Accurate Quantum Chemical Reaction Energies for Lithium-Mediated Electrolyte Decomposition and Evaluation of Density Functional Approximations.
Accurate Quantum Chemical Reaction Energies for Lithium-Mediated Electrolyte Decomposition and Evaluation of Density Functional Approximations.
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DOI：
10.1021/acs.jpca.3c04369
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发表时间：
2023-10
期刊：
影响因子：
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通讯作者：
Sibali Debnath;Verena A. Neufeld;Leif D. Jacobson;Benjamin Rudshteyn;John L. Weber;Timothy C. Berkelbach;R. Friesner
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文献类型：
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作者：
Sibali Debnath;Verena A. Neufeld;Leif D. Jacobson;Benjamin Rudshteyn;John L. Weber;Timothy C. Berkelbach;R. Friesner
与锂离子电池性能相关的一个重要问题是在阳极表面形成固体电解质界面相。这种膜是由电解质分解形成的，并且会对稳定性和性能产生重要影响。在此，我们使用一系列密度泛函近似和相关波函数（WF）方法，包括具有单重、双重和微扰三重激发的耦合簇理论[CCSD(T)]以及辅助场量子蒙特卡罗（AFQMC），评估了碳酸乙烯酯及相关有机电解质分子的分解途径。我们发现，与开环相关的过渡态势垒在不同的泛函之间差异很大，范围从3.01到17.15千卡/摩尔，这可与CCSD(T)预测的12.84千卡/摩尔的值进行比较。这种较大的差异凸显了以精确的波函数方法为基准的重要性。对本研究中使用的所有密度泛函的性能比较表明，M06 - 2X - D3（一种元杂化广义梯度近似）、CAM - B3LYP - D3（一种范围分离杂化）和B2GP - PLYP - D3（一种双杂化）性能最佳，与CCSD(T)相比，平均误差约为1.50 - 1.60千卡/摩尔。我们还比较了比CCSD(T)更具可扩展性的波函数方法的性能，发现具有局域对自然轨道的耦合簇理论[DLPNO - CCSD(T)]和具有密度泛函理论尝试波函数的无相位AFQMC的平均误差分别为1.38千卡/摩尔和1.74千卡/摩尔。
An important concern related to the performance of Li-ion batteries is the formation of a solid electrolyte interphase on the surface of the anode. This film is formed from the decomposition of electrolytes and can have important effects on the stability and performance. Here, we evaluate the decomposition pathway of ethylene carbonate and related organic electrolyte molecules using a series of density functional approximations and correlated wave function (WF) methods, including the coupled-cluster theory with single, double, and perturbative triple excitations [CCSD(T)] and auxiliary-field quantum Monte Carlo (AFQMC). We find that the transition state barrier associated with ring opening varies widely across different functionals, ranging from 3.01 to 17.15 kcal/mol, which can be compared to the value of 12.84 kcal/mol predicted by CCSD(T). This large variation underscores the importance of benchmarking against accurate WF methods. A performance comparison of all of the density functionals used in this study reveals that the M06-2X-D3 (a meta-hybrid GGA), CAM-B3LYP-D3 (a range-separated hybrid), and B2GP-PLYP-D3 (a double hybrid) perform the best, with average errors of about 1.50-1.60 kcal/mol compared to CCSD(T). We also compared the performance of the WF methods that are more scalable than CCSD(T), finding that DLPNO-CCSD(T) and phaseless AFQMC with a DFT trial wave function exhibit average errors of 1.38 and 1.74 kcal/mol, respectively.