锂离子电池材料钛酸锂钠的研究进展

doi:10.19964/j.issn.1006-4990.2020-0598

Abstract

Abstract:

Na₂Li₂Ti₆O₁₄ battery has the characteristics of low potential platform（1.3V） and low economic cost,which is of great significance to portable electronic devices,energy vehicles,ecological environment and other fields.Due to the low intrinsic ionic conductivity of lithium sodium titanate battery,improving the lithium ion diffusion coefficient of lithium sodium titanate battery is the main research direction at present.Therefore,the structure characteristics of lithium sodium titanate and the influence of synthesis methods on the particle size,morphology and electrochemical performance of lithium sodium titanate were reviewed.The effect of different doping ions and surface coating modification on the discharge specific capacity,cycle performance and ion diffusion coefficient of lithium sodium titanate battery were compared.Adding proper amount of niobium led to higher lithium ion diffusion coefficient,and coated carbon nanotubes had higher capacity retention,which was helpful to further improve the electrochemical performance of lithium sodium titanate battery.

Key words: lithium ion battery, anode material, lithium sodium titanate, ion doping, surface coating

CLC Number:

TQ131.11

Liu Yang,Cai Zongying,Cao Weigang,Liu Yuzhao. Research progress on lithium sodium titanate for lithium ion batteries[J]. Inorganic Chemicals Industry, 2021, 53(10): 36-40.

Figures/Tables 3

Fig.1

Table 1

Table 2

References 44

[1]	Kubota K, Kumakura S, Yoda Y, et al. Electrochemistry and solid-state chemistry of NaMeO₂(Me=3 d transition metals)[J]. Advanced Energy Materials, 2018, 8(17).Doi: 10.1002/aenm.201703415. doi: 10.1002/aenm.201703415
[2]	Ohzuku T, Ueda A, Yamamoto N. Zero-strain insertion material of Li[Li_1/3Ti_5/3]O₄ for rechargeable lithium cells[J]. Journal of the Elec-Electrochemical Society, 1995, 142(5):1431-1435.
[3]	Huang S, Wen Z, Zhu X, et al. Preparation and electrochemical per-formance of Ag doped Li₄Ti₅O₁₂[J]. Electrochemistry Communicatio-ns, 2004, 6(11):1093-1097.
[4]	Dambournet D, Belharouak I, Amine K. MLi₂Ti₆O₁₄(M=Sr,Ba,2Na)lithium insertion titanate materials:A comparative study[J]. Inor-ganic Chemistry, 2010, 49(6):2822-2826.
[5]	朱彦荣, 刘思远, 诸荣孙, 等. 锂离子电池 MLi₂Ti₆O₁₄(M=2Na,Sr,Ba)负极材料的研究进展[J]. 化工新型材料, 2018, 46(2):35-39.
[6]	Wu K, Wang D, Lin X, et al. Comparative study of Na₂Li₂Ti₆O₁₄ pre-pared by different methods as advanced anode material for lithium-ion batteries[J]. Journal of Electroanalytical Chemistry, 2014, 717:10-16.
[7]	Torres-Martínez L M, Ibarra J, Loredo J R, et al. Phase formation and crystal structure of ternary compound Na₂Li₂Ti₆O₁₄[J]. Solid St-ate Sciences, 2007, 8(11):1281-1289.
[8]	梁康, 任玉荣, 唐有根, 等. 钛酸锂用于钠离子电池负极的研究进展[J]. 材料导报, 2020, 34(9):9041-9047.
[9]	Yi T F, Zhu Y R, Tao W, et al. Recent advances in the research of MLi₂Ti₆O₁₄(M=2Na,Sr,Ba,Pb) anode materials for Li-ion batteri-es[J]. Journal of Power Sources, 2018, 399:26-41. doi: 10.1016/j.jpowsour.2018.07.086
[10]	Li P, Wu K, Wang P, et al. Preparation,electrochemical character-ization and in-situ kinetic observation of Na₂Li₂Ti₆O₁₄ as anode ma-terial for lithium ion batteries[J]. Ceramics International, 2015, 41(10):14508-14516. doi: 10.1016/j.ceramint.2015.07.095
[11]	Shu J, Wu K, Wang P, et al. Lithiation and delithiation behavior of sodium lithium titanate anode[J]. Electrochimica Acta, 2015, 173:595-606. doi: 10.1016/j.electacta.2015.05.106
[12]	唐好庆, 王皓东, 朱姜涛, 等. 锂离子电池负极材料Li₂Na₂Ti₆O₁₄的制备及其电化学性能研究[C]//中国电子学会化学与物理电源技术分会. 第31届全国化学与物理电源学术年会, 2015.
[13]	Yin S Y, Song L, Wang X Y, et al. Reversible lithium storage in Na₂Li₂Ti₆O₁₄ as anode for lithium ion batteries[J]. Electrochemistry Communications, 2009, 11(6):1251-1254. doi: 10.1016/j.elecom.2009.04.013
[14]	李震春, 邓健秋, 王仲民, 等. 锂离子电池负极材料Na₂Li₂Ti₆O₁₄的嵌脱锂过程动力学研究[J]. 桂林电子科技大学学报, 2012, 32(3):249-253.
[15]	Zhang H, Gao X P, Li G R, et al. Electrochemical lithium storage of sodium titanate nanotubes and nanorods[J]. Electrochimica Ac-ta, 2008, 53(24):7061-7068.
[16]	Zhao F, Xue P, Ge H, et al. Na-doped Li₄Ti₅O₁₂ as an anode materi-al for sodium-ion battery with superior rate and cycling performan-ce[J]. Journal of The Electrochemical Society, 2016, 163(5):A690-A695. doi: 10.1149/2.0781605jes
[17]	王杰. 负极材料钛酸锂的液相制备及性能研究[D]. 合肥: 合肥工业大学, 2018.
[18]	Fan S S, Zhong H, Yu H T, et al. Hollow and hierarchical Na₂Li₂Ti₆O₁₄ microspheres with high electrochemical performance as anode ma-terial for lithium-ion battery[J]. Science China Materials, 2017, 60(5):427-437. doi: 10.1007/s40843-017-9033-5
[19]	杜敏, 宋滇, 谢玲, 等. 静电纺丝在高效可逆离子电池储能中的应用[J]. 材料导报, 2018, 32(19):3281-3294.
[20]	Yan W, Zhang X, Long N, et al. Na₂Li₂Ti₆O₁₄ nanowires as ultra-long cycling performance anode material for lithium ion storage[J]. Ce-ramics International, 2020, 46(10).Doi: 10.1016/j.ceramint.2020.03.022. doi: 10.1016/j.ceramint.2020.03.022
[21]	Wang C, Xin X, Shu M, et al. Scalable synjournal of one-dimensional Na₂Li₂Ti₆O₁₄ nanofibers as ultrahigh rate capability anodes for lithi-um-ion batteries[J]. Inorganic Chemistry Frontiers, 2019, 6(3):646-653. doi: 10.1039/C8QI00973B
[22]	Abbasian A R, Rahimipour M R, Hamnabard Z. Hydrothermal sy-njournal of lithium meta titanate nanocrystallites[J]. Procedia Ma-terials Science, 2015, 11:336-341.
[23]	尹盛玉. 锂离子电池负极材料钛酸盐的合成及电化学性能研究[D]. 武汉: 武汉大学, 2010.
[24]	高利亭, 唐致远, 张新河, 等. 熔盐辅助固相法制备尖晶石型钛酸锂[J]. 电源技术, 2015, 39(3):458-460.
[25]	Yin S Y, Feng C Q, Wu S J, et al. Molten salt synjournal of sodium lithium titanium oxide anode material for lithium ion batteries[J]. Journal of Alloys and Compounds, 2015, 642:1-6. doi: 10.1016/j.jallcom.2015.04.113
[26]	蔡枝英. 新型锂离子电池负极材料 NaLiTi₃O₇ 的制备及其电化学性能研究[D]. 长沙: 中南大学, 2012.
[27]	唐致远, 阳晓霞, 陈玉红, 等. 钛酸锂电极材料的研究进展[J]. 电源技术, 2007, 31(4):332-336.
[28]	Lan H, Qian S, Wang Q, et al. Sr₁-_xNa₂_xLi₂Ti₆O₁₄(0≤x≤1) as anode materials for rechargeable Li-ion batteries[J]. Ceramics Internatio-nal, 2017, 43(1):1552-1557.
[29]	Wang P F, Qian S S, Yi T F, et al. Effect of sodium-site doping on enhancing the lithium storage performance of sodium lithium titanate[J]. ACS Applied Materials & Interfaces, 2016, 8(16):10302-10314.
[30]	Wang P F, Li P, Yi T F, et al. Improved lithium storage performance of lithium sodium titanate anode by titanium site substitution with aluminum[J]. Journal of Power Sources, 2015, 293:33-41. doi: 10.1016/j.jpowsour.2015.05.076
[31]	Lao M, Li P, Wang P, et al. Advanced electrochemical performance of Li_1.95Al_0.05Na₂Ti₆O₁₄ anode material for lithium ion batteries[J]. Electrochimica Acta, 2015, 176:694-704. doi: 10.1016/j.electacta.2015.07.082
[32]	Sun C, Li X, Wu X, et al. Improved the lithium storage capability of Na₂Li₂Ti₆O₁₄ by barium doping[J]. Journal of Electroanalytical Chemistry, 2017, 802:100-108. doi: 10.1016/j.jelechem.2017.09.007
[33]	Tao W, Xu M L, Zhu Y R, et al. Structure and electrochemical per-formance of BaLi₂-_xNa_xTi₆O₁₄(0≤x≤2) as anode materials for lithi- um-ion battery[J]. Science China Materials, 2017, 60(8):728-738. doi: 10.1007/s40843-017-9065-8
[34]	Lao M, Qian S, Yu H, et al. Enhanced electrochemical properties of Mg²⁺ doped Li₂Na₂Ti₆O₁₄ anode material for lithium-ion batteri-es[J]. Electrochimica Acta, 2016, 196:642-652. doi: 10.1016/j.electacta.2016.03.035
[35]	Wang P, Li P, Yi T F, et al. Enhanced lithium storage capability of sodium lithium titanate via lithium-site doping[J]. Journal of Power Sources, 2015, 297:283-294. doi: 10.1016/j.jpowsour.2015.08.007
[36]	Lao M, Lin X, Li P, et al. Preparation and electrochemical charac-terization of Li₂+_xNa₂_-xTi₆O₁₄ (0≤x≤0.2) as anode materials for li-thium-ion batteries[J]. Ceramics International, 2015, 41(2):2900-2907. doi: 10.1016/j.ceramint.2014.10.115
[37]	袁华, 何云蔚, 艾常春. 钛酸锂作为锂离子电池负极材料的改性进展[J]. 武汉工程大学学报, 2014, 36(8):20-26.
[38]	Han X, Gui X, Tao W, et al. Facile strategy to fabricate Na₂Li₂Ti₆O₁₄@Li_0.33La_0.56TiO₃ composites as promising anode materials for lithium-ion battery[J]. Ceramics International, 2018, 44(11).Doi: 10.1016/j.ceramint.2018.04.013. doi: 10.1016/j.ceramint.2018.04.013
[39]	Wu K, Shu J, Lin X, et al. Enhanced electrochemical performance of sodium lithium titanate by coating various carbons[J]. Journal of Power Sources, 2014, 272:283-290. doi: 10.1016/j.jpowsour.2014.08.088
[40]	Wu K, Lin X, Shao L, et al. Copper/carbon coated lithium sodium titanate as advanced anode material for lithium-ion batteries[J]. Journal of Power Sources, 2014, 259:177-182. doi: 10.1016/j.jpowsour.2014.02.097
[41]	Ma W W, Yu H T, Guo C F, et al. Improving the structural stability and electrochemical performance of Na₂Li₂Ti₆O₁₄ nanoparticles via MgF₂ coating[J]. RSC Advances, 2019, 9(28).Doi: 10.1039/C9RA02392E. doi: 10.1039/C9RA02392E
[42]	马薇薇. NaLiTi₃O₇负极材料的形貌控制、表面包覆及电化学性能[D]. 哈尔滨: 黑龙江大学, 2019.
[43]	Qian S, Yu H, Yan L, et al. Ag enhanced electrochemical perfor ma-nce for Na₂Li₂Ti₆O₁₄ anode in rechargeable lithium-ion batteries[J]. Ceramics International, 2016, 42(6):6874-6882. doi: 10.1016/j.ceramint.2016.01.071
[44]	Prihandoko B, Priyono S, Subhan A, et al. Variation of carbon coat-ing on Li₂Na₂Ti₆O₁₄ as anode material of lithium battery[J]. IOP Conference Series:Materials Science and Engineering, 2017, 202.Doi: 10.1088/1757-899X/202/1/012053. doi: 10.1088/1757-899X/202/1/012053

掺杂离子	取代位置	最佳掺杂分子式	初始放电容量/（mA·h·g^-1）	容量保持率/%	锂离子扩散系数/（cm²·s^-1）
Sr^[28]	Na	Sr_0.5Na₂Ti₆O₁₄	184.0（50 mA/g）	96.09	2.365×10^-15
Li、Cu、Y、Ce、Nb^[29]	Na	Na_1.9Nb_0.1Li₂Ti₆O₁₄	259.4（100 mA/g）	94.7	2.44×10^-14
Al、V、Zr^[30]	Ti	Li₂Na₂Ti_5.9Al_0.1O₁₄	240.3（50 mA/g）	88.9	8.38×10^-15
Al^[31]	Li	Li_1.95Al_0.05Na₂Ti₆O₁₄	268.8（100 mA/g）	91.2	5.77×10^-15
Ba^[32]	Na	NaBa_0.5Li₂Ti₆O₁₄	109.6（50 mA/g）	99.1	1.53×10^-17
Ba^[33]	Na、Li	BaLi_0.5Na_1.5Ti₆O₁₄	163.9（50 mA/g）	100	2.1×10^-16（约）
Mg^[34]	Li	Li_1.95Mg_0.05Na₂Ti₆O₁₄	167.4（500 mA/g）	98.8	3.16×10^-15
Na、Mg、Cr、Ti、V^[35]	Li	Na₂Li_1.9Cr_0.1Ti₆O₁₄	262.2（100 mA/g）	91.3	1.95×10^-14
Li^[36]	Na	Na_2.05Li_1.95Ti₆O₁₄	302.9（100 mA/g）	91.6	8.28×10^-15

包覆材料	包覆方法	最佳包覆	形貌特征	初始放电比容量/（mA·h·g^-1）	容量保持率/%	锂离子扩散系数/（cm²·s^-1）
Li_0.33La_0.56TiO₃^[38]	固相法	5%（质量分数）	附着颗粒表面	156.7（500 mA/g）	88.0	5×10^-16
CB/GN/CNT^[39]	固相法	CNT	纳米管穿在颗粒之间	111.4（100 mA/g）	99.1	—
Cu/C^[40]	化学沉积法	0.2 L/g	包裹颗粒表面	140.1（50 mA/g）	85.9	—
MgF₂^[41]	化学沉积法	5.0%（质量分数）	包裹颗粒表面	483.4（50 mA/g）	77.2	2.49×10^-16
Er₂O₃^[42]	溶剂热法	4.0%（质量分数）	包裹颗粒表面	320.0（50 mA/g）	70.1	9.10×10^-15
Ag^[43]	化学沉积法	6.0%（质量分数）	附着颗粒表面	200.3（100 mA/g）	95.0	1.514×10^-15
C（木薯粉）^[44]	热分解法	12;1（原料与碳质量比）	包裹颗粒表面	101.7（0.1C）	61.2	—

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Research progress on lithium sodium titanate for lithium ion batteries

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