水系锌锰电池电解液的电导性质研究  

Study on conductivity of electrolyte in aqueous Zn-Mn battery

作　　者：秦野 刘畅 韩松 王硕 QIN Ye;LIU Chang;HAN Song;WANG Shuo(Shenyang University of Chemical Technology,Shenyang 110142,China)

机构地区：[1]沈阳化工大学材料科学与工程学院,辽宁沈阳110142

出　　处：《无机盐工业》2024年第11期132-138,共7页Inorganic Chemicals Industry

基　　金：辽宁省教育厅项目(LJKMZ20220768);辽宁省组织部项目(XLYC2007157);辽宁省科技厅项目(2023-MSLH-271)。

摘　　要：作为水系锌锰电池的重要组成部分之一,电解液不仅是离子传输的载体,更是参与电化学反应的活性物质,对于提升电池循环寿命和功率密度等性能具有重要影响。研究电解液的热力学性质有助于在不同工作条件下确定最优电解液的组成和质量摩尔浓度,优化电池设计,提升电池的性能。目前,已有对VOSO_(4)电解质水体系的研究,但仍缺乏对MnSO_(4)电解质的相关研究。在283.15~318.15 K条件下,测量了质量摩尔浓度为0.001~0.1 mol/kg的硫酸锰稀溶液电导率。应用Fuoss法和Shedlovsky法,获得了[MnSO_(4)]^(0)离子对的极限摩尔电导率(Λ_(0))和解离常数(K_(d))。与其他二价金属离子相比,计算结果较为可靠。根据K_(d)与温度的经验方程进行拟合,计算得到解离过程的热力学函数,并深入分析Mn^(2+)和SO_(4)^(2-)在解离过程中与水分子的水化作用。[MnSO_(4)]^(0)离子对解离的关键步骤是水分子被固定在Mn^(2+)的水化层周围,使体系秩序性增强的过程。该研究为分析锰电解液中离子作用结构,优化电解液性能提供基础理论支撑。As one of the important components in aqueous Zn-Mn battery(AZMB),the electrolyte is not only a carrier of ion transport but also an active substance involved in electrochemical reactions,which has an important impact on AZMB cycle life and power density.The study of thermodynamic properties is conducive to determine optimal composition and molality under different working conditions in electrolytes,which optimizes battery design and improves performance.There have been research on the water system of VOSO_(4)electrolytes,but there is a lack of relevant studies on MnSO_(4)electrolytes.In this paper,the conductivity of manganese sulfate dilute solution with a molality range of 0.001~0.1 mol/kg was measured at 283.15~318.15 K.Limiting molar conductivity(Λ_(0))and dissociation constant(K_(d))of[MnSO_(4)]^(0)ion pair in the dissociation process were obtained from the Fuoss method and Shedlovsky method.The calculative data was reliable compared with other divalent ions.The thermodynamic function of the dissociation process was obtained by fitting the equation of K_(d)and temperature,and the ionic interaction of Mn^(2+),SO_(4)^(2-),and water molecules during the dissociation process was deeply discussed.The key step of the dissociation of[MnSO_(4)]^(0)ion pair was the process in which water molecules were fixed around the hydration layer of Mn^(2+)to enhance the order of the system.This study provided basic theoretical support for analyzing the ionic structure and optimizing performance in manganese electrolytes.

关 键 词：电导率 摩尔电导率 解离常数 水系锌锰电池 电解液 

分 类 号：TM911[电气工程—电力电子与电力传动]