Computational discovery of superior vanadium-niobate-based cathode materials for next-generation all-solid-state lithium-ion battery applications
Computational discovery of superior vanadium-niobate-based cathode materials for next-generation all-solid-state lithium-ion battery applications
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用于下一代全固态锂离子电池应用的优质钒铌酸盐基正极材料的计算发现
DOI：
10.1039/d3ta08096j
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发表时间：
2024
影响因子：
11.9
通讯作者：
Chakraborty T
中科院分区：
文献类型：
--
作者：
Chakraborty T
全固态锂离子电池（asslib）处于绿色和可持续能源发展研究的前沿。开发asslib用于商业应用的关键挑战之一是寻找具有高容量，高电压和高功率密度的正极材料。结合第一性原理计算和各种晶体结构预测算法，我们探索了LiVO2-Li3NbO4伪二元线，以确定具有改进性能的新型化学计量学，作为ASSLIB应用的正极材料。基于密度泛函理论（DFT）对从头开始随机结构搜索（AIRSS）、遗传算法和构型枚举程序获得的晶体结构进行的超过10000次计算，我们预测了五种新的化学计量，Li23Nb7V2O32、Li10Nb3VO14、Li7Nb2VO10、Li11Nb3V2O16、Li4NbVO6，以及实验已知的化学计量，Li5NbV2O8。所有新的化学计量都被发现具有阳离子无序的岩盐晶体结构，并且每个原子与母体成分的凸壳的距离在30 meV以内。与现有的铌酸钒基电极材料相比，这些新相具有更优越的性能，包括更高的理论容量、更小的带隙、更高的平均锂嵌入电压、完全锂去氢后的体积变化较小、良好的机械和动态稳定性、更好的锂传导激活势垒和高温稳定性。我们的研究结果有望激发进一步的实验，以合成和测试这些特定的铌酸钒基材料作为锂离子阴极材料的实际性能。
All-solid-state lithium-ion batteries (ASSLIBs) are at the forefront of green and sustainable energy development research. One of the key challenges in the development of ASSLIBs for commercial applications is to find cathode materials that have high capacity, voltage and power density. Using a combination of first-principles calculations and various crystal structure prediction algorithms, we explore the LiVO2–Li3NbO4 pseudobinary tieline to identify novel stoichiometries with improved properties as cathode materials for ASSLIB applications. Based on more than 10 000 Density Functional Theory (DFT) calculations using crystal structures obtained from ab initio random structure searching (AIRSS), genetic algorithm, and configuration enumeration procedures, we predict five novel stoichiometries, Li23Nb7V2O32, Li10Nb3VO14, Li7Nb2VO10, Li11Nb3V2O16, Li4NbVO6, along with an experimentally known stoichiometry, Li5NbV2O8. All the novel stoichiometries are found to have cation-disordered rock-salt crystal structures and fall within 30 meV per atom from the convex hull of the parent compositions. These new phases are predicted to have superior properties compared to the current vanadium-niobate-based electrode materials, including a higher theoretical capacity, lower band gap, higher average Li intercalation voltage, minor volume change upon full Li delithiation, good mechanical and dynamical stability, improved Li-conduction activation barrier and high-temperature stability. Our results are anticipated to inspire further experiments to synthesise and test these specific vanadium-niobate-based materials for their actual performance as Li-ion cathode materials.