摘要
超级电容器是一种性能介于传统电容器和电池之间的新型电化学储能器件,因其功率高、循环性能好、充电速度快等优点,有望应用于军事、电动汽车、风能／太阳能发电以及消费类电子产品等诸多领域。在目前报道的超级电容器电极材料中,金属氧化物具有高于碳材料的比容量和优于导电聚合物的循环稳定性,最有潜力成为未来高比能量超级电容器的电极材料。本文根据目前最为常见的金属氧化物电极材料NiO和C0304赝电容性能的特点,设计制备了双金属氧化物及其复合材料,并根据分子式的不同将双金属氧化物分为AB204型、AB04型和A3B208型,分别研究了不同类型双金属氧化物及其复合材料的赝电容行为。
(1)采用溶胶-凝胶方法制备了NiO和C0304电极材料,系统研究了其赝电容性能(NiO具有高比容量,但倍率性能和循环稳定性较差；C0304虽然容量远远低于NiO,却具有良好的倍率性能和循环稳定性)。为了兼备NiO和C0304材料赝电容性能的优点,设计制备了基于Ni.Co元素的AB204型双金属氧化物NiCo2O4;通过控制热处理的温度,分别得到了纯NiCo2O4和NiO/NiCo2O4/Co3O4复合材料。结果显示NiCo2O4不仅具有高于NiO的比容量,同时兼备了良好的倍率性能和循环稳定性；NiO/NiCo2O4/Co3O4复合材料具有更优于NiCo2O4的赝电容性能。说明设计双金属氧化物能使其兼备两种金属元素氧化物的赝电容性能优点,而通过复合则能够进一步提升氧化物材料的赝电容性能。同时,通过对于NiCo2O4中Ni元素的替代,制备了另一种AB204型双金属氧化物MnCo204。MnCo2O4虽然保持了较好的循环稳定性,但比容量和倍率性能远远低于NiCo2O4。说明AB204型双金属氧化物中,A位元素对于其比容量和倍率性能具有明显的影响作用。
(2)为了进一步研究双金属氧化物中A、B两种元素对其赝电容性能的影响,分别设计制备了ABO4型双金属氧化物NiMoO4、CoMoO4、NiWO4和CoW04。通过对于四种双金属氧化物电极材料赝电容性能的研究发现：A位元素对ABO4型双金属氧化物的比容量、倍率性能和循环稳定性具有重要的影响作用,当A位元素变化时,双金属氧化物的比容量、倍率性能和循环稳定性会发生明显变化,双金属氧化物体现出接近于其A位元素氧化物的赝电容特性；当A位元素保持不变,B位元素变化时,双金属氧化物材料的赝电容性能的变化较小,说明B位元素对于双金属氧化物赝电容性能的影响弱于A位元素。
(3)为了证实A位元素对于双金属氧化物赝电容性能的决定性影响作用以及A、B两种元素的比例对于双金属氧化物赝电容性能的影响规律,设计制备了A3B208型双金属氧化物Ni3V2O8和Co3V2O8。通过对于其赝电容性能的表征证实了A位元素对于双金属氧化物赝电容性能的决定性作用,即双金属氧化物材料的赝电容性能主要由处于A位的低价态元素所决定；随着双金属氧化物中A、B元素比例的增加,比容量随之增加。同时通过对于Ni系和Co系双金属氧化物赝电容性能的系统研究总结得出：Ni系双金属氧化物都具有高的比容量,但其倍率性能和循环稳定性较差(除了NiCo2O4具有良好的倍率性能和循环稳定性)；Co系双金属氧化物则容量低,但具有良好的倍率性能和循环稳定性。
(4)为全面提升双金属氧化物电极材料的赝电容性能,根据Ni系和Co系双金属氧化物赝电容性能的优缺点和结构特性设计制备了双金属氧化物复合材料(CoMoO4/NiMoO4和Ni3V2O8/Co3V2O8材料),通过控制材料中Ni系和Co系双金属氧化物相对含量的线性变化,最终探明复合材料的高比容量主要由Ni系双金属氧化物贡献,而良好的倍率储能则主要由Co系双金属氧化物贡献。同时通过具有不同尺寸和结构的Ni系和Co系双金属氧化物的选择以及里外层次(指骨架结构与表面包覆层结构)的设计,确定了复合尺寸和结构次序对于复合材料赝电容性能的贡献作用,即纳米尺寸的复合效果优于微米尺寸的复合；容量高的Ni系适合于作为复合材料的骨架,而倍率性能和循环稳定性较好的Co系更适合于作为表面包覆层。
Supercapacitor is a new type of energy storage equipments which can fill the gap between conventional dielectric capacitors and batteries, it characterized as high-power density, excellent cycle stability, and quick charge-discharge capability. It aroused considerable interest in applications in military field, electric vehicles, wind power generation, solar cells and electronic products. In the range of reported electrode materials for supercapacitor, metal oxides exhibit higher specific capacitance than carbon materials as well as better stability than conducting polymer materials, is one of the most important materials for next generation supercapacitor with high energy density. In this thesis, binary metal oxides and their composites are designed as novel electrode materials according to the reported pseudo-capacitive characteristics of NiO and CO3O4. The binary metal oxides are divided into AB2O4, ABO4, and A3B2O8type according to their molecular formula, and then the pseudo-capacitive properties of them and their composites are investigated.
(1) NiO and CO3O4are synthesized by a sol-gel process and the pseudo capacitive properties of them are studied (Though the specific capacitance of NiO is high, its rate capability and cycle stability are inferior. However, CO3O4shows excellent rate capability and cycle stability, but its specific capacitance is much lower than that of NiO.). in order to combine the advantages of both NiO and CO3O4, the NiCo2O4(AB2O4type binary metal oxide) which based on Ni and Co is designed and synthesized. By controll the calcination temperature, NiCo2O4and NiO/NiCo2O4/Co3O4composite are obtained. The prepared NiCo2O4combines the high specific capacitance, excellent rate capability and good cycle stability, and the NiO/NiCo2O4/Co3O4composite also exhibits superior pseudo-capacitive properties than NiCo2O4. The results indicate that the design of binary metal oxides can combine the advantages of both metal oxides, and design of composites can imropve the pseudo-capacitive properties of the metal oxides. Meanwhile, MnCo2O4(another AB2O4type binary metal oxide) is synthesized by replacing Ni by Co in NiCO2O4, it shows lower specific capacitance and rate capability than NiCo2O4, indicating that the element located in A position has important effects on specific capacitance and rate capability of AB2O4type binary metal oxides.
(2) To further study the contribution of the A and B elements to pseudo-capacitive properties of the binary metal oxides, the ABO4type binary metal oxides of NiMoO4, CoMoO4, NiWO4, and COWO4are designed and synthesized. By study the pseudo-capacitive properties of these binary metal oxides, we found that the element located in A position has important effects on specific capacitance, rate capability, and cycle stability of binary metal oxides. The pseudo-capacitive properties of these binary metal oxides are on the verge of metal oxides which located in A position. The change of the element located in B position has minor influence on pseudo-capacitive properties of binary metal oxides, indicating that the influence of element on pseudo-capacitive properties of binary metal oxides is lower than that of A element.
(3) To confirm the decisive influence effect of the element located in A position to the pseudo-capacitive properties of binary metal oxide, and the effects of A and B ratios on pseudo-capacitive properties of binary metal oxide, the A3B2O8type binary metal oxides (Ni3V2O8and Co3V2O8) are designed and synthesized. The pseudo-capacitive properties of Ni3V2O8and CO3V2O8indicate the decisive effect of the element located in A position to the pseudo-capacitive properties of binary metal oxide, and the effects of A and B ratios on pseudo-capacitive properties of binary metal oxides. That means the pseudo-capacitive properties of binary metal oxides are mainlg determined by the A element, thus the specific capacitance increasing with at higher A/B ratios. At the same time, we also found that the Ni based binary metal oxides show higher specific capacitance but inferior rate capability and cycle stability (except NiCo2O4). Howerver, the Co based binary metal oxides exhibit excellent rate capability and cycle stability but lower specific capacitance.
(4) To improve the pseudo-capacitive properties of binary metal oxides based electrode materials, binary metal oxides composites (CoMoO4/NiMoO4and Ni3V2O8/Co3V2O8nanocomposites) are designed according to the advantages/disadvantages of both Ni and Co based binary metal oxides. By controlling the mass ratios of Ni based binary metal oxides and Co based binary metal oxides in the composites, we found that the high specific capacitance of the composites is contributed by the Ni based binary metal oxides, and the excellent rate capability of the composites is contributed by the Co based binary metal oxides.
Meanwhile, by tail the structure and sizes of Ni and Co based binary metal oxides in the composites, we found that nanosize is more useful to improve the pseudo-capacitive properties of binary metal oxides based composites, and the Ni based binary metal oxides with high specific capacitance are more suitable ro serve as skeleton structure of the composite, but the Co based binary metal oxides with excellent rate capability and cycle stability are suitable to serve as coating structure of the composite.
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