基于基团贡献法和柯普法则估算LiNixCoyMnzO2(x+y+z=1)正极材料的热容  

Heat Capacity Estimation of LiNiCoMnzO(x+y+z=1) Cathode Material Based on Group Contribution Method and Kopp’s Rule

作　　者：杨利新 王大辉[1] 陈怀敬[1,2] 张晓东[1] 许立 俞越山 Yang Lixin;Wang Dahui;Chen Huaijing;Zhang Xiaodong;Xu Li;Yu Yueshan(State Key Laboratory of Advance Processing and Recycling of Nonferrous Metals,Lanzhou University of Technology,Lanzhou 730050,China;College of Science,Lanzhou Un iversity 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》2020年第10期1053-1062,共10页Chinese Journal of Rare Metals

基　　金：国家自然科学基金项目(51864032);沈阳材料科学国家(联合)实验室-有色金属加工与再利用国家重点实验室联合基金项目(18LHZD002)资助。

摘　　要：LiNix Coy Mnz O2(x+y+z=1,0<x,y,z<1)三元正极材料被认为是影响锂离子动力电池性能的关键材料之一,其结构、电化学性能已经有了比较深入的研究报道,但关于其热力学性质,如热容值却极少报道。按照基团贡献法基团划分原则对Ca Al4O7进行拆分,运用热力学原理,提出了估算Ca Al4O7的Cp的数学模型。为了对模型进行检验,采用基团贡献法和柯普法则对54种固体无机化合物的Cp,298进行估算,基团贡献法估算的Cp,298与文献值相比,相对误差绝对值都在5%之内,其中相对误差绝对值小于2%的固体无机化合物有43种。在估算结果令人满意的基础上,利用基团贡献法构建了估算锂离子动力电池正极材料LiNix Coy Mnz O2的Cp的数学模型,并对锂离子动力电池正极材料LiNi1/3Co1/3Mn1/3O2,LiNi0.5Co0.2Mn0.3O2,Li Ni0.6Co0.2Mn0.2O2和Li Ni0.8Co0.1Mn0.1O2在298 K下的Cp,298进行了估算,估算结果分别是78.96,78.69,79.77和75.72 J·mol-1·K-1。采用柯普法则估算Li Ni1/3Co1/3Mn1/3O2,Li Ni0.5Co0.2Mn0.3O2,LiNi0.6Co0.2Mn0.2O2和Li Ni0.8Co0.1Mn0.1O2正极材料Cp,298的结果分别是76.50,76.38,76.12和75.84 J·mol-1·K-1。LiNixCoyMnzO2(x+y+z=1,0<x,y,z<1)ternary cathode material was one of the key materials in the field of lithium ion power battery.Its structure and electrochemical properties were well understood,but its heat capacity was rarely reported.In this paper,the Ca Al4O7was split according to the principle of the group contribution method,and the mathematical model of estimating the Cpof Ca Al4O7was proposed based on thermodynamic principle.In order to test the model,the Cp,298of 54 kinds of solid inorganic compounds were estimated by the group contribution method and the Kopp’s rule.Compared with the literature values,the absolute relative error of Cp,298estimated by the group contribution method was within 5%,among which 43 kinds of solid inorganic compounds had the absolute relative error less than 2%.Based on the satisfactory results,a mathematical model for estimating the Cpof Li Nix Coy MnzO2cathode material for lithium ion power battery was constructed for Li Ni1/3Co1/3Mn1/3O2,Li Ni0.5Co0.2Mn0.3O2,Li Ni0.6Co0.2Mn0.2O2and Li Ni0.8Co0.1Mn0.1O2,and then,the heat capacity of cathode materials Li Nix Coy Mnz O2,such as Li Ni1/3Co1/3Mn1/3O2,Li Ni0.5Co0.2Mn0.3O2,Li Ni0.6Co0.2Mn0.2O2and Li Ni0.8Co0.1Mn0.1O2for lithium ion power battery cathode materials at 298 K were estimated,the estimated results of cathode material Cp,298were 78.96,78.69,79.77 and 75.72 J·mol-1·K-1,respectively.Using Kopp’s rule,the Cp,298of Li Ni1/3Co1/3Mn1/3O2,Li Ni0.5Co0.2Mn0.3O2,Li Ni0.6Co0.2Mn0.2O2and Li Ni0.8Co0.1Mn0.1O2ternary materials were estimated,the results were76.50,76.38,76.12 and 75.84 J·mol-1·K-1,respectively.

关 键 词：基团贡献法 柯普法则 LiNixCoyMnzO2 热容 

分 类 号：O611[理学—无机化学]