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在全电池化学体系中,合金化锗纳米线阳极在很宽的温度范围内显著优于石墨阳极。

Alloying Germanium Nanowire Anodes Dramatically Outperform Graphite Anodes in Full-Cell Chemistries over a Wide Temperature Range.

作者信息

Collins Gearoid A, McNamara Karrina, Kilian Seamus, Geaney Hugh, Ryan Kevin M

机构信息

Department of Chemical Sciences and Bernal Institute, University of Limerick, Limerick V94 T9PX, Ireland.

Department of Physics, University of Limerick, Limerick V94 T9PX, Ireland.

出版信息

ACS Appl Energy Mater. 2021 Feb 22;4(2):1793-1804. doi: 10.1021/acsaem.0c02928. Epub 2021 Feb 2.

Abstract

The electrochemical performance of Ge, an alloying anode in the form of directly grown nanowires (NWs), in Li-ion full cells (vs LiCoO) was analyzed over a wide temperature range (-40 to 40 °C). LiCoO||Ge cells in a standard electrolyte exhibited specific capacities 30× and 50× those of LiCoO||C cells at -20 and -40 °C, respectively. We further show that propylene carbonate addition further improved the low-temperature performance of LiCoO||Ge cells, achieving a specific capacity of 1091 mA h g after 400 cycles when charged/discharged at -20 °C. At 40 °C, an additive mixture of ethyl methyl carbonate and lithium bis(oxalato)borate stabilized the capacity fade from 0.22 to 0.07% cycle. Similar electrolyte additives in LiCoO||C cells did not allow for any gains in performance. Interestingly, the capacity retention of LiCoO||Ge improved at low temperatures due to delayed amorphization of crystalline NWs, suppressing complete lithiation and high-order LiGe phase formation. The results show that alloying anodes in suitably configured electrolytes can deliver high performance at the extremes of temperature ranges where electric vehicles operate, conditions that are currently not viable for commercial batteries without energy-inefficient temperature regulation.

摘要

以直接生长的纳米线(NWs)形式存在的合金负极锗在锂离子全电池(相对于LiCoO₂)中的电化学性能在很宽的温度范围(-40至40°C)内进行了分析。在标准电解质中的LiCoO₂||Ge电池在-20°C和-40°C时的比容量分别是LiCoO₂||C电池的30倍和50倍。我们进一步表明,添加碳酸丙烯酯进一步改善了LiCoO₂||Ge电池的低温性能,在-20°C下充电/放电400次后比容量达到1091 mA h g⁻¹。在40°C时,碳酸甲乙酯和双(草酸根)硼酸锂的添加剂混合物使容量衰减从0.22%/循环稳定到0.07%/循环。在LiCoO₂||C电池中添加类似的电解质添加剂并没有使性能得到任何提升。有趣的是,由于结晶NWs的非晶化延迟,抑制了完全锂化和高阶LiGe相的形成,LiCoO₂||Ge在低温下的容量保持率得到了提高。结果表明,在适当配置的电解质中的合金负极可以在电动汽车运行的极端温度范围内提供高性能,而目前对于没有低效温度调节的商业电池来说,这些条件是不可行的。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/437c/8288911/ad350a0b0229/ae0c02928_0002.jpg

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