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  负极由于其高的理论容量、较低的电化学反应电位和丰富的自然资源而被q泛认ؓ是下一代高能量密度锂离子电池极具应用前景的负极材料之一。然而,颗_在反复地嵌?脱锂q程中会发生巨大的体U变化,DzL硅颗粒出现开裂甚至粉化,造成电解液的不断消耗和SEI膜的反复生长Q得电极表现出较差的@环寿命。研I表明,通过对硅材料q行U米化、合金化、多孔化处理以及与碳基材料的复合{策略可以有效地解决上述问题Q但是复杂的工艺和过高的成本Q依焉制了其实际应用?


成果?/strong>


  日前Q厦门大学王鸣生教授团队直接从粘l剂改进的策略出发,通过使用植酸
(PA)作ؓ交联剂,l合传统?/span>CMC_结剂,?/span>Z强健?/span>CMC/PA交联_结剂网l?/span>用于U硅甉|Q如?/span>1a, b所C。在?/span>设计中,CMC是一U常规的水溶性粘l剂Q含有大量的基位点和羟基官能团?/span>PA通常来源于植物种子,׃含有丰富的羟基官能团Q可?/span>CMC_结?/span>的羧Z点和基官能团Ş成酯键和氢键Q又能够?/span>Si颗粒表面基形成氢键。而且Q不同于U?/span>CMC_结剂,q种枝接?/span>CMC/PA_结剂由于和颗_有更多的接触位点,可以形成更强的氢键。原位电镜及非原位谱学等表征手段充分揭示了:与单U的CMC_结?/span>相比Q?/span>CMC/PA交联_结剂网l具有更强的_附性能和更高的力学强度。因此,使用q种Ҏ的CMC/PA_结剂的电极,在反复电化学循环q程中可以有效地适应zL硅的体U变?/span>Q保持了甉|整体的完整性和SEI膜的E_性,最l表现出较优异的电化学性能?/span>


图文D



?/span>1. (a) CMC?/span>PA~合形成交联CMC/PA_结?/span>?/span>C意图?/span>(b) Si颗粒?/span>CMC/PA_结剂之间的化学键合?/span>(c) Si-CMC?/span>Si-CMC/PA甉|在@环过E中?/span>形貌演变C意图?/span>



?/span>2. (a, b) Si-CMC/PA复合?/span>?/span>TEM囑֒(c) HRTEM?/span>Q以?/span>对应?/span>元素mapping?/span>(d-h)?/span>Si-CMC/PA?/span>Si-CMC甉|的高分LXPS谱图Q?/span>(i) Si 2p?/span>(j) C 1sQ?/span>(k) Si-CMC/PA?/span>P 2p的高分LXPS?/span>?/span>?/span>(l)U?/span>Si?/span>Si-CMC?/span>Si-CMC/PA复合?/span>?/span>FT-IR谱图?/span>



?/span>3. Si-CMC?/span>Si-CMC/PA的流变性能(a)和剥试验结?/span>(b)?/span> CMC?/span>CMC/PA_结剂薄膜的应变-应力曲线(c)Q?/span>杨氏模量(d)和断裂应?/span>(e)?/span>



?/span>4. 电化学性能Q?/span>Si-CMC/PA甉|?/span>CV曲线(a)和充?/span>甉|U?/span>(b)?/span>Si-CMC/PA?/span>Si-CMC?/span>0.5 A g?1下的循环性能(c)Q倍率性能Q?/span>dQ以?/span>?/span>4 A g?1?/span>?/span>?/span>?/span>期@环性能Q?/span>eQ,全电池在1 C下的循环性能(f)?/span>倍率性能(g)?/span>



?/span>5. Si-CMC/PA甉|初始?/span>TEM?/span>(a)?/span>首次锂化不同时刻TEM?/span>(b-d)?/span>首次锂化q程中所标记区的纳c颗_团聚体的长短u长度变化直方?/span>(e)?/span>Si-CMC/PA甉|的选区电子衍射图:(f)初始?/span>Q?/span>(g)首次锂化后和(h)首次脱锂?/span>。另一?/span>Si-CMC/PA甉|三个原位电化学@环的TEM?/span>(i-p)?/span>


?/span>6. Si-CMC/PA甉|?/span>4 A g?1下@?/span>200ơ后的Ş?/span>:(a,b) TEM图,(c,d) HRTEM图,(e) SAED图,(f-l) HAADF图以?/span>对应的元?/span>mapping?/span>?/span>


?/span>7. SEI化学成分Q?/span>Si-CMC/PA甉|不同循环ơ数后的高分辨率XPS谱图(a) C 1s?/span>(b) F 1sQ?/span>Si-CMC甉|不同循环ơ数后的高分辨率XPS谱图(c) C 1s?/span>(d) F 1s?/span>


  该成果近日以?/span>?/span>Constructing Robust Cross-Linked Binder Networks for Silicon Anodes with Improved Lithium Storage Performance?span style="font-family:宋体;">发表?/span>ACS Applied Materials & Interfaces?/span>Q?span style="font-family:;">DOI: 10.1021/acsami.1c14907Q。厦门大学材料学院博士生郑志明ؓ该论文的W一作者,王鸣生教授ؓ本文通讯作者(详见N|站http://mswang.xmu.edu.cnQ?/span>


原文链接

https://doi.org/10.1021/acsami.1c14907

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