铝掺杂LiFePO4的表面成份结构及电化学性能研究

doi:10.13208/j.electrochem.130354

电化学（中英文） ›› 2013, Vol. 19 ›› Issue (6): 558-564. doi: 10.13208/j.electrochem.130354

• 锂离子电池近期研究专辑 (厦门大学杨勇教授主编) • 上一篇下一篇

铝掺杂LiFePO₄的表面成份结构及电化学性能研究

尚怀芳¹，黄伟峰²，储旺盛²，夏定国^3*，吴自玉^2*

1. 北京工业大学环境与能源工程学院环境电化学实验室，北京 100717；2. 中国科技大学国家同步辐射实验室，合肥 230026；3. 北京大学工学院先进电池材料理论与技术北京市重点实验室，北京 100871

收稿日期:2013-05-06 修回日期:2013-05-24 出版日期:2013-12-28 发布日期:2013-12-23
通讯作者: 夏定国 E-mail:dgxia@pku.edu.cn
基金资助:
国家自然科学基金项目(No. 11179001)、北京市自然科学基金项目(No. 20110001)和国家高技术研究发展863计划项目(No. 2011AA11A254，No. 2012AA052201)资助

Surface Composition Structure and Electrochemical Performance of Aluminum Doped LiFePO₄

SHANG Huai-fang¹, HUANG Wei-feng², HU Wang-sheng², XIA Ding-guo^3*, WU Zi-yu^2*

1. College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100022, P. R. China; 2. NSRL, University of Science and Technology of China, Hefei 230026, P. R. China; 3. Key lab of theory and technology for advanced batteries materials, College of Engineering, Peking University, Beijing 100871, P. R. China

Received:2013-05-06 Revised:2013-05-24 Published:2013-12-28 Online:2013-12-23
Contact: XIA Ding-guo E-mail:dgxia@pku.edu.cn

摘要/Abstract

摘要： 锂离子电池正极材料掺杂LiFePO₄的报道已很多，而涉及掺杂LiFePO₄的表面成份及结构的研究仍很少见. 本文采用溶剂热法一步得了表面富Al的LiFePO₄正极材料. TEM测试证实LiFePO₄的表面形成均匀的无定型包覆层；俄歇电子能谱和软X射线吸收谱共同揭示了其表面的自包覆层为部分Al替代Fe的LiFe_1-xAl_xPO₄. 表面富Al（x=0.02）的LiFePO₄显示了较好的电化学倍率性能和低温性能，充放电-10 ^oC的条件下，电压范围2.2 ~ 4.2 V、0.1C倍率电极的放电比容量为98 mAh·g^-1，0.5C倍率放电比容量可达70 mAh·g^-1. 这归因于Al的加入改变了材料体相及表面的电子结构，增加了体相电子的传导及表面离子的传导.

关键词: LiFePO4, 表面包覆, 电化学性能

Abstract: Despite there are many successful reports about the preparation of electrode materials with surface coating for lithium ion batteries, the study in surface self-coating of cathode materials using segregation of doping elements and their electrochemical properties is still very rare. The LiFePO₄ particles with rich-Al on the surface were synthesized by one step solvothermal route. TEM results demonstrated that the surface of the obtained LiFePO₄ particles was well-covered by the amorphous coating. The soft X-ray absorption spectroscopy (XAS) and Auger electron spectroscopy (AES) component analyses revealed that the amorphous coating was composed of LiFe_1-xAl_xPO₄ by part of Al substitution to Fe. The LiFePO₄ material with surface rich-Al showed good electrochemical rate capacity and low temperature performance. This could be attributed to the changes of the bulk and surface electron structures which promote the bulk electron and surface ionic conductivities.

Key words: LiFePO₄, surface coating, electrochemical performances

中图分类号:

O646

尚怀芳，黄伟峰，储旺盛，夏定国*，吴自玉*. 铝掺杂LiFePO₄的表面成份结构及电化学性能研究[J]. 电化学（中英文）, 2013, 19(6): 558-564.

SHANG Huai-fang, HUANG Wei-feng, HU Wang-sheng, XIA Ding-guo*, WU Zi-yu*. Surface Composition Structure and Electrochemical Performance of Aluminum Doped LiFePO₄[J]. Journal of Electrochemistry, 2013, 19(6): 558-564.

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.130354

https://electrochem.xmu.edu.cn/CN/Y2013/V19/I6/558

参考文献

[1] Weinstock I B. Recent advances in the US Department of Energy's energy storage technology research and development programs for hybrid electric and electric vehicles[J]. Journal of Power Sources, 2002, 110(2): 471-474.
[2] Vincent C A. Lithium batteries: A 50-year perspective, 1959-2009[J]. Solid State Ionics, 2000, 134(1/2): 159-167.
[3] Nishi Y. Lithium ion secondary batteries; past 10 years and the future[J]. Journal of Power Sources, 2001, 100(1/2): 101-106.
[4] Zhang Y, Wu X B, Feng H, et al. Effect of nanosized Mg0.8Cu0.20O on electrochemical properties of Li/S rechargeable batteries[J]. International Journal of Hydrogen Energy, 2009, 34(3): 1556-1559.
[5] Padhi A K, Nanjundaswamy K S, Goodenough J B. Phospho-olivines as positive-electrode materials for rechargeable lithium batteries[J]. Journal of the Electrochemical Society, 1997, 144(4): 1188-1194.
[6] Striebel K, Shim J, Srinivasan V, et al. Comparison of LiFePO4 from different sources[J]. Journal of the Electrochemical Society, 2005, 152(4): A664-A670.
[7] Prosini P P, Lisi M, Zane D, et al. Determination of the chemical diffusion coefficient of lithium in LiFePO4[J]. Solid State Ionics, 2002, 148(1/2): 45-51.
[8] Dell’Era A, Pasquali M. Comparison between different ways to determine diffusion coefficient and by solving Fick's equation for spherical coordinates[J]. Journal of Solid State Electrochemistry, 2009, 13(6): 849-859.
[9] Yin Y H, Gao M X. High-rate capability of LiFePO4 cathode materials containing Fe2P and trace carbon[J]. Journal of Power Sources, 2012, 199: 256-262.
[10] Doherty C M, Caryso R A. Colloidal crystal templating to produce hierarchically porous LiFePO4 electrode materials for high power lithium ion batteries[J]. Chemistry Materials, 2009, 21(13): 2895-2903.
[11] Zou H L, Zhang G H, Shen P K. Intermittent microwave heating synthesized high performance spherical LiFePO4/C for Li-ion batteries[J]. Materials Research Bulletin, 2010, 45(2): 149-152.
[12] Kim D H, Kim J. Synthesis of LiFePO4 nanoparticles in polyol medium and their electrochemical properties[J]. Electrochemical and Solid-State Letters, 2006, 9(9): A439-A442.
[13] Meethong N. Size-dependent lithium miscibility gap in nanoscale Li1-xFePO4[J]. Electrochemical and Solid-State Letters, 2001, 10(5): A174-A178.
[14] Chen Z H, Dahn J R. Reducing carbon in LiFePO4/C composite electrodes to maximize specific energy, volumetric energy, and tap density[J]. Journal of the Electrochemical Society, 2002, 149(9): A1184-A1189.
[15] Yamada A, Chung S C, Hinokurna K. Optimized LiFePO4 for lithium battery cathodes[J]. Journal of the Electrochemical Society, 2001, 148(3): A224-A229.
[16] Ni J F, Morishita M, Kawabe Y, et al. Hydrothermal preparation of LiFePO4 nanocrystals mediated by organic acid[J]. Journal of Power Sources, 2010, 195(9): 2877-2882.
[17] Choi D, Kumta P N. Surfactant based sol-gel approach to nanostructured LiFePO4 for high rate Li-ion batteries[J]. Journal of Power Sources, 2007, 163(2): 1064-1069.
[18] Konarova M, Taniguchi I. Synthesis of carbon-coated LiFePO4 nanoparticles with high rate performance in lithium secondary batteries[J]. Journal of Power Sources, 2010, 195(11): 3661-3667.
[19] Zhou W J, He W, Li Z M, et al. Biosynthesis and electrochemical characteristics of LiFePO4/C by microwave processing[J]. Journal of Solid State Electrochemistry, 2009, 13(12): 1819-1823.
[20] Chevrier F, Brochier R, Richter C. Reactivity and magnetism of Fe/In As(100) interfaces[J]. The European Physical Journal B, 2002, 28(3): 305-313.
[21] Zheng S, Hayakawa S, Gohshi Y. An experimental comparison of the total-electron-yield and conversion-electron-yield modes for near-surface characterization using X-ray excitation[J]. Journal of electron spectroscopy and related phenomena, 1997, 87(1): 81-89.
[22] Ankudinov A L, Ravel B, Rehr J J, et al. Real-space multiple-scattering calculation and interpretation of X-ray-absorption near-edge structure[J]. Physical Review B, 1998, 58(12): 7565-757.
[23] Lee P A, Pendry J B. Theory of extended X-ray absorption fine-structure[J]. Physical Review B, 1975, 11(8): 2795-2811.
[24] Natoli C R, Benfatto M, Brouder C, et al. Multichannel multiple-scattering theory with general potentials[J]. Physical Review B, 1990, 42(4): 1944-1968.
[25] Ou X Q, Pan L, Gu H C, et al. Temperature-dependent crystallinity and morphology of LiFePO4 prepared by hydrothermal synthesis[J]. Journal of Materials Chemistry, 2012, 22(18): 9064-9068.
[26] Azib T, Ammar S, Nowak S. Crystallinity of nano C-LiFePO4 prepared by the polyol process[J]. Journal of Power Sources, 2012, 217: 220-228.
[27] Sun C, Rajasekhara S, Goodenough J B, et al. Monodisperse porous LiFePO4 microspheres for a high power Li-ion battery cathode[J]. Journal of the American Chemical Society, 2011, 133(7): 2132-2135.
[28] Laffont L, Delacourt C, Gibot P, et al. Study of the LiFePO4/FePO4 two-phase system by high-resolution electron energy loss spectroscopy[J]. Chemistry of Materials, 2006, 18(23): 5520-5529.
[29] Kang B, Ceder G. Battery materials for ultrafast charging and discharging[J]. Nature, 2009, 458(7235): 190-193.
[30] Shang H F, Chu W S, Cheng J, et al. Surface phase composition of nanosized LiFePO4 and their enhanced electrochemical properties[J]. Journal of Materials Chemistry A, 2013, 1(22): 6635-6641.
[31] Abbate M, Pen H, Czyzyk M T, et al. Soft-X-ray absorption-spectroscopy of vanadium-oxides[J]. Journal of Electron Spectroscopy and Related Phenomena, 1993, 62(1/2): 185-195.
[32] Khang H, Michelle D J. First-principles studies of the effects of impurities on the ionic and electronic conduction in LiFePO4[J]. Journal of Power Sources, 2012, 206: 274-281.
[33] Chen H, Wang S Z. Preparation and electrochemical performance of LiFePO4/C composite with carbon core structure[J]. Materials Letters, 2009, 63(20): 1668-1670.
[34] Muxina K, Izumi T. Preparation of carbon coated LiFePO4 by a combination of spray pyrolysis with planetary ball-milling followed by heat treatment and their electrochemical properties[J]. Powder Technology, 2009, 191(1/2): 111-116.
[35] Liao L X, Zuo P J, Ma Y L, et al. Effects of temperature on charge/discharge behaviors of LiFePO4 cathode for Li-ion batteries[J]. Electrochemical Acta, 2012, 60: 269-273.

铝掺杂LiFePO₄的表面成份结构及电化学性能研究

Surface Composition Structure and Electrochemical Performance of Aluminum Doped LiFePO₄

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

Metrics

[1]	杨云锐, 董欢欢, 郝志强, 何祥喜, 杨卓, 李林, 侴术雷. 高性能锂硫电池用钴/碳复合材料硫宿主[J]. 电化学（中英文）, 2023, 29(4): 2217003-.
[2]	赵刚, 龚正良, 李益孝, 杨勇. 氧化钨和磷钨酸对LiNi_0.96Co_0.02Mn_0.02O₂材料的表面包覆改性研究[J]. 电化学（中英文）, 2023, 29(10): 2204281-.
[3]	贠潇如, 陈宇方, 肖培涛, 郑春满. 关于水系锌离子电池中无氧钒基正极材料的综述[J]. 电化学（中英文）, 2022, 28(11): 2219004-.
[4]	梁振浪, 杨耀, 李豪, 刘丽英, 施志聪. 基于不同前驱体制备的硬碳负极材料的储锂性能[J]. 电化学（中英文）, 2021, 27(2): 177-184.
[5]	吴凯. Na₃V₂(PO₄)₂O₂F的合成及其在钠离子电池中的应用[J]. 电化学（中英文）, 2021, 27(1): 56-62.
[6]	孙梦雷, 张达奇, 冯金奎, 倪江锋. 钒基电极材料研究进展[J]. 电化学（中英文）, 2019, 25(1): 45-54.
[7]	何大平，木士春. 质子交换膜燃料电池铂电催化剂稳定策略[J]. 电化学（中英文）, 2018, 24(6): 655-663.
[8]	王鸿辉，马明洁，冯婕，康黄雅，黄文杰. 钕掺杂二氧化铅复合阳极的电化学性能研究[J]. 电化学（中英文）, 2018, 24(4): 367-374.
[9]	张伶潇，赵惠慧，张丽娟，付予. Ag-TiO₂-MnO₂复合材料的制备与电化学性能研究[J]. 电化学（中英文）, 2018, 24(3): 292-299.
[10]	李全一，杨琪，赵艳红. 二氧化钼-碳复合涂层的电化学性能研究[J]. 电化学（中英文）, 2018, 24(2): 160-165.
[11]	王友，曾一文，钟星，刘星，汤泉. 锂离子电池负极材料Li₃V₂(BO₃)₃/C 复合材料的合成及电化学性能研究[J]. 电化学（中英文）, 2018, 24(2): 174-181.
[12]	刘兴亮，杨茂萍，汪伟伟, 曹勇. 分级过程对LiFePO₄/C电池性能的影响[J]. 电化学（中英文）, 2017, 23(6): 661-666.
[13]	罗化峰，乔元栋. 纤维素微孔锂电隔膜的制备及性能研究[J]. 电化学（中英文）, 2017, 23(5): 610-616.
[14]	程琥, 聂晓燕, 申叶丹, . 哌啶型离子液体混合电解液在Li/LiCoO₂电池中的性能研究[J]. 电化学（中英文）, 2017, 23(1): 59-63.
[15]	杨亚雄，马瑞军，高明霞，潘洪革，刘永锋. 晶态Li₁₂Si₇锂离子电池负极材料的电化学性能研究[J]. 电化学（中英文）, 2016, 22(5): 521-527.