基于基团贡献法估算(富锂)锂离子电池正极材料Li_(1+x)M_(1-x)O_(2)的热力学性质  

Estimation of Thermodynamic Properties of Li_(1+x)M_(1-x)O_(2) Cathode Material for Lithium-Ion Battery(Lithium-Rich)Based on the Group Contribution Method

作　　者：王大辉[1] 甘先豪 陈怀敬[2] 杨立新 胡平平 刘振宁 Wang Dahui;Gan Xianhao;Chen Huaijing;Yang Lixin;Hu Pingping;Liu Zhenning(State Key Laboratory of Advanced Processing and Recycling of Nonferrous Metals,Lanzhou University of Technology,Lanzhou 730050,China;College of Science,Lanzhou University of Technology,Lanzhou 730050,China)

机构地区：[1]兰州理工大学省部共建有色金属先进加工与再利用国家重点实验室,甘肃兰州730050 [2]兰州理工大学理学院,甘肃兰州730050

出　　处：《稀有金属材料与工程》2022年第2期442-451,共10页Rare Metal Materials and Engineering

基　　金：National Natural Science Foundation of China(51864032);Joint Fund Between Shenyang National Laboratory for Materials Science and State Key Laboratory of Advanced Processing and Recycling of Nonferrous Metals(18LHZD002)。

摘　　要：富锂Li_(1+x)M_(1-x)O_(2)材料的研究主要集中在其结构和电化学性能上,而很少关注其热力学性能。开发具有高能量密度和容量的新型富锂材料取决于这种材料的结构、热力学性质和电化学性质之间的固有关系。对富锂材料Li_(1+x)M_(1-x)O_(2)的热力学性质了解不足,使得新型Li_(1+x)M_(1-x)O_(2)材料的开发和利用受到限制。鉴于Li_(1+x)M_(1-x)O_(2)材料缺乏热力学数据,根据基团贡献方法的原理对LiAlO2进行拆分。基于热力学原理,提出了用于估计LiAlO2的ΔG^(θ)_(f,298)、ΔH^(θ)_(f,298)和Cp的数学模型。采用基团贡献法估算了56种固体无机化合物的ΔG^(θ)_(f,298)和ΔH^(θ)_(f,298)以及54种固体无机化合物的C_(p,298),以检验该模型的可靠性和适用性。利用基团贡献法估算了固体无机化合物的数学模型。利用基团贡献法拟合的基团参数选择的实验数据准确可靠。在结果令人满意的基础上,建立了用于估算3种类型的Li_(1+x)M_(1-x)O_(2)材料的ΔG^(θ)_(f,298),ΔH^(θ)_(f,298)和Cp的数学模型,并估算了63种常见Li_(1+x)M_(1-x)O_(2)材料的ΔG^(θ)_(f,298)、ΔH^(θ)_(f,298)和C_(p,298)。Given the lack of thermodynamic data on Li_(1+x)M_(1−x)O_(2)materials,LiAlO2 was split in accordance with the principle of the group contribution method.Mathematical models for estimating theΔG^(θ)_(f,298),ΔH^(θ)_(f,298),and Cp of LiAlO2 were proposed on the basis of thermodynamic principles.The group contribution method was used to estimate theΔG^(θ)_(f,298),andΔH^(θ)_(f,298)of 56 solid inorganic compounds and the C_(p,298)of 54 solid inorganic compounds to test the reliability and applicability of the model.The group contribution method was used to estimate the mathematical model of solid inorganic compounds.Results show that the experimental data selected by fitting group parameters are accurate and reliable,and the group division method is appropriate.Mathematical models for estimating theΔG^(θ)_(f,298),ΔH^(θ)_(f,298),and Cp of three types of Li_(1+x)M_(1−x)O_(2)materials were constructed on the basis of the satisfactory results.TheΔG^(θ)_(f,298),ΔH^(θ)_(f,298),and C_(p,298)of the 63 common Li_(1+x)M_(1−x)O_(2)materials were also estimated.

关 键 词：富锂正极材料 基团贡献法 ΔG^(θ)_(f 298) ΔH^(θ)_(f 298) C_(p 298) 

分 类 号：TQ131.11[化学工程—无机化工] TM912[电气工程—电力电子与电力传动]