晶态Li12Si7锂离子电池负极材料的电化学性能研究

doi:10.13208/j.electrochem.160541

摘要/Abstract

摘要：

通过加热摩尔比为12:7的LiH/Si球磨混合物，避免了Li与Si之间巨大的熔点差异，成功制备了晶态Li₁₂Si₇合金，研究了其电化学性能和储锂机制. 发现Li₁₂Si₇在0.02 ~ 0.6 V的嵌脱锂过程中，只发生晶胞体积的变化，而不产生相变，呈现出明显的固溶储锂机制. 该固溶储锂机制的存在，有效抑制了Si基负极材料嵌脱锂过程中由于相变导致的体积效应，使得晶态Li₁₂Si₇在0.02 ~ 0.6 V电压范围内具有显著改善的电化学性能，其首次库伦效率高达100%，30次循环后的可逆容量保持率约为74%，分别优于相同条件下原始Si电极的55%和37%.

关键词: 锂离子电池, 负极材料, 锂硅合金, 电化学性能, 储锂机制

Abstract:

Crystalline Li₁₂Si₇ is successfully synthesized by heating the mixture of LiH and Si with a molar ratio of 12:7, which avoids the huge difference of the melting points between Li and Si. The electrochemical performance and lithium storage mechanism of the as-prepared Li12Si7 are studied in this work. It is found that only a change in cell volume takes place without a phase change during the lithiation/delithiation of Li₁₂Si₇ at a voltage range of 0.02 ~ 0.6 V, exhibiting a solid-solution lithium storage mechanism. Such a lithium storage process effectively retards the volume effect caused by the phase change during lithiation/delithiation of Si-based anode. This induces significantly the improved electrochemical properties of crystalline Li₁₂Si₇ while cycling at 0.02 ~ 0.6 V. The first Coulombic efficiency of crystalline Li₁₂Si₇ is determined to be as high as 100%, and the capacity retention is 74% after 30 cycles, which are distinctly higher than those of Si anode (55% and 37%, respectively) under identical conditions.

Key words: lithium-ion batteries, anode materials, Li-Si alloys, electrochemical properties, lithium storage mechanism

中图分类号:

TQ126.2
O646

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.

YANG Ya-xiong, MA Rui-jun, GAO Ming-xia, PAN Hong-ge, LIU Yong-feng. Electrochemical Performance of Crystalline Li₁₂Si₇as Anode Material for Lithium Ion Battery[J]. Journal of Electrochemistry, 2016, 22(5): 521-527.

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.160541

https://electrochem.xmu.edu.cn/CN/Y2016/V22/I5/521

参考文献

[1] Etacheri V, Marom R, Elazari R, et al. Challenges in the development of advanced Li-ion batteries: a review[J]. Energy & Environmental Science, 2011, 4(9): 3243-3262.

[2] Nitta N, Wu F X, Lee J T, et al. Li-ion battery materials: present and future[J]. Materials Today, 2015, 18(5): 252-264.

[3] Grande L, Paillard E, Hassoun J, et al. The Lithium/Air Battery: Still an Emerging System or a Practical Reality? [J]. Advanced Materials, 2015, 27(5), 784-800.

[4] Fotouhi A, Auger D J, Propp K, et al. A review on electric vehicle battery modelling: From Lithium-ion toward Lithium–Sulphur[J]. Renewable and Sustainable Energy Reviews, 2016, 56: 1008-1021.

[5] Abada S, Marlair G, Lecocq A, et al. Safety focused modeling of lithium-ion batteries: A review[J]. Journal of Power Sources, 2016, 306: 178-192.

[6] Zhang W J. A review of the electrochemical performance of alloy anodes for lithium-ion batteries[J]. Journal of Power Sources, 2011, 196(1): 13-24.

[7] Ji L W, Lin Z, Alcoutlabi M, et al. Recent developments in nanostructured anode materials for rechargeable lithium-ion batteries[J]. Energy & Environmental Science, 2011, 4(8): 2682-2699.

[8] Yang Y, Jeong S, Hu L, et al. Transparent lithium-ion batteries[J]. Proceedings of the National Academy of Sciences of the United States of America, 2011, 108(32): 13013-13018.

[9] Park C M, Kim J H, Kim H, et al. Li-alloy based anode materials for Li secondary batteries[J]. Chemical society reviews, 2010, 39(8): 3115-3141.

[10] Liang B, Liu Y P, Xu Y H. Silicon-based materials as high capacity anodes for next generation lithium ion batteries[J]. Journal of Power Sources, 2014, 267: 469-490.

[11] Ryu J H, Kim J W, Sung Y E, et al. Failure modes of silicon powder negative electrode in lithium secondary batteries[J]. Electrochemical and solid state letters. 2004, 7(10), A306-A309.

[12] Obrovac M N, Krause L J. Reversible cycling of crystalline silicon powder[J]. Journal of the electrochemical society, 2007, 154(2), A103-A108.

[13] Tian H J, Tan X J, Xin F X, et al. Micro-sized nano-porous Si/C anodes for lithium ion batteries[J]. Nano Energy, 2015, 11: 490-499.

[14] Liu Y F, Yan P, Ma R J, et al. Electrochemical properties of the ternary alloy Li₅AlSi₂ synthesized by reacting LiH, Al and Si as an anodic material for lithium-ion batteries[J]. Journal of Power Sources, 2015, 283: 54-60.

[15] Ma R J, Liu Y F, Yang Y X, et al. Mg₂Si anode for Li-ion batteries: Linking structural change to fast capacity fading[J]. Applied physics letters, 2014, 105: 213901-1-4.

[16] Yan J M, Huang H Z, Zhang J, et al. The study of Mg₂Si/carbon composites as anode materials for lithium ion batteries[J]. Journal of Power Sources, 2008, 175(1): 547-552.

[17] Liu Y F, Ma R J, He Y P, et al. Synthesis, structure transformation, and electrochemical properties of Li₂MgSi as a novel anode for Li-lon Batteries[J]. Advanced functional materials, 2014, 24(25): 3944-3952.

[18] Liu L, Obrovac M N. Structural changes in LiAlSi during electrochemical cycling[J]. ECS Electrochemistry Letters, 2012, 1(1): A10-A12.

[19] Lacroix-Orio L, Tillard M, Belin C. Synthesis, crystal and electronic structure of Li₁₃Ag₅Si₆, a potential anode for Li-ion batteries[J]. Solid State Sciences, 2008, 10(1): 5-11.

[20] Spina L, Jia Y Z, Ducourant B, et al. Compositional and structural variations in the ternary system Li-Al-Si[J]. Zeitschrift fur Kristallographie, 2003, 218(11): 740-746.

[21] Alcántara R, Tillard-Charbonnel M, Spina L, et al. Electrochemical reactions of lithium with Li₂ZnGe and Li₂ZnSi[J]. Electrochimica Acta, 2002, 47(7): 1115-1120.

[22] Hwang C, Park J. Electrochemical properties of Si-Ge-Mo anode composite materials prepared by magnetron sputtering for Lithium ion batteries[J]. Electrochimica Acta, 2011, 56(19): 6737-6747.

[23] Wang J, Du N, Zhang H, et al. Cu-Si_1-xGe core-shell nanowire arrays as three-dimensional electrodes for high-rate capability lithium-ion batteries[J]. Journal of Power Sources, 2012, 208: 434-439.

[24] Ma R J, Liu Y F, He Y P, et al. Chemical preinsertion of lithium: an approach to improve the intrinsic capacity retention of bulk Si anodes for Li-ion batteries[J]. Journal of Physical Chemistry Letters, 2012, 3(23): 3555-3558.

[25] Liu Y F, He Y P, Ma R J, et al. Improved lithium storage properties of Mg₂Si anode material synthesized by hydrogen-driven chemical reaction[J]. Electrochemistry communications, 2012, 25: 15-18.

[26] Li J, Dahn J R. An in situ X-ray diffraction study of the reaction of Li with crystalline Si[J]. Journal of the Electrochemical Society, 2007, 154(3): A156-A161.

[27] Liu X H, Zhang L Q, Zhong L, et al. Ultrafast electrochemical lithiation of individual Si nanowire anodes[J]. Nano Letters, 2011, 11(6): 2251-2258.

[28] Wang C, Li X, Wang Z, et al. In situ TEM investigation of congruent phase transition and structural evolution of nanostructured silicon/carbon anode for lithium ion batteries[J]. Nano Letters, 2012, 12(3): 1624-1632.

[29] McDowell M T, Lee S W, Harris J T, et al. In situ TEM of two-phase lithiation of amorphous silicon nanospheres[J]. Nano Letters, 2013, 13(2): 785-764.

[30] Zhang T, Gao J, Fu L J, et al. Natural graphite coated by Si nanoparticles as anode materials for lithium ion batteries[J]. Journal of Materials Chemistry, 2007, 17(13): 1321-1325.

[31] Liu X H, Zhong L, Huang S, et al. Size-dependent fracture of silicon nanoparticles during lithiation[J]. ACS Nano, 2012, 6(2): 1522-1531.

[32] Wang J W, He Y, Fan F, et al. Two-phase electrochemical lithiation in amorphous silicon[J]. Nano Letters, 2013, 13(2): 709-715.

[33] Lee S W, McDowell M T, Berla L A, et al. Fracture of crystalline silicon nanopillars during electrochemical lithium insertion[J]. Proceedings of the National Academy of Sciences of the United States of America, 2012, 109(11): 4080-4085.

[34] Zhao K, Pharr M, Wan Q, et al. Concurrent reaction and plasticity during initial lithiation of crystalline silicon in lithium-ion batteries[J]. Journal of the Electrochemical Society, 2012, 159(3): A238-A243.

[35]Liu X H, Fan F, Yang H, et al. Self-limiting lithiation in silicon nanowires[J]. ACS Nano, 2013, 7(2): 1495-1503.

晶态Li₁₂Si₇锂离子电池负极材料的电化学性能研究

Electrochemical Performance of Crystalline Li₁₂Si₇as Anode Material for Lithium Ion Battery

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]	范佳琪, 宋焕巧, 安佳莹, 阿依达娜·阿曼太, 陈默. 碳限域Li₃VO₄纳米材料的制备及其储锂性能[J]. 电化学（中英文）, 2023, 29(11): 211203-.
[3]	殷秀平, 赵玉峰, 张久俊. 钠离子电池硬碳基负极材料的研究进展[J]. 电化学（中英文）, 2023, 29(10): 2204301-.
[4]	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-.
[5]	陈思, 郑淞生, 郑雷铭, 张叶涵, 王兆林. 水热法制备锂电池Si@C负极材料的工艺优化研究[J]. 电化学（中英文）, 2022, 28(8): 2112221-.
[6]	王京玥, 王睿, 王诗琦, 王立帆, 詹纯. 一步固相法合成锂离子电池高镍层状正极材料[J]. 电化学（中英文）, 2022, 28(8): 2112131-.
[7]	谯渭川, 李芳儒, 肖瑾林, 屈丽娟, 赵晓, 张梦, 庞春雷, 李子坤, 任建国, 贺雪琴. 硅氧材料的膨胀性能研究和改善[J]. 电化学（中英文）, 2022, 28(5): 2108121-.
[8]	王加义, 郭胜楠, 王新, 谷林, 苏东. 锂离子电池高镍层状氧化物正极结构失效机制[J]. 电化学（中英文）, 2022, 28(2): 2108431-.
[9]	郭瑞琪, 吴锋, 王欣然, 白莹, 吴川. 多电子反应材料推动高能量密度电池发展：材料与体系创新[J]. 电化学（中英文）, 2022, 28(12): 2219011-.
[10]	朱振威, 邱景义, 王莉, 曹高萍, 何向明, 王京, 张浩. 人工智能在锂离子电池研发中的应用[J]. 电化学（中英文）, 2022, 28(12): 2219003-.
[11]	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-.
[12]	侯廷政, 陈翔, 蒋璐, 唐城. 当前和下一代锂离子电池电解液的原子尺度微观认识和研究进展[J]. 电化学（中英文）, 2022, 28(11): 2219007-.
[13]	李丹丹, 纪翔宇, 陈明, 杨燕茹, 王晓东, 冯光. 低聚离子液体的体相与界面及其电化学储能应用[J]. 电化学（中英文）, 2022, 28(11): 2219002-.
[14]	骆晨旭, 师晨光, 余志远, 黄令, 孙世刚. 富锂锰基层状正极材料的合成及其首周过充下的结构演化[J]. 电化学（中英文）, 2022, 28(1): 2006131-.
[15]	李姝谨, 曹志康, 王文凯, 张晓菡, 向兴德. 硫酸盐功能电解液增强水系钠离子电池NaTi₂(PO₄)₃/C负极材料电化学性能的研究[J]. 电化学（中英文）, 2021, 27(6): 605-613.