硅材料因其高的理论比容量(4200 mAh/g)而成为极具发展潜力的锂离子电池负极材料之一。纳米硅负极材料可有效避免材料在循环过程中的粉化现象,同时具有较短的Li+和电子传输路径,相应电极的电化学性能与微米硅电极相比显著提升,但是纳米结构硅材料比表面积过大、振实密度低等特点限制了其在实际生产中的应用。近年来,使用纳米结构硅材料作为一次结构单元构建微/纳复合结构硅基负极材料的策略被广泛研究。本文综述了微/纳复合结构硅基负极材料的研究进展,总结了微/纳复合结构硅基负极材料中一次颗粒和二次颗粒的选择与结构设计要素,并对具有代表性的微/纳复合结构硅基负极材料物理和电化学性能进行了介绍,提出优化的材料结构和电极设计方案。最后,对微/纳复合结构硅基负极材料存在问题进行简单分析并展望了其研究前景。
Due to high theoretical specific capacity(4200 mAh/g), silicon is considered as one of the most promising materials for lithium-ion battery negative electrodes. Nano-silicon negative materials can effectively avoid the pulverization of the particles during cycling and have shorter Li+ and electron transport paths. The electrochemical performance of the corresponding electrodes is significantly improved compared to that of the micro-sized silicon based electrodes. However, the specific surface area of nano-materials is too large while the tap density is low, that limits the application of nano-silicon negative materials in practical production. In recent years, the strategy of using nano-structured silicon materials as building units to construct nano/micro structured silicon-based negative materials has been widely studied. The development of nano/micro structured silicon-based materials for lithium-ion batteries is reviewed. The selection and structural design elements of nano-sized primary particles as well as micro-sized secondary particles are summarized. The physical and electrochemical properties of representative nano/micro structured silicon-based materials are also introduced. Moreover, an optimized design of the nano/micro structured silicon-based material structure and electrode structure is proposed. Finally, challenges and problems existing in nano/micro structured silicon-based negative materials are briefly analyzed and prospects of them as negative materials for lithium-ion batteries are discussed.
Contents
1 Introduction
2 Structure of primary particles in nano/micro structured silicon-based negative materials
2.1 Primary particles of nano-silicon
2.2 Void space in primary particles
3 Design elements of secondary particles in nano/micro structured silicon-based negative materials
3.1 Void space in secondary particles
3.2 Surface coating of secondary particles
3.3 Size optimization of secondary particles
4 Conclusion and outlook
[1] Huggins R A, Boukamp B A. Journal of the Electrochemical Society, 1981, 128(4):725.
[2] Winter M, Besenhard J O, Spahr M E, Novak P. Advanced Materials, 1998, 10(10):725.
[3] Wu H, Chan G, Choi J W, Ryu I, Yao Y, McDowell M T, Lee S W, Jackson A, Hu L B, Cui Y. Nature Nanotechnology, 2012, 7(5):310.
[4] Liu X H, Zhong L, Huang S, Mao S X, Zhu T, Huang J Y. ACS Nano, 2012, 6(2):1522.
[5] Ji H, Kim J W, Sung Y E, Oh S M. Electrochemical and Solid-State Letters, 2004, 7(10):A306.
[6] Oh S W, Myung S T, Bang H J, Chong S Y, Amine K, Sun Y K. Electrochemical and Solid-State Letters, 2009, 12(9):A181.
[7] Nam K T, Kim D W, Yoo P J, Chiang C Y, Meethong N,Hammond P T, Chiang Y M, Belcher A M. Science, 2006,312(5775):885.
[8] Xue D J, Xin S, Yan Y, Jiang K C, Yin Y X, Guo Y G, Wan L J. Journal of the American Chemical Society, 2012, 134(5):2512.
[9] Seng K H, Park M H, Guo Z P, Liu H K, Cho J. Angewandte Chemie, 2012, 124(23):5755.
[10] Su L W, Jing Y, Zhou Z. Nanoscale, 2011, 3(10):3967.
[11] Lin D C, Lu Z D, Hsu P C, Lee H R, Liu N, Zhao J, Wang H T, Liu C, Cui Y. Energy & Environmental Science, 2015, 8(8):2371.
[12] Wang Y G, Li H Q, He P, Hosono E, Zhou H S. Nanoscale, 2010, 2(8):1294.
[13] Guo Y G, Hu Y S, Maier J. Chemical Communications, 2006, 26(26):2783.
[14] Guo Y G, Hu Y S, Sigle W, Maier J. Advanced Materials, 2007, 19(16):2087.
[15] Guo Y G, Hu J S, Wan L J. Advanced Materials, 2008, 20:2878.
[16] Liou S H, Tsou T C, Wang S L, Li L A, Chiang H C, Li W F, Lin P P, Lai C H, Lee H L, Lin M H, Hsu J H, Chen C R, Shih T S, Liao H Y, Chung Y T. Journal of Nanoparticle Research, 2012, 14(8):544,
[17] Dobashi R. Journal of Physics Conference Series, 2009, 170:012029.
[18] Yoshio M, Wang H, Fukuda K, Umeno T, Abe T, Ogumi Z. Journal of Materials Chemistry, 2004, 14(11):1754.
[19] Yang S B, Song H H, Chen X H. Electrochimica Acta, 2006, 8(1):137.
[20] Bao Z H, Weatherspoon M R, Shian S, Cai Y, Graham P D, Allan S M, Ahmad G, Dickerson M B, Church B C, Kang Z T, Abernathy H W, Summers C J, Liu M L, Sandhage K H. Nature, 2007, 446(7132):172.
[21] Bang B M, Kim H, Song H K, Cho J, Park S. Energy and Environmental Science, 2011, 4(12):5013.
[22] Bang B M, Lee J I, Kim H, Cho J, Park S. Advanced Energy Materials, 2012, 2(7):878.
[23] Zhu X, Chen H, Wang Y, Xia L, Tan Q, Li H, Zhong Z, Su F, Zhao X S. Journal of Materials Chemistry C, 2013, 1(14):4483.
[24] Yin Y X, Xin S, Wan L J, Li C J, Guo Y G. Journal of Materials Chemistry C, 2011, 115(29):14148.
[25] Shin K, Park D J, Lim H S, Sun Y K, Suh K D. Electrochimica Acta, 2011, 58(1):578.
[26] Lee J H, Kim W J, Kim J Y, Lim S H, Lee S M. Journal of Power Sources, 2008, 176(1):353.
[27] Lee J I, Choi N S, Park S. Energy & Environmental Science, 2012, 5(7):7878.
[28] Hu Y S, Demircakan R, Titirici M M, Müller J O, Schlögl R, Antonietti M, Maiera J. Angewandte Chemie International Edition, 2008, 47(9):1645.
[29] Ren W F, Zhang Z L, Wang Y H, Tan Q Q, Zhong Z Y, Su F B. Journal of Materials Chemistry A, 2015, 3(11):5859.
[30] Jung S C, Choi J W, Han Y K. Nano Letters, 2012, 12(10):5342.
[31] McDowell M T, Lee S W, Harris J T, Korgel B A, Wang C M, Nix W D, Cui Y. Nano Letters, 2013, 13(2):758.
[32] Wang J W, He Y, Fan F F, Liu X H, Xia S M, Liu Y, Harris T, Li H, Huang J Y, Mao S X, Zhu T. Nano Letters, 2013, 13(2):709.
[33] Kim H, Seo M, Park M H, Cho J. Angewandte Chemie, 2010, 49(12):2146.
[34] Li H. Electrochemical and Solid-State Letters, 1999, 2(11):547.
[35] Mazouzi D, Lestriez B, Roue De' L, Guyomard D. Electrochemical and Solid-State Letters, 2009, 12(11):A215.
[36] Yang J, Winter M, Besenhard J O. Solid State Ionics, 1996, 90(1/4):281.
[37] Kasavajjula U, Wang C S, Appleby A J. Journal of Power Sources, 2007, 163(2):1003.
[38] Park M H, Kim M G, Joo J, Kim K, Kim J, Ahn S, Cui Y, Cho J. Nano Letters, 2009, 9(11):3844.
[39] Peng K, Jie J, Zhang W, Lee S T. Applied Physics Letters, 2008, 93(3):033105.
[40] Chan C K, Peng H, Liu G, McIlwrath K, Zhang X F, Huggins R A, Cui Y. Nature Nanotechnology, 2008, 3(1):31.
[41] Chan C K, Ruffo R, Hong S S, Huggins R A, Cui Y. Journal of Power Sources, 2009, 189(1):34.
[42] Cui L F, Ruffo R, Chan C K, Peng H, Cui Y. Nano Letters, 2009, 9(1):491.
[43] Song T, Xia J L, Lee J H, Lee D H, Kwon M S, Choi J M, Wu J, Doo S K, Chang H, Park W I, Zang D S, Kim H, Huang Y G, Hwang K C, Rogers J A, Paik U. Nano Letters, 2010, 10(5):1710.
[44] Li J C, Dozier A K, Li Y C, Yang F Q, Cheng Y T. Journal of the Electrochemical Society, 2011, 158(6):A689.
[45] Ohara S, Suzuki J, Sekine K, Takamura T. Journal of Power Sources, 2004, 136(2):303.
[46] Takamura T, Ohara S, Uehara M, Suzuki J, Sekine K. Journal of Power Sources, 2004, 129(1):96.
[47] Yi R, Dai F, Gordin M L, Chen S R, Wang D H. Advanced Energy Materials, 2013, 3(3):295.
[48] Yi R, Dai F, Gordin M L, Sohn H, Wang D H. Advanced Energy Materials, 2013, 3(11):1507.
[49] Gauthier M, Mazouzi D, Reyter D, Lestriez B, Moreau P, Guyomard D, Rou De' L. Energy & Environmental Science, 2013, 6(7):2145.
[50] Chen X X, Li X L, Ding F, Xu W, Xiao J, Cao Y L, Meduri P, Liu J, Graff G L, Zhang J G. Nano Letters, 2012, 12(8):4124.
[51] Dai F, Yi R, Gordin M, Chen S R, Wang D H. RSC Advances, 2012, 2(33):12710.
[52] Liu N, Lu Z D, Zhao J, McDowell M T, Lee H W, Zhao W T, Cui Y. Nature Nanotechnology, 2014, 9(3):187.
[53] Sohn H, Dong H K, Yi R, Tang D, Li S E, Jung Y S, Wang D H. Journal of Power Sources, 2016, 334:128.
[54] Kim S Y, Lee J, Kim B H, Kim Y J, Yang K S, Park M S. ACS Applied Materials & Interfaces, 2016, 8(19):12109.
[55] Yao Y, McDowell M T, Ryu I, Wu H, Liu N, Hu L B, Nix W D, Cui Y. Nano Letters, 2011, 11(7):2949.
[56] Xiao Q, Gu M, Yang H, Li B, Zhang C, Liu Y, Liu F, Dai F, Yang L, Liu Z, Xiao X, Liu G, Zhao P, Zhang S, Wang C, Lu Y, Cai M. Nature Communications, 2015, 6:8844.
[57] Chen D Y, Mei X, Ji G, Lu M H, Xie J P, Lu J M, Lee J Y. Angewandte Chemie International Edition, 2012, 51(10):2409.
[58] Liu N, Wu H, McDowell M T, Yao Y, Wang C M, Cui Y. Nano Letters, 2012, 12(6):3315.
[59] Li X L, Meduri P, Chen X X, Qi W, Engelhard M H, Xu W, Ding F, Xiao J, Wang W, Wang C M, Zhang J G, Liu J. Journal of Materials Chemistry, 2012, 22(22):11014.
[60] Pan L, Wang H B, Gao D C, Chen S Y, Tan L, Li L. Chemical Communications, 2014, 50(44):5878.
[61] Tao H C, Fan L Z, Song W L, Wu M, He X B, Qu X H. Nanoscale, 2014, 6(6):3138.
[62] Zhou X Y, Tang J J, Yang J, Xie J, Ma L L. Electrochimica Acta, 2013, 87(1):663.
[63] Feng X J, Cui H M, Miao R R, Yan N F, Ding T D, Xiao Z Q. Ceramics International, 2015, 42(1):589.
[64] Magasinski A, Dixon P, Hertzberg B, Kvit A, Ayala J, Yushin G. Nat. Mater., 2010, 9(4):353.
[65] Jung D S, Hwang T H, Park S B, Choi J W. Nano Letters, 2013, 13(5):2092.
[66] Yoo J K, Kim J, Choi M J, Park Y U, Hong J, Baek K M, Kang K, Jung Y S. Advanced Energy Materials, 2014, 4(16):1400622.
[67] Feng X J, Yang J, Bie Y T, Wang J L, Nuli Y, Lu W. Nanoscale, 2014, 6(21):12532.
[68] Ko M, Chae S, Ma J, Kim N, Lee H W, Cui Y, Cho J. Nature Energy, 2016, 1(9):16113.
[69] Yoshio M, Wang H Y, Fukuda K, Umeno T, Dimov N, Ogumi Z. Journal of the Electrochemical Society, 2002, 149(12):A1598.
[70] Dimov N, Fukuda K, Umeno T, Kugino S, Yoshino M. Journal of Power Sources, 2003, 114(1):88.
[71] Wu X D, Wang Z X, Chen L Q, Huang X J. Electrochemistry Communications, 2003, 5(11):935.
[72] Kwon E, Lim H S, Sun Y K, Suh K D. Solid State Ionics, 2013, 237(16):28.
[73] Chen H X, Xiao Y, Wang L, Yang Y. Journal of Power Sources, 2011, 196(16):6657.
[74] Park S E, Kim B E, Lee S W, Lee J K. 中国有色金属学报(Transactions of Nonferrous Metals Society of China), 2009, 19(4):1023.
[75] Jeong G, Kim J G, Park M S, Seo M, Hwang S M, Kim Y U, Kim Y J, Kim J H, Dou S X. ACS Nano, 2014, 8(3):2977.
[76] Fang S, Shen L F, Xu G Y, Nie P, Wang J, Dou H, Zhang X G. ACS Applied Materials & Interfaces, 2014, 6(9):6497.
[77] Nguyen H T, Zamfir M R, Duong L D, Lee Y H, Bondavalli P, Pribat D. Journal of Materials Chemistry, 2012, 22(47):24618.
[78] Shao D, Tang D P, Mai Y J, Zhang L Z. Journal of Materials Chemistry A, 2013, 1(47):15068.
[79] Wang D S, Gao M X, Pan H G, Wang J H, Liu Y F. Journal of Power Sources, 2014, 256(12):190.
[80] Yen Y C, Chao S C, Wu H C, Wu N L. Journal of the Electrochemical Society, 2009, 156(2):A95.
[81] Xu Y H, Yin G P, Ma Y L, Zuo P J, Cheng X Q. Journal of Materials Chemistry, 2010, 20(16):3216.
[82] Chen S R, Gordin M L, Yi R, Howlett G, Sohn H, Wang D H. Physical Chemistry Chemical Physics, 2012, 14(37):12741.
[83] Park Y W, Choi N S, Park S J, Woo S H, Sim S J, Jang B Y, Oh S M, Park S J, Cho J P, Lee K T. Advanced Energy Materials, 2013, 3(2):206.
[84] Kim J W, Ji H R, Lee K T, Oh S M.Journal of Power Sources, 2005, 147(1/2):227.
[85] Liu Y, Hudak N S, Huber D L, Limmer S J, Sullivan J P, Huang J Y. Nano Lett, 2011, 11:4188
[86] Guo Z P, Wang J Z, Liu H K, Dou S X. Journal of Power Sources, 2005, 146(1):448.
[87] Lu Z D, Liu N, Lee H W, Zhao J, Li W Y, Li Y Z, Cui Y. ACS Nano, 2015, 9(3):2540.
[88] Li S, Qin X Y, Zhang H R, Wu J X, He Y B, Li B H, Kang F Y. Electrochemistry Communications, 2014, 49(49):98.
[89] Song J X, Chen S R, Zhou M J, Xu T, Lv D P, Gordin M L, Long T J, Melnyk M, Wang D H. Journal of Materials Chemistry A, 2013, 2(5):1257.
[90] Xu Z L, Gang Y, Garakani M A, Abouali S, Huang J Q, Kim J K. Journal of Materials Chemistry A, 2016, 4(16):6098.
[91] Wu H, Zheng G Y, Liu N, Carney T J, Yang Y, Cui Y. Nano Letters, 2012, 12(2):904.
[92] Li Y Z, Yan K, Lee H W, Lu Z D, Liu N, Cui Y. Nature Energy, 2016, 1(2):15029.
[93] Luo F, Liu B N, Zheng J Y, Chu G, Zhong K F, Li H, Huang X J, Chen L Q. Journal of the Electrochemical Society, 2015, 162(14):A2509.
[94] Vijayaraghavan B, Ely D R, Chiang Y M, Garc'la-Garc'la R, Garc'la R E. Journal of the Electrochemical Society, 2012, 159(5):A548.
[95] Srinivasan V, Newman J. Journal of the Electrochemical Society, 2004, 151(10):A1517.
[96] Darling R, Newman J. Journal of the Electrochemical Society, 1997, 144(12):4201.
[97] Farkhondeh M, Delacourt C. Journal of the Electrochemical Society, 2012, 159(2):177.
[98] Doyle M, Fuller T F, Newman J S. Journal of the Electrochemical Society, 1993, 140(6):1526.
[99] Farkhondeh M, Safari M, Pritzker M, Fowler M, Han T, Wang J, Delacourt C. Journal of the Electrochemical Society, 2014, 161(3):A201.
[100] Zavalis T G, Klett M, Kjell M H, Behm M, Lindström R W, Lindbergh G. Electrochimica Acta, 2013, 110(6):335.
[101] Rinaldo S G, Urchaga P, Hu J, Lee W, Stumper J, Rice C, Eikerling M. Physical Chemistry Chemical Physics, 2014, 16(48):26876.
[102] Röder F, Sonntag S, Schröder D, Krewer U. Energy Technology, 2016, 4:1588.
[103] Chung D W, Shearing P R, Brandon N P, Harris S J, Garcia R E. Journal of the Electrochemical Society, 2014, 161(3):A422.
[104] Smith M, Garci Di' A R E, Horn Q C. Journal of the Electrochemical Society, 2009, 156(11):A896.
[105] Kim S O, Manthiram A. Journal of Materials Chemistry A, 2014, 3(5):2399.
[106] Cho I, Choi J, Kim K, Ryou M H, Yong M L. RSC Advances, 2015, 5(115):95073.
[107] Zhang L, Wang Y H, Kan G W, Zhang Z L, Wang C G, Zhong Z Y, Su F B. RSC Advances, 2014, 4(81):43114.
[108] Wang H, Xie J, Zhang S C, Cao G S, Zhao X B. RSC Advances, 2016, 6(74):69882.
[109] Xu Q, Li J Y, Sun J K, Yin Y X, Wan L J, Guo Y G. Advanced Energy Materials, 2016,7(3):1601481.
[110] Zheng T, Liu Y H, Fuller E W, Tseng S, Sacken U V, Dahn J R. Journal of the Electrochemical Society, 1995, 142(8):2581.
[111] De Volder M F, Tawfick S H, Baughman R H, Hart A J. Science, 2013, 339(6119):535.
[112] Gogotsi Y, Simon P. Science, 2011, 334(6058):917.
[113] Li X L, Gu M, Hu S Y, Kennard R, Yan P F, Chen X L, Wang C M, Sailor M J, Zhang J G, Liu J. Nature Communications, 2014, 5(5):4105.
[114] Hu L B, Wu H, Hong S S, Cui L F, McDonough J R, Bohy S, Cui Y. Chemical Communications, 2011, 47(1):367.
[115] Ji J Y, Ji H X, Zhang L L, Zhao X, Bai X, Fan X B, Zhang F, Ruoff R S. Advanced Materials, 2013, 25(33):4673.
[116] Gowda S R, Pushparaj V, Herle S, Girishkumer G, Gordon J G, Gullapalli H. Nano Letters, 2012, 12(12):6060.
[117] 武兆辉(Wu Z H), 杨娟玉(Yang J Y), 闫坤(Yan K), 于冰(Yu B), 方升(Fang S), 史碧梦(Shi B M). 稀有金属(Rare Materials), 2016, 40(8):838.
[118] Wang C, Wu H, Chen Z, McDowell M T, Cui Y, Bao Z N. Nature Chemistry, 2013, 5(12):1042.
[119] Chen Z, Wang C, Lopez J, Lu Z D, Cui Y, Bao Z N. Advanced Energy Materials, 2015, 5(8):1401826.
[120] Kwon T W, You K J, Lee I, Kim T S, Choi J W, Coskun A. Advanced Materials, 2014, 26(47):7979.