Ga掺杂FeNb11O29材料的制备及其电化学性能

摘要/Abstract

摘要： FeNb₁₁O₂₉由于其高的理论充电容量(400 mAh·g^-1),作为锂离子电池(LIBs)负极材料具有很大的应用前景。然而,目前报道的FeNb₁₁O₂₉实际容量仅有168~273 mAh·g^-1。因此,有必要进一步提高其电化学性能。本文介绍了一种制备Ga掺杂FeNb₁₁O₂₉材料的方法,成功合成了Ga_xFe_1-xNb₁₁O₂₉(x=0.1,0.2)。结果表明,Ga_0.2Fe_0.8Nb₁₁O₂₉的电导率比FeNb₁₁O₂₉提高了两个数量级。X射线衍射结果显示,Ga掺杂不会改变FeNb₁₁O₂₉的正交剪切ReO₃晶体结构。扫描电镜结果显示,材料的微观形貌没有发生明显改变。电化学实验表明,Ga_0.2Fe_0.8Nb₁₁O₂₉具有较好的电化学性能,在电流密度为0.1 C时,Ga_0.2Fe_0.8Nb₁₁O₂₉充电容量为290 mAh·g^-1,当电流密度达到5 C时容量仍能保持145 mAh·g^-1,此外,Ga_0.2Fe_0.8Nb₁₁O₂₉具有良好的循环稳定性,在电流密度为5 C时循环1 000圈之后,容量保持率为91.0%,而不掺杂的FeNb₁₁O₂₉的充电容量仅有107 mAh·g^-1,容量保持率仅为55.9%。利用Ga掺杂改善FeNb₁₁O₂₉负极材料的电化学性能在锂离子电池中具有广阔的应用前景。

关键词: FeNb₁₁O₂₉, Ga掺杂, 锂离子电池, 电化学性能, 电流密度

Abstract: FeNb₁₁O₂₉ is a promising anode material for lithium-ion batteries (LIBs) due to its high theoretical capacity (400 mAh·g^-1). However, the reported practical capacities of FeNb₁₁O₂₉ are only 168 mAh·g^-1 to 273 mAh·g^-1. Therefore, it is very necessary to further improve the electrochemical performance of FeNb₁₁O₂₉. A simple and effective Ga-doped method was demonstrated in this study, which enhanced the electrochemical performances of FeNb₁₁O₂₉ materials successfully. XRD results show that Ga-doped doesn't change the orthogonal shear ReO₃ crystal structure of FeNb₁₁O₂₉. Scanning electron microscopy characterization indicats that no significant change in morphology is observed. Ga³⁺ could replace Fe³⁺ in FeNb₁₁O₂₉, the electronic conductivity of Ga_0.2Fe_0.8Nb₁₁O₂₉ is enhanced by two orders of magnitude compared with FeNb₁₁O₂₉. Consequently, Ga_0.2Fe_0.8Nb₁₁O₂₉ exhibits excellent electrochemical performances. At the current density at 0.1 C, the charge capacity of Ga_0.2Fe_0.8Nb₁₁O₂₉ reaches 290 mAh·g^-1, which remains 145 mAh·g^-1 when the current density rose to 5 C. Moreover, Ga_0.2Fe_0.8Nb₁₁O₂₉ presents outstanding cycling stability with a capacity retention of 91.0% at 5 C after 1 000 cycles. In contrast, undoped FeNb₁₁O₂₉ only possesses a charge capacity of 107 mAh·g^-1 with a capacity retention of 55.9% at 5 C after 1 000 cycles. The research indicates that the electrochemical performances of FeNb₁₁O₂₉improves significantly by Ga-doped, and Ga_0.2Fe_0.8Nb₁₁O₂₉ has wide application in LIBs in the future.

Key words: FeNb₁₁O₂₉, Ga-doped, lithium-ion battery, electrochemical performance, current density

中图分类号:

TM912

黄晋萍, 陈庆, 李建保, 骆丽杰, 陈拥军. Ga掺杂FeNb₁₁O₂₉材料的制备及其电化学性能[J]. 硅酸盐通报, 2021, 40(8): 2740-2747.

HUANG Jinping, CHEN Qing, LI Jianbao, LUO Lijie, CHEN Yongjun. Fabrication and Electrochemical Performances of Ga-Doped FeNb₁₁O₂₉ Materials[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2021, 40(8): 2740-2747.

参考文献

[1] ARMAND M, TARASCON J M. Building better batteries[J]. Nature, 2008, 451(7179): 652-657.
[2] DUNN B, KAMATH H, TARASCON J M. Electrical energy storage for the grid: a battery of choices[J]. Science, 2011, 334(6058): 928-935.
[3] AUGUSTYN V, COME J, LOWE M A, et al. High-rate electrochemical energy storage through Li⁺ intercalation pseudocapacitance[J]. Nature Materials, 2013, 12(6): 518-522.
[4] LI J L, DANIEL C, WOOD D. Materials processing for lithium-ion batteries[J]. Journal of Power Sources, 2011, 196(5): 2452-2460.
[5] LIU Z, GUO R T, MENG J S, et al. Facile electrospinning formation of carbon-confined metal oxide cube-in-tube nanostructures for stable lithium storage[J]. Chemical Communications, 2017, 53: 8284-8287.
[6] CAPSONI D, BINI M, MASSAROTTI V, et al. Cations distribution and valence states in Mn-substituted Li₄Ti₅O₁₂ structure[J]. Chemistry of Materials, 2008, 20 (13): 4291-4298.
[7] NCUBE N M, MHLONGO W T, MCCRINDLE R I, et al. The electrochemical effect of Al-doping on Li₄Ti₅O₁₂ as anode material for lithium-ion batteries[J]. Materials Today: Proceedings, 2018, 5(4): 10592-10601.
[8] PINUS I, CATTI M, RUFFO R, et al. Neutron diffraction and electrochemical study of FeNb₁₁O₂₉/Li₁₁FeNb₁₁O₂₉for lithium battery anode applications[J]. Chemistry of Materials, 2014, 26(6): 2203-2209.
[9] ZHENG R T, QIAN S S, CHENG X, et al. FeNb₁₁O₂₉ nanotubes: superior electrochemical energy storage performance and operating mechanism[J]. Nano Energy, 2019, 58: 399-409.
[10] LOU X M, LIN C F, LUO Q, et al. Crystal structure modification enhanced FeNb₁₁O₂₉ anodes for lithium-ion batteries[J]. ChemElectroChem, 2017, 4(12): 3171-3180.
[11] LOU X M, XU Z H, LUO Z B, et al. Exploration of Cr_0.2Fe_0.8Nb₁₁O₂₉ as an advanced anode material for lithium-ion batteries of electric vehicles[J]. Electrochimica Acta, 2017, 245: 482-488.
[12] 肖和,张文展,邱小林,等.Mg²⁺和F^-共掺杂提高LiNi_0.8Co_0.15Al_0.05O₂电化学性能[J].硅酸盐通报,2020,39(3):890-895.
XIAO H, ZHANG W Z, QIU X L, et al. Electrochemical performance of LiNi_0.8Co_0.15Al_0.05O₂ enhanced by Mg²⁺ and F^- co-doping[J]. Bulletin of the Chinese Ceramic Society, 2020, 39(3): 890-895 (in Chinese).
[13] 刘文刚,许云华,杨蓉,等.锂离子电池正极材料Li₂Mn_0.95Mg_0.05SiO₄的合成和电化学性能[J].硅酸盐通报,2009,28(3):464-467.
LIU W G, XU Y H, YANG R, et al. Preparation and electrochemical performance of Li₂Mn_0.95Mg_0.05SiO₄ cathode material for lithium ion batteries[J]. Bulletin of the Chinese Ceramic Society, 2009, 28(3): 464-467 (in Chinese).
[14] HAN J T, GOODENOUGH J B. 3-V full cell performance of anode framework TiNb₂O₇/spinel LiNi_0.5Mn_1.5O₄[J]. Chemistry of Materials, 2011, 23(15): 3404-3407.
[15] 孙宁,刘小伟,刘湘林,等.铋离子掺杂固体氧化物燃料电池阴极材料的研究进展[J].硅酸盐通报,2020,39(12):3958-3963.
SUN N, LIU X W, LIU X L, et al. Research progress of bismuth ion doped cathode materials for solid oxide fuel cell[J]. Bulletin of the Chinese Ceramic Society, 2020, 39(12): 3958-3963 (in Chinese).
[16] LIN X H, ZHAO Y M, KUANG Q, et al. Synthesis and electrochemical properties of Co-doped Li₉V₃(P₂O₇)₃(PO₄)₂/C as cathode materials for lithium-ion batteries[J]. Solid State Ionics, 2014, 259: 46-52.
[17] 闫小童,侯育花,郑寿红,等.Ga,Ge,As掺杂对锂离子电池正极材料Li₂CoSiO₄的电化学特性和电子结构影响的第一性原理研究[J].物理学报,2019,68(18):187101.
YAN X T, HOU Y H, ZHENG S H, et al. First-principles study of effects of Ga, Ge and As doping on electrochemical properties and electronic structure of Li₂CoSiO₄ serving as cathode material for Li-ion batteries[J]. Acta Physica Sinica, 2019, 68(18): 187101 (in Chinese).
[18] SONG H, KIM Y T. A Mo-doped TiNb₂O₇ anode for lithium-ion batteries with high rate capability due to charge redistribution[J]. Chemical Communications, 2015, 51(48): 9849-9852.
[19] ITURRONDOBEITIA A, GOÑI A, PALOMARES V, et al. Effect of doping LiMn₂O₄ spinel with a tetravalent species such as Si(IV) versus with a trivalent species such as Ga(III). Electrochemical, magnetic and ESR study[J]. Journal of Power Sources, 2012, 216: 482-488.
[20] LALA S M, MONTORO L A, LEMOS V, et al. The negative and positive structural effects of Ga doping in the electrochemical performance of LiCoO₂[J]. Electrochimica Acta, 2005, 51(1): 7-13.
[21] TONG D G, CAO J L, LAI Q Y, et al. Synthesis and characterization of LiCo_0.3-xGa_xNi_0.7O₂ (x=0, 0.05) as a cathode material for lithium ion battery[J]. Materials Chemistry and Physics, 2006, 100(2/3): 217-223.
[22] SHIN D W, BRIDGES C A, HUQ A, et al. Role of cation ordering and surface segregation in high-voltage spinel LiMn_1.5Ni_0.5-xM_xO₄ (M=Cr, Fe, and Ga) cathodes for lithium-ion batteries[J]. Chemistry of Materials, 2012, 24(19): 3720-3731.
[23] LIANG G S, JIN X X, HUANG C H, et al. Cr³⁺-doped Li₃VO₄ for enhanced Li⁺ storage[J]. Functional Materials Letters, 2020, 13(2): 2050005.
[24] LIN C F, LAI M O, LU L, et al. Structure and high rate performance of Ni²⁺ doped Li₄Ti₅O₁₂ for lithium ion battery[J]. Journal of Power Sources, 2013, 244: 272-279.
[25] LIN C F, YU S, WU S Q, et al. Ru_0.01Ti_0.99Nb₂O₇ as an intercalation-type anode material with a large capacity and high rate performance for lithium-ion batteries[J]. Journal of Materials Chemistry A, 2015, 3(16): 8627-8635.
[26] LIN C F, FAN X Y, XIN Y L, et al. Li₄Ti₅O₁₂-based anode materials with low working potentials, high rate capabilities and high cyclability for high-power lithium-ion batteries: a synergistic effect of doping, incorporating a conductive phase and reducing the particle size[J]. J Mater Chem A, 2014, 2(26): 9982-9993.
[27] ZHU X Z, XU J, LUO Y P, et al. MoNb₁₂O₃₃ as a new anode material for high-capacity, safe, rapid and durable Li⁺ storage: structural characteristics, electrochemical properties and working mechanisms[J]. Journal of Materials Chemistry A, 2019, 7(11): 6522-6532.
[28] LOU X M, FU Q F, XU J, et al. GaNb₁₁O₂₉ nanowebs as high-performance anode materials for lithium-ion batteries[J]. ACS Applied Nano Materials, 2018, 1(1): 183-190.
[29] LOU X, LI R, ZHU X, et al. New anode material for lithium-ion batteries: aluminum niobate (AlNb₁₁O₂₉)[J]. ACS Applied Materials & Interfaces, 2019, 11(6): 6089-6096.
[30] FU Q F, LIU X, HOU J R, et al. Highly conductive CrNb₁₁O₂₉ nanorods for use in high-energy, safe, fast-charging and stable lithium-ion batteries[J]. Journal of Power Sources, 2018, 397: 231-239.
[31] ZHU X Z, FU Q F, TANG L F, et al. Mg₂Nb₃₄O₈₇ porous microspheres for use in high-energy, safe, fast-charging, and stable lithium-ion batteries[J]. ACS Applied Materials & Interfaces, 2018, 10(28): 23711-23720.

Ga掺杂FeNb₁₁O₂₉材料的制备及其电化学性能

Fabrication and Electrochemical Performances of Ga-Doped FeNb₁₁O₂₉ Materials

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	查成, 张天宇, 季雨辰, 刘树和. 锂硫电池正极材料的研究进展[J]. 硅酸盐通报, 2021, 40(4): 1352-1360.
[2]	黄均艳;王小丽;黄美英;夏明星. 乙酸锌活化制备柚子皮衍生活性碳及其电化学和吸附性能研究[J]. 硅酸盐通报, 2020, 39(7): 2335-2342.
[3]	王春源;黄杜斌;宋波涛;程宏飞. 硅藻土涂层改性锌负极及其在锌离子电池中的应用[J]. 硅酸盐通报, 2020, 39(6): 1909-1915.
[4]	王万玺;王凤英;王刚;李海宾. 富锂锰基正极材料的形貌与结构调控及电化学性能研究[J]. 硅酸盐通报, 2020, 39(3): 885-889.
[5]	肖和;张文展;邱小林;陆志香. Mg2+和F-共掺杂提高LiNi0.8Co0.15Al0.05O2电化学性能[J]. 硅酸盐通报, 2020, 39(3): 890-895.
[6]	李晓俊;张金华;郑刚;汪伟;倪江秀;王金龙. 石墨烯复合碳纳米管添加量对锂离子电池性能的影响[J]. 硅酸盐通报, 2020, 39(3): 896-900.
[7]	张丽娜;张平;张山;袁明珞. TiO2/In2S3复合薄膜的制备及光电化学性能研究[J]. 硅酸盐通报, 2019, 38(8): 2403-240.
[8]	曹婷;李东林;王艳茹;孔祥泽;李童心;张世龙;樊小勇;苟蕾. 三维有序大孔Ni-Co-Mn过渡金属氧化物锂离子电池负极材料制备及电化学性能[J]. 硅酸盐通报, 2019, 38(5): 1295-130.
[9]	李瑞锋;王文娟;刘诚;黄康;李纯;鲁自鼎. LaBaCoFeO5+δ-Ce0.8Sm0.2O1.9复合阴极的电化学性能研究[J]. 硅酸盐通报, 2019, 38(4): 1012-101.
[10]	杨森;杨绍斌;董伟;沈丁. 天然微晶石墨提纯工艺及可逆储锂性能[J]. 硅酸盐通报, 2019, 38(4): 1148-115.
[11]	季鸣童;王晓爽. 多孔氮掺杂石墨烯/MnO2的制备及其电化学性能[J]. 硅酸盐通报, 2019, 38(12): 3814-382.
[12]	谢丹丹;周静;吴智;沈杰. 铌镁酸钡缓冲层对锆钛酸铅薄膜漏电流的抑制[J]. 硅酸盐通报, 2019, 38(11): 3403-340.
[13]	梁文彪;李世友;崔孝玲;魏媛;解静. 高电压LiNi0.5Mn1.5O4正极材料现状及展望[J]. 硅酸盐通报, 2019, 38(11): 3450-345.
[14]	郝涛;张英杰;董鹏;梁风;段建国;孟奇;许斌. 废旧三元动力锂离子电池正极材料回收的研究进展[J]. 硅酸盐通报, 2018, 37(8): 2450-2456.
[15]	张悦;陈龙;张楠;刘逸藤;李线线;张健;王雅东;潘牧. 锂离子电池核壳结构硅基负极材料的研究进展[J]. 硅酸盐通报, 2018, 37(5): 1615-1624.