Electrochemical Cycling of Redox-Active Boron Cluster-Based Materials in the Solid State
Electrochemical Cycling of Redox-Active Boron Cluster-Based Materials in the Solid State
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DOI：
10.1021/jacs.3c03065
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发表时间：
2023-06-23
影响因子：
15
通讯作者：
Spokoyny，Alexander M.
中科院分区：
文献类型：
--
作者：
Ready，Austin D.;Irshad，Ahamed;Spokoyny，Alexander M.
这项工作证明了第一次成功的电化学循环的氧化还原活性硼簇基材料在固态。具体而言，我们设计并合成了醚官能化的十二硼酸酯簇B12（OCH 3）12，这是B12（OR）12家族中最小的氧化还原活性结构单元。这种物质在溶液中可以可逆地进入四种氧化态，从二价阴离子到自由基阳离子。我们表明，一个化学隔离和特征的中性[B12（OCH 3）12] 0集群可以用作阴极活性材料在PEO基可充电全固态电池与锂金属阳极。该电池表现出令人印象深刻的活性材料利用率接近95%，在C/20率，96%的高库仑效率，和可逆性，只有4%的容量衰减后，16天的循环。这项工作代表了电化学存储的氧化还原活性成分的发展的概念出发，并作为一个切入点，以更广泛的一类硼烷基材料。
This work demonstrates the first successful electrochemical cycling of a redox-active boron cluster-based material in the solid state. Specifically, we designed and synthesized an ether-functionalized dodecaborate cluster, B12(OCH3)12, which is the smallest redox-active building block in the B12(OR)12family. This species can reversibly access four oxidation states in solution, ranging from a dianion to a radical cation. We show that a chemically isolated and characterized neutral [B12(OCH3)12]0cluster can be utilized as a cathode active material in a PEO-based rechargeable all-solid-state cell with a lithium metal anode. The cell exhibits an impressive active material utilization close to 95% at C/20 rate, a high Coulombic efficiency of 96%, and reversibility, with only 4% capacity fade after 16 days of cycling. This work represents a conceptual departure in the development of redox-active components for electrochemical storage and serves as an entry point to a broader class of borane-based materials.