纳米层状二氧化锰的制备及其性能研究
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摘要
润滑油添加剂是一种具有良好的减摩抗磨性能和较高的承载能力得以及对摩擦副表面有良好的修复性能的材料。纳米粒子因其具有的一些特殊性质而作为润滑油添加剂能明显提高基础油的摩擦学性能。超级电容器是近年来出现的一种介于传统电容器与电池之间的新概念能力储存容器,因为具有高功率、能量密度和长循环寿命等优点,在移动通信、消费电子、电动汽车、航空航天和国防等领域有广阔的应用,在世界范围内引起了极大的关注。
本文利用反歧化反应：强氧化剂KMnO4氧化MnCl2与碱溶液反应产生悬浮物。通过水热合成法和液相沉淀法两种制备工艺制备了纳米Mn02,考察了水热合成法制备工艺中的反应物、水热温度、水热时间与表面修饰剂处理对产物的影响。通过X射线衍射(XRD)、扫描电子显微镜(SEM)等手段对样品的结构及形貌进行了表征,发现水热合成法和液相沉淀法制备的纳米MnO2主要成分为金红石结构的δ-MnO2———钠水锰矿(Syn.Birnessite)Nao.58Mn204·1.5H2O、KMn2O4·1.4H2O。
本文利用沉降实验、四球摩擦磨损实验等摩擦学测试方法,通过金相显微镜和SEM等分析手段对钢-钢摩擦副表面进行分析,研究了MnO2纳米粒子作为润滑油添加剂添加到液体石蜡中的摩擦学性能和作用机理。结果表明,Mn02纳米粒子的加入对润滑油的承载能力无明显影响,但是它却能在一定程度上降低摩擦副的磨斑直径,具有较好减摩性能。经过表面修饰剂改性过后的Mn02,摩擦性能都比没有改性Mn02的好。其中在润滑油中经过酸改性过后陈化的MnO2纳米粒子浓度达到0.1%时,磨斑直径下降值最大,从670.3μm下降到441.7μm；在润滑油中SDS改性后水热制备Mn02纳米粒子浓度达到0.75%时,摩擦系数从0.0073下降到0.0058。
通过循环伏安法等电化学测试方法以及BET比表面分析等研究手段研究了层状二氧化锰的微观结构对其电化学电容量的影响。通过循环伏安测试表明Mn02电极材料在Na2SO4溶液中具有优异的电容特性,陈化后酸改性制备的MnO2电极,在5mV/s的扫速下其比电容达到了263.6F/g。比电容最小的水热后酸改性制备Mn02电极,在5mV/s的扫速下其比电容也达到了203.9F/g。研究结果表明,比电容量随着吸附孔平均直径的增大而增大。
Oil additive is a kind of material with good antiwear properties, high load-carrying capacity and self-repair of the worn surface. Nanoparticles because of its special nature can improve the oil tribological properties as oil additives. The supercapacitors is a new storage containers whose capability between traditional capacitor and battery capacity. It contains high-power, energy density and long cycle life. The promising application of supercapacitors in the fields such as mobile telecommnication, consumer electronics, electric cehicle, aviation and national defense, has been attention through out the world.
Strong oxidant KMnO4 was used to effect the MnCl2 and alkali solution's suspended solids in the redox reaction. Nanometer layered MnO2 was prepared by using hydrothermal method and liquid precipitation method. The effects of reactants, temperature, time and surface chemical treatments on products were investigated. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to determine the crystal structure and morphology of nanoparticles. It was found that the main phase of as synthesized powder was rutile structure ofδ-MnO2—Syn.Birnessite Na0.58Mn204·1.5H2O, KMn2O4·1.4H2O.
Sedimentation experiment and four-ball wear testing were used to investigate the tribology properties. And optical microscopy and SEM were used to observed the surface of steel-steel friction pair. The results show that MnO2 nanoparticles had no effect on the carrying capacity of lubricating oil. But it can reduce the wear scar diameter and has good antiwear ability. The modified MnO2 have better tribological properties. When the concentration of MnO2 nanoparticles which was modified by H2SO4 and prepared by aging, is 0.1%, the wear scar diameter decline largest and decreases from 670.3μm to 441.7μm. When the concentration of MnO2 nanoparticles which is modified by SDS and prepared by hydrothermal synthesis, is 0.75%, friction coefficient decreases from 0.0073 to 0.0058.
The cyclic voltammetry (CV) testing and BET surface area analysis are used to invest the impact of layered manganese dioxide's microstructure on the electrochemical capacitance. The CV testing shows that the MnO2 electrode material's capacitance in the Na2SO4 solution has excellent capacitance characteristics. The discharge capacity of the MnO2 electrode which is prepared by aging and modified by H2SO4, is 263.6 F/g when the scan speed is 5mV/s. Even the lowest discharge capacity of MnO2 which is prepared by hydrothermal synthesis and modified by H2SO4, is 203.9 F/g at 5mV/s scan speed. The results show that capacitance data shows that the discharge capacity of MnO2 increases with the average adsorption pore diameter.
本文利用反歧化反应：强氧化剂KMnO4氧化MnCl2与碱溶液反应产生悬浮物。通过水热合成法和液相沉淀法两种制备工艺制备了纳米Mn02,考察了水热合成法制备工艺中的反应物、水热温度、水热时间与表面修饰剂处理对产物的影响。通过X射线衍射(XRD)、扫描电子显微镜(SEM)等手段对样品的结构及形貌进行了表征,发现水热合成法和液相沉淀法制备的纳米MnO2主要成分为金红石结构的δ-MnO2———钠水锰矿(Syn.Birnessite)Nao.58Mn204·1.5H2O、KMn2O4·1.4H2O。
本文利用沉降实验、四球摩擦磨损实验等摩擦学测试方法,通过金相显微镜和SEM等分析手段对钢-钢摩擦副表面进行分析,研究了MnO2纳米粒子作为润滑油添加剂添加到液体石蜡中的摩擦学性能和作用机理。结果表明,Mn02纳米粒子的加入对润滑油的承载能力无明显影响,但是它却能在一定程度上降低摩擦副的磨斑直径,具有较好减摩性能。经过表面修饰剂改性过后的Mn02,摩擦性能都比没有改性Mn02的好。其中在润滑油中经过酸改性过后陈化的MnO2纳米粒子浓度达到0.1%时,磨斑直径下降值最大,从670.3μm下降到441.7μm；在润滑油中SDS改性后水热制备Mn02纳米粒子浓度达到0.75%时,摩擦系数从0.0073下降到0.0058。
通过循环伏安法等电化学测试方法以及BET比表面分析等研究手段研究了层状二氧化锰的微观结构对其电化学电容量的影响。通过循环伏安测试表明Mn02电极材料在Na2SO4溶液中具有优异的电容特性,陈化后酸改性制备的MnO2电极,在5mV/s的扫速下其比电容达到了263.6F/g。比电容最小的水热后酸改性制备Mn02电极,在5mV/s的扫速下其比电容也达到了203.9F/g。研究结果表明,比电容量随着吸附孔平均直径的增大而增大。
Oil additive is a kind of material with good antiwear properties, high load-carrying capacity and self-repair of the worn surface. Nanoparticles because of its special nature can improve the oil tribological properties as oil additives. The supercapacitors is a new storage containers whose capability between traditional capacitor and battery capacity. It contains high-power, energy density and long cycle life. The promising application of supercapacitors in the fields such as mobile telecommnication, consumer electronics, electric cehicle, aviation and national defense, has been attention through out the world.
Strong oxidant KMnO4 was used to effect the MnCl2 and alkali solution's suspended solids in the redox reaction. Nanometer layered MnO2 was prepared by using hydrothermal method and liquid precipitation method. The effects of reactants, temperature, time and surface chemical treatments on products were investigated. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to determine the crystal structure and morphology of nanoparticles. It was found that the main phase of as synthesized powder was rutile structure ofδ-MnO2—Syn.Birnessite Na0.58Mn204·1.5H2O, KMn2O4·1.4H2O.
Sedimentation experiment and four-ball wear testing were used to investigate the tribology properties. And optical microscopy and SEM were used to observed the surface of steel-steel friction pair. The results show that MnO2 nanoparticles had no effect on the carrying capacity of lubricating oil. But it can reduce the wear scar diameter and has good antiwear ability. The modified MnO2 have better tribological properties. When the concentration of MnO2 nanoparticles which was modified by H2SO4 and prepared by aging, is 0.1%, the wear scar diameter decline largest and decreases from 670.3μm to 441.7μm. When the concentration of MnO2 nanoparticles which is modified by SDS and prepared by hydrothermal synthesis, is 0.75%, friction coefficient decreases from 0.0073 to 0.0058.
The cyclic voltammetry (CV) testing and BET surface area analysis are used to invest the impact of layered manganese dioxide's microstructure on the electrochemical capacitance. The CV testing shows that the MnO2 electrode material's capacitance in the Na2SO4 solution has excellent capacitance characteristics. The discharge capacity of the MnO2 electrode which is prepared by aging and modified by H2SO4, is 263.6 F/g when the scan speed is 5mV/s. Even the lowest discharge capacity of MnO2 which is prepared by hydrothermal synthesis and modified by H2SO4, is 203.9 F/g at 5mV/s scan speed. The results show that capacitance data shows that the discharge capacity of MnO2 increases with the average adsorption pore diameter.
引文
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