纳米La_（1-x）Sr_xMnO_3材料制备和性能研究
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摘要
氧还原催化剂是金属空气电池和电化学制氧空气电极的核心材料。本文用溶胶凝胶法制备了高性能纳米La_(1-x)Sr_xMnO_3钙钛矿型氧化物催化剂，对材料制备技术及应用性能进行了研究。
研究了溶胶凝胶制备工艺中pH值、水浴温度、凝胶干燥方法和烧结方式对纳米La_(1-x)Sr_xMnO_3晶体结构影响，确定催化剂最佳制备工艺为：金属离子与柠檬酸的摩尔比为1：2，溶于150ml蒸馏水中，初始溶液pH值为0.5，制备成溶胶，在80℃恒温水浴中蒸发5.5h得到湿凝胶，真空100℃下干燥10h得到干凝胶，最后在700℃烧结3h，得到催化剂样品。经透射电镜观察，催化剂样品平均粒径为20～50nm。
通过超声波分散法使软团聚状态的纳米La_(1-x)Sr_xMnO_3分散，并均匀负载在活性炭载体上，提高材料的利用率。并通过电极热处理工艺，明显提高电极孔隙率、改善三相界面，提高了催化性能。
采用稳态极化曲线测试方法研究Sr的掺杂对La_(1-x)Sr_xMnO_3催化性能的影响。发现Sr的掺杂可使LaMnO_3结构发生畸变，其晶体中氧空位(V_0)浓度、Mn~(4+)／Mn~(3+)比例和La_(1-x)Sr_xMnO_3顺磁性的变化是影响La_(1-x)Sr_xMnO_3催化性能的主要因素。研究结果表明：La_(1-x)Sr_xMnO_3催化性能随Sr掺杂量的增加先增大后减小，当x=0.4时催化性能最强，在常温碱性电解液中，-200mV极化电压下，电流密度达到324mA／cm~2。
研究认为在电极中有两个反应过程：一是，La_(1-x)Sr_xMnO_3中的氧空位将氧气还原为过氧氢根离子，Mn~(4+)／Mn~(3+)还原过氧氢根离子为氢氧根离子；二是，高比表面积的活性炭还原氧气为过氧氢根离子，然后过氧氢根离子被La_(1-x)Sr_xMnO_3还原为氢氧根离子。通过活性炭和La_(1-x)Sr_xMnO_3联合催化，完成氧气还原的二电子反应历程，实现了氧气的四电子转移；高性能的催化，使电极具有氧还原的类四电子反应历程。
催化剂应用于电化学制氧机取得了良好效果。
The oxygen reduction catalyst is the key material of air electrode used in the metal-air battery and the electrochemical oxygen generator. In this paper, nanometer La1-xSrxMnO3 catalyst of perovskite type with high property was prepared by sol-gel method, and the preparation and properties of the material were studied as well.
In this paper, the optimum conditions of catalyst preparation were found by studying the influences of the sol-gel process parameters on the crystal structure of the nanometer La1-xSrxMnO3, such as the value of pH, the temperature of water bath, the drying method of gel and the sintering mode of sol. The catalyst with good performance were prepared as follows: mixed the metal ion and citric acid together by molar ratio of 1:2, then the mixture was dissolved in 150ml water with original solution pH value of 0.5 to prepare the sol; then the water in the sol was vaporized for 5.5h in water bath at temperature of 80 ℃, and the gel is dried in vacuum for 10h at the temperature of 100 ℃. At last, the catalyst is prepared after roasting the gel for 3h at 700℃. The average diameter of the catalysts, observed by the Transmission Electron Microscope (TEM),is 20~50nm.
The softly coacervated nanometer La1-xSrxMnO3 was separated by ultrasonic separating and supported on active carbon uniformly thus the usage ratio of the material was increased. The voidage of the electrode was improved and the three phases boundary was ameliorated by the thermal annealing process of air electrode, and the performance of catalyst was improved as a result.
The influence of the doping Sr on the catalytic performance was studied by measuring the steady-state polarization curve of the air cathode. According to the results, the main factors affecting the catalyst's performance are the deformation of the La1-xSrxMnO3 structure by the doping of Sr, the concentration of oxygen vacancies in the crystal, the ratio of Mn4+/Mn3+ and the change of La1-xSrxMnO3 paramagnetism. The catalytic performance of La1-xSrxMnO3
increased with the amount of doping Sr at first, and the performance was best when x=0.4, then it decreased. The current density reached 324mA/cm2 at -200mV vs Hg/HgO while electrolyte is alkaline solution at the normal tempreture.
The study shows that there are two reaction processes in the air electrode: First, the oxygen vacancies in La1-xSrxMnO3 deacidize oxygen into HO2-, and the Mn4 +/Mn3+deacidizes HO2- into OH-. Second, active carbon with high surface area deacidizes oxygen into HO2- , and the La1-xSxMnO3 deacidizes HO2- into OH- With the associated catalyzing of active carbon and La1-xSrxMnO3, the oxygen is deacidized into OH" by two electrons reaction process and the transformation of four electrons is realized. The catalyzing of the highly performanced catalysts made reaction a quasi four electrons process.
The catalyst was applied in the electrochemical oxygen generator and the effect was very good.
研究了溶胶凝胶制备工艺中pH值、水浴温度、凝胶干燥方法和烧结方式对纳米La_(1-x)Sr_xMnO_3晶体结构影响，确定催化剂最佳制备工艺为：金属离子与柠檬酸的摩尔比为1：2，溶于150ml蒸馏水中，初始溶液pH值为0.5，制备成溶胶，在80℃恒温水浴中蒸发5.5h得到湿凝胶，真空100℃下干燥10h得到干凝胶，最后在700℃烧结3h，得到催化剂样品。经透射电镜观察，催化剂样品平均粒径为20～50nm。
通过超声波分散法使软团聚状态的纳米La_(1-x)Sr_xMnO_3分散，并均匀负载在活性炭载体上，提高材料的利用率。并通过电极热处理工艺，明显提高电极孔隙率、改善三相界面，提高了催化性能。
采用稳态极化曲线测试方法研究Sr的掺杂对La_(1-x)Sr_xMnO_3催化性能的影响。发现Sr的掺杂可使LaMnO_3结构发生畸变，其晶体中氧空位(V_0)浓度、Mn~(4+)／Mn~(3+)比例和La_(1-x)Sr_xMnO_3顺磁性的变化是影响La_(1-x)Sr_xMnO_3催化性能的主要因素。研究结果表明：La_(1-x)Sr_xMnO_3催化性能随Sr掺杂量的增加先增大后减小，当x=0.4时催化性能最强，在常温碱性电解液中，-200mV极化电压下，电流密度达到324mA／cm~2。
研究认为在电极中有两个反应过程：一是，La_(1-x)Sr_xMnO_3中的氧空位将氧气还原为过氧氢根离子，Mn~(4+)／Mn~(3+)还原过氧氢根离子为氢氧根离子；二是，高比表面积的活性炭还原氧气为过氧氢根离子，然后过氧氢根离子被La_(1-x)Sr_xMnO_3还原为氢氧根离子。通过活性炭和La_(1-x)Sr_xMnO_3联合催化，完成氧气还原的二电子反应历程，实现了氧气的四电子转移；高性能的催化，使电极具有氧还原的类四电子反应历程。
催化剂应用于电化学制氧机取得了良好效果。
The oxygen reduction catalyst is the key material of air electrode used in the metal-air battery and the electrochemical oxygen generator. In this paper, nanometer La1-xSrxMnO3 catalyst of perovskite type with high property was prepared by sol-gel method, and the preparation and properties of the material were studied as well.
In this paper, the optimum conditions of catalyst preparation were found by studying the influences of the sol-gel process parameters on the crystal structure of the nanometer La1-xSrxMnO3, such as the value of pH, the temperature of water bath, the drying method of gel and the sintering mode of sol. The catalyst with good performance were prepared as follows: mixed the metal ion and citric acid together by molar ratio of 1:2, then the mixture was dissolved in 150ml water with original solution pH value of 0.5 to prepare the sol; then the water in the sol was vaporized for 5.5h in water bath at temperature of 80 ℃, and the gel is dried in vacuum for 10h at the temperature of 100 ℃. At last, the catalyst is prepared after roasting the gel for 3h at 700℃. The average diameter of the catalysts, observed by the Transmission Electron Microscope (TEM),is 20~50nm.
The softly coacervated nanometer La1-xSrxMnO3 was separated by ultrasonic separating and supported on active carbon uniformly thus the usage ratio of the material was increased. The voidage of the electrode was improved and the three phases boundary was ameliorated by the thermal annealing process of air electrode, and the performance of catalyst was improved as a result.
The influence of the doping Sr on the catalytic performance was studied by measuring the steady-state polarization curve of the air cathode. According to the results, the main factors affecting the catalyst's performance are the deformation of the La1-xSrxMnO3 structure by the doping of Sr, the concentration of oxygen vacancies in the crystal, the ratio of Mn4+/Mn3+ and the change of La1-xSrxMnO3 paramagnetism. The catalytic performance of La1-xSrxMnO3
increased with the amount of doping Sr at first, and the performance was best when x=0.4, then it decreased. The current density reached 324mA/cm2 at -200mV vs Hg/HgO while electrolyte is alkaline solution at the normal tempreture.
The study shows that there are two reaction processes in the air electrode: First, the oxygen vacancies in La1-xSrxMnO3 deacidize oxygen into HO2-, and the Mn4 +/Mn3+deacidizes HO2- into OH-. Second, active carbon with high surface area deacidizes oxygen into HO2- , and the La1-xSxMnO3 deacidizes HO2- into OH- With the associated catalyzing of active carbon and La1-xSrxMnO3, the oxygen is deacidized into OH" by two electrons reaction process and the transformation of four electrons is realized. The catalyzing of the highly performanced catalysts made reaction a quasi four electrons process.
The catalyst was applied in the electrochemical oxygen generator and the effect was very good.
引文
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