Co_3O_4超细粉体的制备及应用研究
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摘要
随着能源危机的加剧,越来越多的研究者致力于开发能够实现能量的高效存储及转化的装置,而锂离子电池和超级电容器就是常用的此类装置。Co_3O_4超细粉体性能优良,是锂离子电池和超级电容器所用的主要原料。Co_3O_4超细粉体的性能直接影响到锂离子电池和超级电容器的性能,因此可应用于锂离子电池和超级电容器的合格的Co_3O_4超细粉体的制备显得非常重要。
采用电化学方法成功制备了可望应用于锂离子电池的Co_3O_4超细粉体。当煅烧温度为400℃、煅烧时间为2h时,前躯体Co(OH)2基本转化为Co_3O_4。研究了工艺参数如Co(NO3)2浓度、电流密度、添加剂种类及浓度、电解温度及时间对Co_3O_4的粒径分布的影响,并由此得到了最佳工艺参数: Co(NO3)2浓度为0.3mol·L-1、电流密度为600A·m-2、添加剂为0.03mol·L-1NH4H2PO4、电解温度为35℃及电解时间为2h。XRD分析表明:最佳工艺条件下制得的Co_3O_4晶型为面心立方晶型,无杂质峰。SEM结果表明:样品颗粒尺寸为4μm-8μm,形貌为四面体,分散性好。
采用反相微乳液法成功制备了可望应用于超级电容器的Co_3O_4超细粉体。反相微乳液体系组成部分中的S种类、O种类和AS种类均能影响体系的增溶量,反相微乳液的最佳配方是S为TritonX-100、O为环己烷、AS为正丁醇。研究了m(AS): m(S)、温度、CoCl2浓度及氨水浓度对反相微乳液区域面积的影响,确定了适用于制备超细Co_3O_4的反相微乳液即m(AS):m(S)=1:1、CoCl2浓度为0.5mol·L-1、氨水浓度为5%,体系反应温度为25℃。电导率测试结果表明时间为2h时体系反应基本完成,SEM结果表明R值的变化不仅能改变样品的粒径而且还能改变其形貌。XRD结果表明最佳反应条件下制得的样品为面心立方晶型Co_3O_4,SEM结果表明产品的粒径大小约为190nm,形貌为球形。恒流充放电测试结果表明该材料的最大比电容为216F·g-1。
采用反相微乳液法成功制备了掺杂锆的Co_3O_4超细粉体,并研究了掺杂量对样品的物相组成、形貌和电化学性能的影响。SEM结果表明锆的掺杂在一定程度上能够降低晶体尺寸,但对样品的形貌不产生影响且均为球形。XRD结果表明掺杂并未改变Co_3O_4的晶相结构,Co_3O_4的晶型均为面心立方型,掺杂量高时XRD谱图中会出现单斜相ZrO2的特征峰。循环伏安、电化学阻抗及恒流充放电测试结果表明锆的适量掺杂能降低电极材料的电荷传递电阻,增强电极材料导电性和可逆性,增大电极材料的比电容。未掺杂的电极材料的最大比电容为216F·g-1,当摩尔比Zr:Co=5:95时,电极材料最高比电容达451F·g-1,即比未掺杂提高了67%。循环800次后,未掺杂的电极材料衰退了22.2%,而掺杂后电极材料的比电容仅衰退了4.21%,即掺杂大大提高了电极材料的循环寿命。
More and more researchers committed to develop a kind of device, which can achieve efficient storage and transformation of energy, with intensified crisis of energy sources. Lithium-ion battery and super capacitor are such devices, which are commonly used. The performance of Co_3O_4 ultra-fine powder is excellent, it can be used as the main raw material to make lithium-ion battery and super capacitor, and the performance of Co_3O_4 ultra-fine powder can directly affect the performance of lithium-ion battery and super capacitor, so it is very important to prepare qualified Co_3O_4 powder to make lithium-ion battery and super capacitor.
Co_3O_4 ultra-fine powder, which was expected to be used as the main raw material for lithium-ion battery, was successfully prepared by electrochemical method. The precursor Co(OH)2 basiclly converted to Co_3O_4 when calcination temperature was 400℃and calcinations time was 2 hours. The influence of parameters on the distribution of particle size of Co_3O_4 powder was studied, the parameters included the concentration of Co(NO3)2、current density、the kinds and concentration of additive、reaction temperature and reaction time. The optimal parameters was that the concentration of Co(NO3)2 was 0.3mol·L-1, current density was 600A·m-2, the additive was NH4H2PO4 and its concentration was 0.03mol·L-1 , reaction temperature was 35℃, reaction time was 2 hours. The result of XRD showed that the crystal of the product was face centered cubic phase. The result of SEM showed that the range of the particle size of the product was 4μm to 8μm, the morphology was tetrahedron, and it had good dispersion.
Co_3O_4 ultra-fine powder, which was expected to be used as the main raw material for super capacitor, was successfully prepared by reverse microemulsion method.The components of reverse microemulsion could affect solubilization capacity, the components included the kinds of S、O and AS. The optimal components of reverse microemulsion was that S was TritonX-100, O was cyclohexane, AS was butanol. The influence of parameters on the regional area of reverse microemulsion was studied, the parameters included the mass ratio of AS to S、the concentration of CoCl2、the concentration of ammonia、temperature.The optimal parameters was that the mass ratio of AS to S was 1, the concentration of CoCl2 was 0.5mol·L-1, the concentration of ammonia was 5%, temperature was 25℃. Conductivity test showed that the reaction was basically completed when time was 2 hours. The result of SEM showed that the particle size and the morphology of the product would change when the value of R was changed. The result of XRD showed that that the crystal of the product was face centered cubic phase. The result of SEM showed that the particle size of the product was 190nm, and the morphology was sphere. galvanostatic current charge and discharge test showed that the maximum specific capacitance was 216F·g-1.
Zr doped Co_3O_4 ultra-fine powder was successfully prepared by reverse microemulsion method. The influence of doping Zr on the morphology, phase composition, electrochemical properties of the products was studied. The result of SEM showed that the particle size of the product was to be smaller with doping Zr to some extent, the morphology of all products was sphere.The result of XRD showed that doping Zr could not change the crystal of the product, the crystal of all products were face centered cubic phase, and it would appear characteristic peak of monoclinic phase ZrO2 with high doping amount. Cyclic voltammetry (CV)、electrochemical impedance spectrometry (EIS) and galvanostatic charge-discharge tests indicated that the charge transfer resistance was to be smaller, the reversible was enhanced, the specific capacitance was increased, and the cycle life was improved with doping certain amount of Zr. The specific capacitance of the undoped product was 216F·g-1, The highest specific capacitance of 451F·g-1 was obtained when the molar ratio of Zr to Co was 5 to 95, which was 67% higher than that of the undoped product. After 800 charge-discharge cycles, the specific capacitance was only decreased 4.21%, while the specific capacitance of the undoped product was decreased 22.2%.
采用电化学方法成功制备了可望应用于锂离子电池的Co_3O_4超细粉体。当煅烧温度为400℃、煅烧时间为2h时,前躯体Co(OH)2基本转化为Co_3O_4。研究了工艺参数如Co(NO3)2浓度、电流密度、添加剂种类及浓度、电解温度及时间对Co_3O_4的粒径分布的影响,并由此得到了最佳工艺参数: Co(NO3)2浓度为0.3mol·L-1、电流密度为600A·m-2、添加剂为0.03mol·L-1NH4H2PO4、电解温度为35℃及电解时间为2h。XRD分析表明:最佳工艺条件下制得的Co_3O_4晶型为面心立方晶型,无杂质峰。SEM结果表明:样品颗粒尺寸为4μm-8μm,形貌为四面体,分散性好。
采用反相微乳液法成功制备了可望应用于超级电容器的Co_3O_4超细粉体。反相微乳液体系组成部分中的S种类、O种类和AS种类均能影响体系的增溶量,反相微乳液的最佳配方是S为TritonX-100、O为环己烷、AS为正丁醇。研究了m(AS): m(S)、温度、CoCl2浓度及氨水浓度对反相微乳液区域面积的影响,确定了适用于制备超细Co_3O_4的反相微乳液即m(AS):m(S)=1:1、CoCl2浓度为0.5mol·L-1、氨水浓度为5%,体系反应温度为25℃。电导率测试结果表明时间为2h时体系反应基本完成,SEM结果表明R值的变化不仅能改变样品的粒径而且还能改变其形貌。XRD结果表明最佳反应条件下制得的样品为面心立方晶型Co_3O_4,SEM结果表明产品的粒径大小约为190nm,形貌为球形。恒流充放电测试结果表明该材料的最大比电容为216F·g-1。
采用反相微乳液法成功制备了掺杂锆的Co_3O_4超细粉体,并研究了掺杂量对样品的物相组成、形貌和电化学性能的影响。SEM结果表明锆的掺杂在一定程度上能够降低晶体尺寸,但对样品的形貌不产生影响且均为球形。XRD结果表明掺杂并未改变Co_3O_4的晶相结构,Co_3O_4的晶型均为面心立方型,掺杂量高时XRD谱图中会出现单斜相ZrO2的特征峰。循环伏安、电化学阻抗及恒流充放电测试结果表明锆的适量掺杂能降低电极材料的电荷传递电阻,增强电极材料导电性和可逆性,增大电极材料的比电容。未掺杂的电极材料的最大比电容为216F·g-1,当摩尔比Zr:Co=5:95时,电极材料最高比电容达451F·g-1,即比未掺杂提高了67%。循环800次后,未掺杂的电极材料衰退了22.2%,而掺杂后电极材料的比电容仅衰退了4.21%,即掺杂大大提高了电极材料的循环寿命。
More and more researchers committed to develop a kind of device, which can achieve efficient storage and transformation of energy, with intensified crisis of energy sources. Lithium-ion battery and super capacitor are such devices, which are commonly used. The performance of Co_3O_4 ultra-fine powder is excellent, it can be used as the main raw material to make lithium-ion battery and super capacitor, and the performance of Co_3O_4 ultra-fine powder can directly affect the performance of lithium-ion battery and super capacitor, so it is very important to prepare qualified Co_3O_4 powder to make lithium-ion battery and super capacitor.
Co_3O_4 ultra-fine powder, which was expected to be used as the main raw material for lithium-ion battery, was successfully prepared by electrochemical method. The precursor Co(OH)2 basiclly converted to Co_3O_4 when calcination temperature was 400℃and calcinations time was 2 hours. The influence of parameters on the distribution of particle size of Co_3O_4 powder was studied, the parameters included the concentration of Co(NO3)2、current density、the kinds and concentration of additive、reaction temperature and reaction time. The optimal parameters was that the concentration of Co(NO3)2 was 0.3mol·L-1, current density was 600A·m-2, the additive was NH4H2PO4 and its concentration was 0.03mol·L-1 , reaction temperature was 35℃, reaction time was 2 hours. The result of XRD showed that the crystal of the product was face centered cubic phase. The result of SEM showed that the range of the particle size of the product was 4μm to 8μm, the morphology was tetrahedron, and it had good dispersion.
Co_3O_4 ultra-fine powder, which was expected to be used as the main raw material for super capacitor, was successfully prepared by reverse microemulsion method.The components of reverse microemulsion could affect solubilization capacity, the components included the kinds of S、O and AS. The optimal components of reverse microemulsion was that S was TritonX-100, O was cyclohexane, AS was butanol. The influence of parameters on the regional area of reverse microemulsion was studied, the parameters included the mass ratio of AS to S、the concentration of CoCl2、the concentration of ammonia、temperature.The optimal parameters was that the mass ratio of AS to S was 1, the concentration of CoCl2 was 0.5mol·L-1, the concentration of ammonia was 5%, temperature was 25℃. Conductivity test showed that the reaction was basically completed when time was 2 hours. The result of SEM showed that the particle size and the morphology of the product would change when the value of R was changed. The result of XRD showed that that the crystal of the product was face centered cubic phase. The result of SEM showed that the particle size of the product was 190nm, and the morphology was sphere. galvanostatic current charge and discharge test showed that the maximum specific capacitance was 216F·g-1.
Zr doped Co_3O_4 ultra-fine powder was successfully prepared by reverse microemulsion method. The influence of doping Zr on the morphology, phase composition, electrochemical properties of the products was studied. The result of SEM showed that the particle size of the product was to be smaller with doping Zr to some extent, the morphology of all products was sphere.The result of XRD showed that doping Zr could not change the crystal of the product, the crystal of all products were face centered cubic phase, and it would appear characteristic peak of monoclinic phase ZrO2 with high doping amount. Cyclic voltammetry (CV)、electrochemical impedance spectrometry (EIS) and galvanostatic charge-discharge tests indicated that the charge transfer resistance was to be smaller, the reversible was enhanced, the specific capacitance was increased, and the cycle life was improved with doping certain amount of Zr. The specific capacitance of the undoped product was 216F·g-1, The highest specific capacitance of 451F·g-1 was obtained when the molar ratio of Zr to Co was 5 to 95, which was 67% higher than that of the undoped product. After 800 charge-discharge cycles, the specific capacitance was only decreased 4.21%, while the specific capacitance of the undoped product was decreased 22.2%.
引文
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