beyond[J].Chemical Reviews，2014，114（23）:11503-11618.
[3]	周兰，李旺，廖文俊.界面化学对镍锰酸锂正极材料电化学性能影响的研究现状及分析[J].无机盐工业，2021，53（11）:17-24.
	ZHOU Lan， LI Wang， LIAO Wenjun.Research status and analysis of effect of interfacial chemistry on electrochemical properties of LiNi_0.5Mn_1.5O₄ cathode materials[J].Inorganic Chemicals Industry，2021，53（11）:17-24.
[4]	WINTER M， BARNETT B， XU Kang.Before Li ion batteries[J].Chemical Reviews，2018，118（23）:11433-11456.
[5]	LI Jianyuan， LIN Cong， WENG Mouyi， et al.Structural origin of the high⁃voltage instability of lithium cobalt oxide[J].Nature Nano⁃ technology，2021，16（5）:599-605.
[6]	ZHU Zhi， WANG Hua， LI Yao， et al.A surface Se-substituted LiCo[O_2– _δ Se _δ ]cathode with ultrastable high⁃voltage cycling in pouch full⁃cells[J].Advanced Materials，2020，32（50）.Doi: 10.1002/adma.202005182. doi: 10.1002/adma.202005182.
[7]	GUO Xiaolong， SONG Bin， YU Guoping， et al.Size⁃dependent me⁃mory effect of the LiFePO₄ electrode in Li-ion batteries[J].ACS Applied Materials & Interfaces，2018，10（48）:41407-41414.
[8]	JENSEN K M Ø， CHRISTENSEN M， GUNNLAUGSSON H P， et al.Defects in hydrothermally synthesized LiFePO₄ and LiFe_1- _x Mn _x PO₄ cathode materials[J].Chemistry of Materials，2013，25（11）:2282-2290.
[9]	WANG Renheng， LI Xinhai， WANG Zhixing， et al.Manganese dissolution from LiMn₂O₄ cathodes at elevated temperature:Methylene methanedisulfonate as electrolyte additive[J].Journal of Solid State Electrochemistry，2016，20（1）:19-28.
[10]	PUT B， VEREECKEN P M， LABYEDH N， et al.High cycling stability and extreme rate performance in nanoscaled LiMn₂O₄ thin films[J].ACS Applied Materials & Interfaces，2015，7（40）:22413-22420.
[11]	WARBURTON R E， IDDIR H， CURTISS L A， et al.Thermodynamic stability of low- and high⁃index spinel LiMn₂O₄ surface ter⁃minations[J].ACS Applied Materials & Interfaces，2016，8（17）:11108-11121.
[12]	FANG Guozhao， ZHU Chuyu， CHEN Minghui， et al.Suppressing manganese dissolution in potassium manganate with rich oxygen defects engaged high⁃energy⁃density and durable aqueous zinc-ion battery[J].Advanced Functional Materials，2019，29（15）.Doi:10.1002/adfm.201808375. doi: 10.1002/adfm.201808375.
[13]	GAO Aolei， SUN Zhenhua， LI Shaopeng， et al.The mechanism of manganese dissolution on Li_1.6Mn_1.6O₄ ion sieves with HCl[J].Dalton Transactions:Cambridge，England:2003，2018，47（11）:3864-3871.
[14]	WANG Jing， YU Yangyang， LI Bing， et al.Thermal synergy effect between LiNi_0.5Co_0.2Mn_0.3O₂ and LiMn₂O₄ enhances the safety of blended cathode for lithium ion batteries[J].ACS Applied Materials & Interfaces，2016，8（31）:20147-20156.
[15]	PENG Linfeng， REN Haotian， ZHANG Junzhao， et al.LiNbO₃-coated LiNi_0.7Co_0.1Mn_0.2O₂ and chlorine⁃rich argyrodite enabling high⁃performance solid⁃state batteries under different temperatures[J].Energy Storage Materials，2021，43:53-61.
[16]	OHTA S， KOMAGATA S， SEKI J， et al.All⁃solid⁃state lithium ion battery using garnet⁃type oxide and Li₃BO₃ solid electrolytes fabricated by screen⁃printing[J].Journal of Power Sources，2013，238:53-56.
[17]	CADY C W， GARDNER G， MARON Z O， et al.Tuning the electrocatalytic water oxidation properties of AB₂O₄ spinel nanocrystals:A（Li，Mg，Zn） and B（Mn，co） site variants of LiMn₂O₄ [J].ACS Catalysis，2015，5（6）:3403-3410.
[18]	OHTA S， SEKI J， YAGI Y， et al.Co-sinterable lithium garnet⁃type oxide electrolyte with cathode for all⁃solid⁃state lithium ion battery[J].Journal of Power Sources，2014，265:40-44.

项目		R₁/Ω	R₂/Ω	R₃/Ω
25 ℃	未包覆	11.3	3.2	17.7
25 ℃	Li₃BO₃包覆	11.5	3.8	17.9
60 ℃	未包覆	11.4	8.6	18.1
60 ℃	Li₃BO₃包覆	11.1	3.3	17.6

首页

全国无机盐信息中心

中国化工学会

无机酸碱盐专业委员会