Citation: . CCS Chemistry | 接触-消融，给锂电极穿上保护“镓”[J]. CCS Chemistry, ;2020, 2(0): 686-695. doi: 10.31635/ccschem.020.202000182 shu

CCS Chemistry | 接触-消融，给锂电极穿上保护“镓”

Figures(1)

武汉大学付磊课题组设计了一种基于液态金属的保护层，首次利用液态金属的脆化和快速扩散等特性，显著抑制锂枝晶的生长，从而保护锂金属电池在高倍率下稳定长循环。

由于锂离子电池的能量密度已经难以满足日益增长的社会需求，具备更高能量密度的新一代电池在近年来受到越来越多的关注。其中，锂金属电池凭借锂金属电极超高理论比容量和极低电化学电位跻身前列。但是在长时间充放电过程中，锂金属电极的本征特性（包括极高反应活性和严重的体积膨胀）使其难以避免锂枝晶生长，而尖锐的枝晶极易刺穿隔膜，造成电池爆炸，这一严重的安全隐患也阻碍了锂金属电池的实际应用。

液态金属在新型电池中已经崭露头角，诺奖得主Goodenough教授在2016年提出钠钾合金作为室温液态金属电极。其流动性和自愈性能够抑制电极表面产生枝晶，但是这类材料的高反应活性、电极封装等问题仍亟待解决。那么针对现有蓬勃发展的锂金属电极，液态金属是否能为抑制枝晶生长给出另一份答卷呢？

近期，武汉大学付磊课题组另辟蹊径，聚焦于典型的液态金属——镓（Ga），制备出Ga基复合膜作为锂金属负极的保护层。该组提出了接触−消融机制，当枝晶刺入保护层时，即可触发Ga发生独特的脆化现象，合金化接触区域，抑制枝晶向上生长的应力，从而实现均匀的锂沉积。通过精心设计和优化膜结构，将Ga液滴限域于分级多孔的聚二甲基硅氧烷（PDMS）膜中，仅2 μm的膜厚实现Ga的稳定过冷态（熔点降低至–16.6oC），使其在长循环中保持液态性质。同时，PDMS的电绝缘性避免Ga参与电化学反应，而多孔通道确保了锂离子的快速传输，提高电解液浸润性（图1）。

图1

通过X射线光电子能谱的深度分析，作者证实了合金化产物是Ga14Li3。这与Ga发生电化学反应的产物截然不同，且锂在该合金中处于特殊的非键合状态，有利于在循环过程中锂离子的可逆脱出。二次离子质谱验证了锂沉积集中于保护层下方，说明锂离子能通过保护层并在其下方实现均匀沉积（图2）。

图2

作者进一步对比不同电流密度下对称电池的长循环性能来确认保护层的作用（图3）。在2 mA cm−2的电流密度下，未修饰的锂金属负极和纯PDMS修饰的锂负极均在较短时间内发生短路。而保护层作用下的锂电极寿命可超过2000 h。值得一提的是，即使在超高电流密度（10 mA cm−2）和大容量（5 mA h cm−2）下，受Ga基保护层作用的对称电池仍能维持极其稳定的电压曲线，这证实了接触−消融机制在高锂离子通量下的稳定性。此外，在保护层作用下，全电池也展现出优异的倍率性能和循环稳定性，说明了其实际应用的潜力。

图3

综上所述，该研究工作提供了一种可以接触消融锂枝晶的保护层，为锂金属负极提供实时保护。这些结果强调了与枝晶直接反应的重要性，并且该保护层可与其他抑制手段强强联手，有望完全实现金属负极的无枝晶生长。该工作以research article 的形式发表在CCS Chemistry，并在CCS Chemistry官网“Just Published”栏目上线。

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Citation: CCS Chem. 2020, 2, 686–695
Link：https://doi.org/10.31635/ccschem.020.202000182
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