非水锂一氧二次电池纳米二氧化锰阴极的研究
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摘要
本论文针对目前锂离子电池比功率低和锂氧电池存在充放电电压差过大和循环性能差的主要问题,选择高比功率和高比能量锂二次电池纳米电极材料制备进行研究,采用溶胶凝胶模板法合成了钛酸锂纳米阵列电极材料,常压水溶液沉淀法合成了纳米二氧化锰材料。在锂氧电池阴极材料中选用纳米二氧化锰双功能催化剂、制备氧扩散阴极极片、选择非水电解液等构建锂氧测试电池,对非水锂氧二次电池纳米二氧化锰阴极性能进行了研究。
首先,使用电化学阳极氧化铝箔的方法制备出有序纳米微孔氧化铝模板。通过溶胶填充模板法制备出了Li4Ti5O12纳米线阵列,使用SEM、EDS等手段对纳米线组成和晶型形貌进行了表征。实验结果表明：以孔径为100nm的氧化铝有序微孔薄膜为模板,于-0.1MPa的真空条件下填充浓度为0.8mol/L Li4Ti5O12溶胶,于80℃干燥,900℃空气中焙烧20h,重复溶胶填充-烘干-焙烧过程四次,制得了平均直径约为70nm的尖晶石结构的Li4Ti5O12纳米线阵列。
以高锰酸钾和硫酸锰水溶液化学沉淀法制备纳米二氧化锰,结合使用XRD、SEM和BET等表征手段研究了反应物摩尔比、反应温度及反应时间对生成二氧化锰晶型和形貌的影响。控制适当反应物摩尔比、反应温度、反应时间可分别制得不同晶型和形貌的纳米级二氧化锰颗粒。以反应物摩尔比nKMnO4：nMnSO4=2：3,控制反应温度90℃反应6h可制得直径为30nm,长约1000nm,比表面积为77.241m2/g的纳米线状α-MnO2；以反应物摩尔比nKMnO4：/nMnSO4=2：1.5,控制反应温度80℃反应4h可制得粒径约为300nm,比表面积为70.474m2/g的层状δ-MnO2；以反应物摩尔比nKMnO4：nMnSO4=2：12,控制反应温度80℃反应4h可制备出粒径约为100nm,比表面积为33.303m2/g的不规则纳米γ-Mn02微粒。
然后,以旋转圆盘玻碳电极为工作电极,采用三电极体系研究纳米α,γ,δ-Mn02分别在组成为LiPF6(1mol/L)+EC/DEC/DMC(Vol.1:1:1)、 LiPF6(1mol/L)+PC/DME(W.1:1)和LiPF6(1mol/L)+PC/DME(W.1:2)三种非水电解液中的催化氧还原和氧化过氧化钾的电化学性能。电极在使用前用A1203悬浮液充分擦拭表面。称取10mg Mn02颗粒,加5mL超纯水混合并超声匀化分散10分钟。用移液管移取10.0μL悬浮液滴涂于干净的圆盘电极表面,在氮气气氛中控温105℃烘干。再移取10.0μL浓度为0.2750g·L-1的Nafion (5wt.%)乳液,涂于催化剂薄膜层上于105℃烘干即得到电化学实验工作电极。在氩气气氛的真空手套箱中组装三电极测试体系。以玻碳电极为工作电极,以Ag/AgCl电极为参比电极,对电极为铂丝,控制扫描速度为100mV/s,扫描范围为-2～2V(vs. Ag/AgCl)。控制测试体系温度为25℃,为保持电解液中有一定浓度的氧气,在测定前1小时给电解液连续通氧气。实验结果表明,纳米α,γ,δ-MnO2在三种非水电解液中催化氧还原峰峰电流密度大小顺序均为为α-MnO2>γ-MnO2>δ-MnO2。α-MnO2在前二种非水电解液中催化氧还原峰峰电流密度分别为-8.715、-18.54mA·mg-1,在第三种电解液中出现二个还原峰,在OV时形成较宽的氧还原峰,其电流密度为-16.79mA·mg-1、在-0.71V出现的还原峰电流密度为-21.71mA·mg-1。以相同的测试方法,在以上三种电解液中加入过量的过氧化锂制得饱和了过氧化锂的非水电解液,测定纳米α,γ,δ-MnO2催化氧化过氧化锂的电化学性能。实验结果显示,在LiPF6(1mol/L)+EC/DEC/DMC(Vol.1:1:1)电解液中δ-MnO2有明显的氧化峰,峰电流密度为6.569mA·mg-1,而α-MnO2和γ-MnO2均无；在LiPF6(1mol/L)+PC/DME (W.1:1)电解液中γ-MnO2、α-MnO2和8-MnO2氧化峰均强,峰电流密度分别为27.93、24.44、19.13mA·mg-1;在LiPF6(1mol/L)+PC/DME(W.1：2)电解液中,δ-MnO2、γ-MnO2和a-Mn02氧化峰电流密度分别为33.712、32.075、1.272mA·mg-1。实验表明,α-MnO2和δ-MnO2在LiPF6(1mol/L)+PC/DME (W.1:2)电解液中,对氧还原和过氧化锂的氧化有较强的催化作用。故此,本论文锂氧电池性能研究选择LiPF6(1mol/L)+PC/DME (W.1:2)为电解液,选择α-MnO2+δ-MnO2(质量比1：1)混合晶体为阴极氧还原和过氧化锂氧化的双功能催化剂。
称取0.35g ketjen碳黑、0.15g α,δ-MnO2、15g聚偏氟乙烯胶(0.056g PVDF粉末+15gNMP+10ml异丙醇)分别倒入50ml烧杯中充分搅拌混合,制得浆态阴极承载料。取二组直径为2.5cm的泡沫镍基体放置其中载料,超声处理15分钟后取出并除去表层多余浆态阴极料,于烘干箱80℃干燥2小时,取出冷却后再次放入浆态阴极料中进行二次载料操作,超声15分钟,取出除去表层多余浆态物,于80℃十燥2小时至恒重,然后取出,其中一组用3MPa压力压制,而后放入烘箱中恒温175℃加热处理2小时后既得测试用多孔阴极。取出称量电极质量并计算阴极单位面积或体积载碳／二氧化锰的质量。
最后,以锂箔为阳极、LiPF6(1mol/L)+PC/DME(W.1:2)电解液、Celgard-2500高分子聚合物膜为隔膜及制备的阴极装入电池模具构建非水锂-氧电池。在25℃-65℃条件下,以常压纯氧为阴极反应物测试锂-氧电池首次放电和充放电循环行为研究其电化学性能。
以低电流密度(0.1m A/cm2)研究温度对锂氧电池首次放电容量的影响。恒电流首次放电性能结果显示,25℃时,电池容量为2822mAh·g-1,随着测试温度(25℃～-65℃)升高电池容量随之升高,50℃时达最大值3870mAh·g-1,再升高温度因电解液不稳定等原因致使容量下降。且在50℃时,具有较高的放电平台(2.81V)和较低的充电电压平台(4.22V)；以优化的条件制备阴极并组装电池,在50℃以恒电流密度0.1mA·cm-2对锂氧电池充放电循环性能进行测试。结果显示,共完成了五次较完整的循环过程。
综合分析首次放电和循环充放电实验、剖析电池和使用XRD表征放电终止阴极结果表明：测试温度对锂氧电池首次放电容量、LiPF6(1mol/L)+PC/DME(W.1:2)电解液稳定性有很大影响作用,是影响非水锂氧二次电池纳米二氧化锰阴极性能最关键的因素。筛选和制备稳定的电解液将是今后的重要课题。
This thesis focuses on the problems of lithium-oxygen battery that low specific power, huge gap between charge and discharge voltage and poor cycling performance.Dual-function catalyst of the MnO2was used in the cathode material. High specific power and energy lithium secondary battery nano electrode material preparation was chosen to studied.Sol-gel template synthesis method was used to produce the lithium titanate nanoarray electrode materials, atmospheric water solution precipitation was used to synthesize nanometer MnO2material. Take using nano-MnO2bifunctional catalyst for the cathode materials, making oxygen diffusion cathode piece, choosing nonaqueous electrolyte and other optimization conditions were used to investigate the nano-MnO2cathode performance in nonaqueous lithium-oxygen secondary battery.
First, AAO film in this paper was prepared by electrochemical anodic oxide method; Li4Ti5O12nanoarrays were prepared with the method of Sol-filling AAO template. The morphology and structure of Li4Ti5O12nanoarrays were characterized by SEM, EDS et al. The experimental results show that spinel Li4Ti5O12nanoarrays with mean diameter of70nm were synthesized by immersing the porous AAO in sol of0.8mol/L under-0.1MP and drying at80℃then roasting at900℃for20h in the air after repeating steps above for four times.
KMnO4and MnSO4were used to produce nano-MnO2through Chemical precipitation. Combined with the characterization methods such as XRD, SEM and BET to discover the influence of reactants molar ratio, reaction temperature and reaction time to produce manganese dioxide crystal form and morphology. Different crystal structure and morphology of nanoscale MnO2particles were produced by controlling appropriate reactant molar ratio, reaction temperature and reaction time. The reactant ratio was nKMnO4:nMnSO4=2:3, and reaction temperature control90℃for6h. A kind of diameter of about30nm, length about1000nm, specific surface area of77.241m2/g nano linear α-MnO2was obtained; The reactant ratio was nKMnO4:nMnso4=2:1.5, and reaction temperature controlled80℃for4h. A kind of diameter of about300nm, specific surface area of77.474m2/g nano layered δ-MnO2was obtained; The reactant ratio was nKMnO4:nMnSO4=2:12, and reaction temperature controlled80℃for4h. A kind of diameter of about100nm, specific surface area of33.303m2/g nano layered γ-MnO2was obtained.
Rotating disk glassy carbon electrode as the working electrode, a three-electrode system was used to research catalytic oxygen reduction and oxidation of lithium oxide electrochemical performance of nano-α,γ,δ-MnO2in the three kinds of nonaqueous electrolyte:LiPF6(1mol/L)+EC/DEC/DMC (Vol.1:1:1)、LiPF6(1moI/L)+PC/DME(W.1:1) and LiPF6(1moI/L)+PC/DME (W.1:2). Al2O3suspension was used fully wipe the surface before the electrode using. lOmg MnO2particles weighted, plus5mL ultra-pure water were mixed,homogenized and dispersed for10minutes by ultrasonic. Pipetted pipette10.0μL of suspended droplets applied to the clean surface of the disc electrode, the temperature control105℃drying in a nitrogen atmosphere. Pipetted10.1μL concentration of0.2750g·L-1of Nafion (5wt.%) emulsion, applied it to the catalyst film layer and dried at105℃,there got the electrochemical experiments working electrode. Test the system of the three-electrode assembly in a vacuum glove box of the argon atmosphere. Glassy carbon electrode as the working electrode, the counter electrode was a platinum wire, a Ag/AgCl electrode as reference electrode, and controlled the scan speed of100mV/s, the scan range of-2to2V (vs. Ag/AgCl). Control testing system temperature of25℃, in order to maintain the electrolyte a certain concentration of oxygen, the oxygen was continuously to the electrolyte solution one hour before measurement. Experimental results showed that the order of nano-α,γ,δ-MnO2catalytic oxygen reduction peak current density in the three kinds of non-aqueous electrolyte. The former two kinds of nonaqueous electrolyte solution of the α-MnO2catalytic oxygen reduction peak current densities were-8.715、-18.54mA·mg-1, Two reduction peak appeared in the third electrolyte, a wide oxygen reduction peak formed at OV when the current density was-16.79mA·mg-1, and a reduction peak appeared at-0.71V when the current density was-21.71mA·mg-1. In the same test method, adding an excess of lithium peroxide obtained in the above three electrolyte saturated non-aqueous electrolyte lithium peroxide to test the catalytic oxidation electrochemical properties of α,γ,δ-MnO2to the lithium oxide. Experimental results showed that δ-MnO2had an obvious oxidation peak in the LiPF6(1mol/L)+EC/DEC/DMC(Vol.1:1:1) the peak current density was6.569mA·mg-1, no α-MnO2and γ-MnO2; γ-MnO2, α-MnO2and δ-MnO2oxidation peak were strong in the LiPF6(1mol/L)+PC/DME(W.1:1) electrolyte, The peak current density were27.93,24.44,19.13mA·mg-1; δ-MnO2, γ-MnO2and α-MnO2oxidation peak current density were33.712,32.075,1.272mA·mg-1in LiPF6(1mol/L)+PC/DME (W.1:2) electrolyte. Above all,α-MnO2and δ-MnO2had strong catalytic on oxygen reduction and lithium peroxide oxidation in LiPF6(1mol/L)+PC/DME (W.1:2) electrolyte. Therefore, in this paper LiPF6(1mol/L)+PC/DME (W.1:2)was selected as the electrolyte to study the lithium oxygen battery performance, α-MnO2+δ-Mn02(w.1:1) mixed crystal was chosen as cathode and the oxygen reduction and lithium peroxide oxidation of the dual-function catalyst.
Weighed0.35g ketjen carbon black and0.15g α,δ-MnO2,15g poly vinylidene fluoride vinyl plastic(0.056g PVDF powder+15gNMP+10ml isopropanol), poured respectively into50ml beakers and sufficiently stirred and mixed to produce the slurry cathode bearing-material. Took two sets of diameter2.5cm nickel foam substrates to fill with bearing-material by15minutes sonication. After that took the substrates out and clear the excess pulp state cathode material, dried at80℃for2hours; Repeat the above steps once. One group suppressed under3MPa pressure, then put it into the oven for2hours thermostat heated at175℃,there got the test porous cathode. Weighed electrodes quality and calculated the quality of the cathode unit area or volume contained carbon/MnO2.
With lithium foil anode, LiPF6(lmol/L)+PC/DME(w.1:2) electrolyte, Celgard2500polymer membrane for diaphragm and preparation of the cathode load cell mould constructed non water lithium-oxygen battery. In25℃-65℃condition, With pure oxygen at atmospheric pressure as cathode reactant tested lithium-oxygen battery first discharge and recharge cycles behavior studied the electrochemical performance.
Studied temperature on lithium oxygen battery first discharge capacity at low current density (0.1mA/cm2). The first time constant current discharge performance results showed the battery capacity increased with testing temperature (25℃-65℃) increased, when the temperature reached to50℃the battery capacity grow up to maximum of3870mAh·g-1, However, when the temperature continue rising, the battery capacity declined, the reason for this is electrolyte unstable. In addition, the battery had the high discharge platform (2.81V) and low charging voltage platform (4.22V) in50℃; with the optimum conditions prepared cathode and assembled battery, In50℃, with the constant current density of0.1mA·cm-2, the lithium battery charging and discharging cycle to oxygen performance test results show that completed five times more complete cycle process.
The first discharge and circulation charge and discharge experiments were conducted and discharge termination cathode was characterized by SEM and XRD. The results showed that:Test temperatures had a great influence on first discharging capacity and lithium-oxygen cell electrochemical performance;(3) Carbonic acid esters LiPF6nonaqueous electrolyte used in lithium-oxygen battery system existed two defects. One was after the charge and discharge termination electrolyte in battery anode zone had withered evidences, which showed that the solvent volatile was larger at50℃and the electrolyte loss was serious in the charge and discharge process. So the transfer channels of lithium ion between cathode and anode were lost, which was the main reason of charging and discharging cycle termination of lithium oxygen batteries. The another was electrolyte property was not stable and solvent and solute participated in reactions in cathode, which affected the formation of pure lithium peroxide in the process of the cathode discharge reaction. As a result, complex lithium compound formed among cathode discharge sediment, which was the key factor that influenced the charge and discharge process and cycle performance.
In short, in nonaqueous lithium oxygen electrochemical system, temperature which had great influence on cathode catalyst activity and the stability of the electrolyte, was one of the key factors that affected the lithium oxygen cell electrochemical performance. The composition of electrolyte and stability of lithium oxygen system were key factors that influenced charging and discharging electrochemical reaction and cycle numbers, and also determined the battery specific capacity and charging and discharging current density. We believe that the primary task of the future research for lithium oxygen batteries and improving the electrochemical performance is to screen the electrolyte with more stable physical and chemical properties.
首先,使用电化学阳极氧化铝箔的方法制备出有序纳米微孔氧化铝模板。通过溶胶填充模板法制备出了Li4Ti5O12纳米线阵列,使用SEM、EDS等手段对纳米线组成和晶型形貌进行了表征。实验结果表明：以孔径为100nm的氧化铝有序微孔薄膜为模板,于-0.1MPa的真空条件下填充浓度为0.8mol/L Li4Ti5O12溶胶,于80℃干燥,900℃空气中焙烧20h,重复溶胶填充-烘干-焙烧过程四次,制得了平均直径约为70nm的尖晶石结构的Li4Ti5O12纳米线阵列。
以高锰酸钾和硫酸锰水溶液化学沉淀法制备纳米二氧化锰,结合使用XRD、SEM和BET等表征手段研究了反应物摩尔比、反应温度及反应时间对生成二氧化锰晶型和形貌的影响。控制适当反应物摩尔比、反应温度、反应时间可分别制得不同晶型和形貌的纳米级二氧化锰颗粒。以反应物摩尔比nKMnO4：nMnSO4=2：3,控制反应温度90℃反应6h可制得直径为30nm,长约1000nm,比表面积为77.241m2/g的纳米线状α-MnO2；以反应物摩尔比nKMnO4：/nMnSO4=2：1.5,控制反应温度80℃反应4h可制得粒径约为300nm,比表面积为70.474m2/g的层状δ-MnO2；以反应物摩尔比nKMnO4：nMnSO4=2：12,控制反应温度80℃反应4h可制备出粒径约为100nm,比表面积为33.303m2/g的不规则纳米γ-Mn02微粒。
然后,以旋转圆盘玻碳电极为工作电极,采用三电极体系研究纳米α,γ,δ-Mn02分别在组成为LiPF6(1mol/L)+EC/DEC/DMC(Vol.1:1:1)、 LiPF6(1mol/L)+PC/DME(W.1:1)和LiPF6(1mol/L)+PC/DME(W.1:2)三种非水电解液中的催化氧还原和氧化过氧化钾的电化学性能。电极在使用前用A1203悬浮液充分擦拭表面。称取10mg Mn02颗粒,加5mL超纯水混合并超声匀化分散10分钟。用移液管移取10.0μL悬浮液滴涂于干净的圆盘电极表面,在氮气气氛中控温105℃烘干。再移取10.0μL浓度为0.2750g·L-1的Nafion (5wt.%)乳液,涂于催化剂薄膜层上于105℃烘干即得到电化学实验工作电极。在氩气气氛的真空手套箱中组装三电极测试体系。以玻碳电极为工作电极,以Ag/AgCl电极为参比电极,对电极为铂丝,控制扫描速度为100mV/s,扫描范围为-2～2V(vs. Ag/AgCl)。控制测试体系温度为25℃,为保持电解液中有一定浓度的氧气,在测定前1小时给电解液连续通氧气。实验结果表明,纳米α,γ,δ-MnO2在三种非水电解液中催化氧还原峰峰电流密度大小顺序均为为α-MnO2>γ-MnO2>δ-MnO2。α-MnO2在前二种非水电解液中催化氧还原峰峰电流密度分别为-8.715、-18.54mA·mg-1,在第三种电解液中出现二个还原峰,在OV时形成较宽的氧还原峰,其电流密度为-16.79mA·mg-1、在-0.71V出现的还原峰电流密度为-21.71mA·mg-1。以相同的测试方法,在以上三种电解液中加入过量的过氧化锂制得饱和了过氧化锂的非水电解液,测定纳米α,γ,δ-MnO2催化氧化过氧化锂的电化学性能。实验结果显示,在LiPF6(1mol/L)+EC/DEC/DMC(Vol.1:1:1)电解液中δ-MnO2有明显的氧化峰,峰电流密度为6.569mA·mg-1,而α-MnO2和γ-MnO2均无；在LiPF6(1mol/L)+PC/DME (W.1:1)电解液中γ-MnO2、α-MnO2和8-MnO2氧化峰均强,峰电流密度分别为27.93、24.44、19.13mA·mg-1;在LiPF6(1mol/L)+PC/DME(W.1：2)电解液中,δ-MnO2、γ-MnO2和a-Mn02氧化峰电流密度分别为33.712、32.075、1.272mA·mg-1。实验表明,α-MnO2和δ-MnO2在LiPF6(1mol/L)+PC/DME (W.1:2)电解液中,对氧还原和过氧化锂的氧化有较强的催化作用。故此,本论文锂氧电池性能研究选择LiPF6(1mol/L)+PC/DME (W.1:2)为电解液,选择α-MnO2+δ-MnO2(质量比1：1)混合晶体为阴极氧还原和过氧化锂氧化的双功能催化剂。
称取0.35g ketjen碳黑、0.15g α,δ-MnO2、15g聚偏氟乙烯胶(0.056g PVDF粉末+15gNMP+10ml异丙醇)分别倒入50ml烧杯中充分搅拌混合,制得浆态阴极承载料。取二组直径为2.5cm的泡沫镍基体放置其中载料,超声处理15分钟后取出并除去表层多余浆态阴极料,于烘干箱80℃干燥2小时,取出冷却后再次放入浆态阴极料中进行二次载料操作,超声15分钟,取出除去表层多余浆态物,于80℃十燥2小时至恒重,然后取出,其中一组用3MPa压力压制,而后放入烘箱中恒温175℃加热处理2小时后既得测试用多孔阴极。取出称量电极质量并计算阴极单位面积或体积载碳／二氧化锰的质量。
最后,以锂箔为阳极、LiPF6(1mol/L)+PC/DME(W.1:2)电解液、Celgard-2500高分子聚合物膜为隔膜及制备的阴极装入电池模具构建非水锂-氧电池。在25℃-65℃条件下,以常压纯氧为阴极反应物测试锂-氧电池首次放电和充放电循环行为研究其电化学性能。
以低电流密度(0.1m A/cm2)研究温度对锂氧电池首次放电容量的影响。恒电流首次放电性能结果显示,25℃时,电池容量为2822mAh·g-1,随着测试温度(25℃～-65℃)升高电池容量随之升高,50℃时达最大值3870mAh·g-1,再升高温度因电解液不稳定等原因致使容量下降。且在50℃时,具有较高的放电平台(2.81V)和较低的充电电压平台(4.22V)；以优化的条件制备阴极并组装电池,在50℃以恒电流密度0.1mA·cm-2对锂氧电池充放电循环性能进行测试。结果显示,共完成了五次较完整的循环过程。
综合分析首次放电和循环充放电实验、剖析电池和使用XRD表征放电终止阴极结果表明：测试温度对锂氧电池首次放电容量、LiPF6(1mol/L)+PC/DME(W.1:2)电解液稳定性有很大影响作用,是影响非水锂氧二次电池纳米二氧化锰阴极性能最关键的因素。筛选和制备稳定的电解液将是今后的重要课题。
This thesis focuses on the problems of lithium-oxygen battery that low specific power, huge gap between charge and discharge voltage and poor cycling performance.Dual-function catalyst of the MnO2was used in the cathode material. High specific power and energy lithium secondary battery nano electrode material preparation was chosen to studied.Sol-gel template synthesis method was used to produce the lithium titanate nanoarray electrode materials, atmospheric water solution precipitation was used to synthesize nanometer MnO2material. Take using nano-MnO2bifunctional catalyst for the cathode materials, making oxygen diffusion cathode piece, choosing nonaqueous electrolyte and other optimization conditions were used to investigate the nano-MnO2cathode performance in nonaqueous lithium-oxygen secondary battery.
First, AAO film in this paper was prepared by electrochemical anodic oxide method; Li4Ti5O12nanoarrays were prepared with the method of Sol-filling AAO template. The morphology and structure of Li4Ti5O12nanoarrays were characterized by SEM, EDS et al. The experimental results show that spinel Li4Ti5O12nanoarrays with mean diameter of70nm were synthesized by immersing the porous AAO in sol of0.8mol/L under-0.1MP and drying at80℃then roasting at900℃for20h in the air after repeating steps above for four times.
KMnO4and MnSO4were used to produce nano-MnO2through Chemical precipitation. Combined with the characterization methods such as XRD, SEM and BET to discover the influence of reactants molar ratio, reaction temperature and reaction time to produce manganese dioxide crystal form and morphology. Different crystal structure and morphology of nanoscale MnO2particles were produced by controlling appropriate reactant molar ratio, reaction temperature and reaction time. The reactant ratio was nKMnO4:nMnSO4=2:3, and reaction temperature control90℃for6h. A kind of diameter of about30nm, length about1000nm, specific surface area of77.241m2/g nano linear α-MnO2was obtained; The reactant ratio was nKMnO4:nMnso4=2:1.5, and reaction temperature controlled80℃for4h. A kind of diameter of about300nm, specific surface area of77.474m2/g nano layered δ-MnO2was obtained; The reactant ratio was nKMnO4:nMnSO4=2:12, and reaction temperature controlled80℃for4h. A kind of diameter of about100nm, specific surface area of33.303m2/g nano layered γ-MnO2was obtained.
Rotating disk glassy carbon electrode as the working electrode, a three-electrode system was used to research catalytic oxygen reduction and oxidation of lithium oxide electrochemical performance of nano-α,γ,δ-MnO2in the three kinds of nonaqueous electrolyte:LiPF6(1mol/L)+EC/DEC/DMC (Vol.1:1:1)、LiPF6(1moI/L)+PC/DME(W.1:1) and LiPF6(1moI/L)+PC/DME (W.1:2). Al2O3suspension was used fully wipe the surface before the electrode using. lOmg MnO2particles weighted, plus5mL ultra-pure water were mixed,homogenized and dispersed for10minutes by ultrasonic. Pipetted pipette10.0μL of suspended droplets applied to the clean surface of the disc electrode, the temperature control105℃drying in a nitrogen atmosphere. Pipetted10.1μL concentration of0.2750g·L-1of Nafion (5wt.%) emulsion, applied it to the catalyst film layer and dried at105℃,there got the electrochemical experiments working electrode. Test the system of the three-electrode assembly in a vacuum glove box of the argon atmosphere. Glassy carbon electrode as the working electrode, the counter electrode was a platinum wire, a Ag/AgCl electrode as reference electrode, and controlled the scan speed of100mV/s, the scan range of-2to2V (vs. Ag/AgCl). Control testing system temperature of25℃, in order to maintain the electrolyte a certain concentration of oxygen, the oxygen was continuously to the electrolyte solution one hour before measurement. Experimental results showed that the order of nano-α,γ,δ-MnO2catalytic oxygen reduction peak current density in the three kinds of non-aqueous electrolyte. The former two kinds of nonaqueous electrolyte solution of the α-MnO2catalytic oxygen reduction peak current densities were-8.715、-18.54mA·mg-1, Two reduction peak appeared in the third electrolyte, a wide oxygen reduction peak formed at OV when the current density was-16.79mA·mg-1, and a reduction peak appeared at-0.71V when the current density was-21.71mA·mg-1. In the same test method, adding an excess of lithium peroxide obtained in the above three electrolyte saturated non-aqueous electrolyte lithium peroxide to test the catalytic oxidation electrochemical properties of α,γ,δ-MnO2to the lithium oxide. Experimental results showed that δ-MnO2had an obvious oxidation peak in the LiPF6(1mol/L)+EC/DEC/DMC(Vol.1:1:1) the peak current density was6.569mA·mg-1, no α-MnO2and γ-MnO2; γ-MnO2, α-MnO2and δ-MnO2oxidation peak were strong in the LiPF6(1mol/L)+PC/DME(W.1:1) electrolyte, The peak current density were27.93,24.44,19.13mA·mg-1; δ-MnO2, γ-MnO2and α-MnO2oxidation peak current density were33.712,32.075,1.272mA·mg-1in LiPF6(1mol/L)+PC/DME (W.1:2) electrolyte. Above all,α-MnO2and δ-MnO2had strong catalytic on oxygen reduction and lithium peroxide oxidation in LiPF6(1mol/L)+PC/DME (W.1:2) electrolyte. Therefore, in this paper LiPF6(1mol/L)+PC/DME (W.1:2)was selected as the electrolyte to study the lithium oxygen battery performance, α-MnO2+δ-Mn02(w.1:1) mixed crystal was chosen as cathode and the oxygen reduction and lithium peroxide oxidation of the dual-function catalyst.
Weighed0.35g ketjen carbon black and0.15g α,δ-MnO2,15g poly vinylidene fluoride vinyl plastic(0.056g PVDF powder+15gNMP+10ml isopropanol), poured respectively into50ml beakers and sufficiently stirred and mixed to produce the slurry cathode bearing-material. Took two sets of diameter2.5cm nickel foam substrates to fill with bearing-material by15minutes sonication. After that took the substrates out and clear the excess pulp state cathode material, dried at80℃for2hours; Repeat the above steps once. One group suppressed under3MPa pressure, then put it into the oven for2hours thermostat heated at175℃,there got the test porous cathode. Weighed electrodes quality and calculated the quality of the cathode unit area or volume contained carbon/MnO2.
With lithium foil anode, LiPF6(lmol/L)+PC/DME(w.1:2) electrolyte, Celgard2500polymer membrane for diaphragm and preparation of the cathode load cell mould constructed non water lithium-oxygen battery. In25℃-65℃condition, With pure oxygen at atmospheric pressure as cathode reactant tested lithium-oxygen battery first discharge and recharge cycles behavior studied the electrochemical performance.
Studied temperature on lithium oxygen battery first discharge capacity at low current density (0.1mA/cm2). The first time constant current discharge performance results showed the battery capacity increased with testing temperature (25℃-65℃) increased, when the temperature reached to50℃the battery capacity grow up to maximum of3870mAh·g-1, However, when the temperature continue rising, the battery capacity declined, the reason for this is electrolyte unstable. In addition, the battery had the high discharge platform (2.81V) and low charging voltage platform (4.22V) in50℃; with the optimum conditions prepared cathode and assembled battery, In50℃, with the constant current density of0.1mA·cm-2, the lithium battery charging and discharging cycle to oxygen performance test results show that completed five times more complete cycle process.
The first discharge and circulation charge and discharge experiments were conducted and discharge termination cathode was characterized by SEM and XRD. The results showed that:Test temperatures had a great influence on first discharging capacity and lithium-oxygen cell electrochemical performance;(3) Carbonic acid esters LiPF6nonaqueous electrolyte used in lithium-oxygen battery system existed two defects. One was after the charge and discharge termination electrolyte in battery anode zone had withered evidences, which showed that the solvent volatile was larger at50℃and the electrolyte loss was serious in the charge and discharge process. So the transfer channels of lithium ion between cathode and anode were lost, which was the main reason of charging and discharging cycle termination of lithium oxygen batteries. The another was electrolyte property was not stable and solvent and solute participated in reactions in cathode, which affected the formation of pure lithium peroxide in the process of the cathode discharge reaction. As a result, complex lithium compound formed among cathode discharge sediment, which was the key factor that influenced the charge and discharge process and cycle performance.
In short, in nonaqueous lithium oxygen electrochemical system, temperature which had great influence on cathode catalyst activity and the stability of the electrolyte, was one of the key factors that affected the lithium oxygen cell electrochemical performance. The composition of electrolyte and stability of lithium oxygen system were key factors that influenced charging and discharging electrochemical reaction and cycle numbers, and also determined the battery specific capacity and charging and discharging current density. We believe that the primary task of the future research for lithium oxygen batteries and improving the electrochemical performance is to screen the electrolyte with more stable physical and chemical properties.
引文
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