多功能粘结剂稳定高容量硅碳负极材料的研究

电动汽车和智能电子产品对高能量密度锂离子电池的需求日益迫切。硅是最具发展前途的下一代高容量负极材料。但硅充放电过程体积变化大，引起电极结构崩塌和表面固体电解质界面（SEI）膜碎裂等难题，导致容量衰减快，严重阻碍了其商业化应用。目前工业化应用的石墨负极粘结剂羧甲基纤维素/丁苯橡胶（CMC/SBR）体系对硅的粘结性不强，无法满足高容量硅负极需求。本文将高弹性水性聚氨酯（PU）引入高粘性聚丙烯酸（PAA）基粘结剂，改善PAA的脆性，得到兼具高弹性、高粘性的水溶性多功能粘结剂（PAU），稳定高容量硅碳负极的电极结构及表面SEI膜。

首先对比研究了PAA和PAU的理化和电化学性能。PU与PAA基通过氢键和Li+形成弹性的交联网络结构，断裂形变达到490%，足以容纳硅300%的体积膨胀率；Si/C@PAU电极的平均粘结力达到188 N m-1，远高于对比样Si/C@PAA电极（105 N m-1）。PAU有效提升了高容量硅碳负极的电化学性能。在1 C大电流密度（1000 mAh g-1）下，Si/C@PAU初始容量达到759 mAh g-1，循环400圈后，容量保持率为83.5%；Si/C@PAU表现出优异的倍率特性，5 C的比容量达到593 mAh g-1，对比样仅有92 mAh g-1。

然后研究了PAU稳定硅碳负极材料的作用机理。PAU可增强硅碳电极耐辊压性能，并在长循环过程中维持电极结构稳定。这主要是PAU的弹性网络结构耗散了辊压外力、硅嵌脱锂大体积膨胀应力对电极结构的冲击。弹性网络结构的高响应性还使电极在反复形变过程中，始终保持良好的导电网络，使Si/C@PAU具有高倍率性能。对Si/C表面SEI膜结构和成分进行分析，发现PAU能促进硅碳颗粒表面形成均匀而致密的SEI膜。这主要是PAU的酰胺基、氨基、酯基增强了其与硅碳的界面作用力，使其在硅碳表面形成具有优良韧性的超薄聚合物保护膜，优化了原生SEI膜结构和组分。

高弹性PU赋予PAU大形变率；PU、PAA丰富的官能团使PAU与硅活性颗粒界面具有良好的作用力；两者协同作用，有效提升高容量硅碳的长循环性能和倍率性能。本论文的研究成果为设计超高容量硅碳负极用高性能粘结剂提供了新思路。

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