金属氧化物电化学电容器电极材料的研究
摘要
超级电容器作为一种新型的储能器件,因其功率密度高、循环寿命长、绿色环保等优点,被广泛应用到工业大型UPS电源系统、电动汽车以及航空航天等领域。本论文是分别以V_2O_5、TiO_2和NiO为电化学电容器的电极材料,系统研究制备方法及掺杂复合对V_2O_5、TiO_2和NiO电化学性能的影响。
本论文主要进行了以下几方面的研究工作:
1.本文采用化学沉淀法和溶胶凝胶法制备亚微米级V_2O_5粉末材料。溶胶凝胶法制备的V_2O_5材料在LiClO_4、LiPF_6、四氟硼酸胺三种有机电解液体系中,表现出良好的电容性能,通过CV和恒流充放电研究表明,在1M LiClO_4中的性能最好,比能量为20.20Wh/kg。
2.通过掺杂镍、锡和炭材料对V_2O_5的改性,提高V_2O_5的比容量和比功率。镍、锡掺入到V_2O_5中,比表面积分别为92m~2/g和121m~2/g。比能量得到提高,分别为15.6Wh/kg和54.5Wh/kg。碳材料掺杂比表面积增大达到499m~2/g,导电性增加,循环性能提高。
3.通过对TiO_2粉末掺杂Ni、C制备出具有锐钛矿型的TiO_2复合电极材料。采用XRD、SEM、CV、交流阻抗和恒流充放电循环等测试手段,考察了Ni、C掺杂对TiO_2晶型结构及电化学性能的影响。
4.本文采用球磨法制备Ni(OH)_2,比表面积达100m~2/g。CV、交流阻抗和恒流充放电研究表明Ni(OH)_2具有赝电容特性。在250℃热处理得到NiO,比表面积为175m~2/g,比功率952.2W/kg。采用NiO和活性炭为正负极材料,制备成SC型钢壳电化学电容器,对其进行串并联组合进行电化学性能研究。
5.采用微波法制备NiO电极材料,对微波功率和反应时间进行考察,480W微波加热135秒的NiO材料的电容性能最好。将硫酸镍与含有掺杂元素的化合物混合,利用微波法制备掺杂NiO,掺Al/Ni=0.3的NiO材料的比表面积为202m~2/g,掺Co/Ni=0.4的NiO材料的比表面积为146m~2/g。
Super capacitors as a new kind of maintaining power device are attracting more attention for their advantages such as high power density, long cycle life, green environment protection, etc. Super capacitors are widely used in industrial large UPS power supply, electric vehicle, aerospace, etc. In this paper, the author investigates the effects of the preparation methods and doping on the performance of super capacitors used V_2O_5, TiO_2 and NiO as the electrode materials.
This paper has mainly been performed though the following aspects:
1. Liquid phase method and sol-gel method were used to prepare the submicron V_2O_5 powder material, and the electrochemical characteristics of prepared V_2O_5 were studied. The V_2O_5 prepared by sol-gel method showed good capacitance characteristic in LiCIO4 or LiPF6 or Et4NBF4 electrolyte. The results of CV and constant current discharge show that the V_2O_5 capacitors have best characteristic in 1M LiClO4 electrolyte and the specific energy reaches 20.2Wh/kg.
2. The capability and power characteristics of V_2O_5 are improved by doping Ni and Sn, the specific surface area of V_2O_5 doped Sn or Ni complex material is 92m2/g and 121m2/g, respectively. The specific power is respective 15.6Wh/kg and 54.5Wh/kg. The specific surface area after carbon doped achieves 499m2/g and the conductivity is improved.
3. The anatase TiO_2 complex electrode was prepared by doping the Ni or C element into TiO_2. The author used XRD, SEM, CV, EIS and constant current discharging method to check the influence of doping Ni or C elements on the crystal structure and electrochemical characteristic of TiO_2.
4. Ball milling method was used to prepare the Ni(OH)_2, and the specific surface area of the material is 100.37m2/g. The results of CV, EIS and constant current discharging test show that the Ni(OH)_2 has pseudo capacitance characteristics. After 250℃treatment, the electrochemical test shows that the specific power and the specific surface area of NiO is 952.2W/kg and 175m2/g, respectively. The author first made the material into slurry, and then coated it onto the Ni foam, and finally made SC steel shell electrochemical capacitors. And the series-parallel characteristics were tested and the effects of series-parallel on power characteristics were discussed.
5. Research on NiO elelctrode materials prepared by the microwave method. The effects of the microwave power and reaction time on the performance of prepared NiO materials were studied. The best preparation condition is 135s with 640W. The preparation method is that the Ni_2SO_4 and some certain compounds containing doping elements were mixed, NiO was prepared with microwave method. The specific surface area of NiO with the proportion Al/Ni= 0.3 is 202m~2/g, with Co/Ni=0.4 is 146m~2/g, The best proportions are found to be Al/Ni=0.3 and Co/Ni=0.4.
本论文主要进行了以下几方面的研究工作:
1.本文采用化学沉淀法和溶胶凝胶法制备亚微米级V_2O_5粉末材料。溶胶凝胶法制备的V_2O_5材料在LiClO_4、LiPF_6、四氟硼酸胺三种有机电解液体系中,表现出良好的电容性能,通过CV和恒流充放电研究表明,在1M LiClO_4中的性能最好,比能量为20.20Wh/kg。
2.通过掺杂镍、锡和炭材料对V_2O_5的改性,提高V_2O_5的比容量和比功率。镍、锡掺入到V_2O_5中,比表面积分别为92m~2/g和121m~2/g。比能量得到提高,分别为15.6Wh/kg和54.5Wh/kg。碳材料掺杂比表面积增大达到499m~2/g,导电性增加,循环性能提高。
3.通过对TiO_2粉末掺杂Ni、C制备出具有锐钛矿型的TiO_2复合电极材料。采用XRD、SEM、CV、交流阻抗和恒流充放电循环等测试手段,考察了Ni、C掺杂对TiO_2晶型结构及电化学性能的影响。
4.本文采用球磨法制备Ni(OH)_2,比表面积达100m~2/g。CV、交流阻抗和恒流充放电研究表明Ni(OH)_2具有赝电容特性。在250℃热处理得到NiO,比表面积为175m~2/g,比功率952.2W/kg。采用NiO和活性炭为正负极材料,制备成SC型钢壳电化学电容器,对其进行串并联组合进行电化学性能研究。
5.采用微波法制备NiO电极材料,对微波功率和反应时间进行考察,480W微波加热135秒的NiO材料的电容性能最好。将硫酸镍与含有掺杂元素的化合物混合,利用微波法制备掺杂NiO,掺Al/Ni=0.3的NiO材料的比表面积为202m~2/g,掺Co/Ni=0.4的NiO材料的比表面积为146m~2/g。
Super capacitors as a new kind of maintaining power device are attracting more attention for their advantages such as high power density, long cycle life, green environment protection, etc. Super capacitors are widely used in industrial large UPS power supply, electric vehicle, aerospace, etc. In this paper, the author investigates the effects of the preparation methods and doping on the performance of super capacitors used V_2O_5, TiO_2 and NiO as the electrode materials.
This paper has mainly been performed though the following aspects:
1. Liquid phase method and sol-gel method were used to prepare the submicron V_2O_5 powder material, and the electrochemical characteristics of prepared V_2O_5 were studied. The V_2O_5 prepared by sol-gel method showed good capacitance characteristic in LiCIO4 or LiPF6 or Et4NBF4 electrolyte. The results of CV and constant current discharge show that the V_2O_5 capacitors have best characteristic in 1M LiClO4 electrolyte and the specific energy reaches 20.2Wh/kg.
2. The capability and power characteristics of V_2O_5 are improved by doping Ni and Sn, the specific surface area of V_2O_5 doped Sn or Ni complex material is 92m2/g and 121m2/g, respectively. The specific power is respective 15.6Wh/kg and 54.5Wh/kg. The specific surface area after carbon doped achieves 499m2/g and the conductivity is improved.
3. The anatase TiO_2 complex electrode was prepared by doping the Ni or C element into TiO_2. The author used XRD, SEM, CV, EIS and constant current discharging method to check the influence of doping Ni or C elements on the crystal structure and electrochemical characteristic of TiO_2.
4. Ball milling method was used to prepare the Ni(OH)_2, and the specific surface area of the material is 100.37m2/g. The results of CV, EIS and constant current discharging test show that the Ni(OH)_2 has pseudo capacitance characteristics. After 250℃treatment, the electrochemical test shows that the specific power and the specific surface area of NiO is 952.2W/kg and 175m2/g, respectively. The author first made the material into slurry, and then coated it onto the Ni foam, and finally made SC steel shell electrochemical capacitors. And the series-parallel characteristics were tested and the effects of series-parallel on power characteristics were discussed.
5. Research on NiO elelctrode materials prepared by the microwave method. The effects of the microwave power and reaction time on the performance of prepared NiO materials were studied. The best preparation condition is 135s with 640W. The preparation method is that the Ni_2SO_4 and some certain compounds containing doping elements were mixed, NiO was prepared with microwave method. The specific surface area of NiO with the proportion Al/Ni= 0.3 is 202m~2/g, with Co/Ni=0.4 is 146m~2/g, The best proportions are found to be Al/Ni=0.3 and Co/Ni=0.4.
引文
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