(中南大學(xué) 粉末冶金國(guó)家重點(diǎn)實(shí)驗(yàn)室， 長(zhǎng)沙 410083)
摘 要: 根據(jù)化合物單相嵌鋰時(shí)的晶體結(jié)構(gòu)和嵌鋰能的變化特征，采用熱力學(xué)和統(tǒng)計(jì)物理的分析方法， 推導(dǎo)了任意嵌入式化合物的嵌鋰電壓的表達(dá)式， 并用它來預(yù)測(cè)了Li1+xV3O8的嵌鋰電壓。對(duì)該式中各參數(shù)的分析及Li1+xV3O8嵌鋰電壓的計(jì)算結(jié)果表明：嵌鋰電壓主要取決于空位嵌鋰能， 嵌鋰過程中的組態(tài)熵變對(duì)電壓的貢獻(xiàn)較小； 已嵌入的鋰離子及其鄰近陽離子的還原所導(dǎo)致的嵌鋰能的變化是影響電壓平穩(wěn)性的關(guān)鍵因素。
關(guān)鍵字: 嵌入; 電壓; 組態(tài)能; 熵
LIU Zhi-jian, QU Xuan-hui
（State Key Laboratory for Powder Metallurgy, Central South University, Changsha 410083, China）
Abstract:Based on characteristic changes of crystalline structure and intercalation energy when Li+ was inserted into anyone single-phase compound, an expression of intercalation voltage was deduced using statistic thermodynamics method, and was used to predict the intercalation voltage of Li1+xV3O8. The results show that the voltage is affected mostly by vacancy intercalation energy; and that the configurational entropy plays a small effect. The voltage stability is basically restricted by the change of intercalation energy that results from inserted lithium ions and the deoxidization of cations.
Key words: intercalation; voltage; configurational energy; entropy
