摘要
超级电容器是一种随着材料科学的发展而出现的新一代功率型储能元件。它既具有传统电容器的大电流快速充放电的特性,又具备蓄电池的高储能密度特性,在电动车、脉冲功率系统、电能武器、UPS和叉式升降机等领域有着广泛的应用,是能源技术研究的热点。
本文以近年来国外出现的混合型超级电容器为研究背景,比较深入地研究了这种新型超级电容器的建模、制备及其测试。首先,本文在Conway模型和电极的物理结构的基础上建立了二氧化钌/活性炭复合电极的模型,着重分析了超级电容器的恒流放电特性,探究在不同配比下二氧化钌和活性炭的复合电极的阻抗性能和电容特性的基本变化规律。同时,针对目前典型的压覆电极薄膜的特点,进一步修正和改进模型,分析由压覆式电极组成的超级电容器的特性,并在理论上初步探讨超级电容器内阻、电容量和相角的影响因素。
超级电容器的核心技术在于其电极制备,通常多孔电极材料的物理特征决定着电极的电化学性能。本文通过对不同孔径和形状的多孔电极的静电场仿真计算,得到了多孔电极内部电场的分布情况。仿真结果表明通过控制孔径和孔形状等参数可改善多孔电极的电场分布,提高电极的电容量。
为了提高超级电容器的工作电压使之满足脉冲功率源的要求,本文设计并研制了混合型超级电容器单元。它将电解电容器的阳极和超级电容器的阴极结合,所以同时具有电解电容器和超级电容器的优点,从本质上提高了超级电容器的工作电压,进一步提高了储能密度。实验结果表明,该单元工作电压可达到100V以上,最大储能密度和功率密度分别为0.37J/g、8250W/g。在此单元基础上,进一步设计了由100只混合型超级电容器单元并联构成的储能模块。通过仿真分析,验证了储能单元的放电性能可以满足大电流快速充放电的要求。当该模块向0.38 mΩ/10 mH的电感性负载放电时,放电电流可以达到2kA,放电功率达200KW。在此仿真结果的基础上,制备出性能参数为0.06F/3mΩ/0.3kJ的超级电容器储能模块样品,并进行了实验研究。测试结果表明由混合型超级电容器单元组成的储能装置可以满足脉冲功率系统的要求。
二氧化钌是目前所有超级电容器电极材料中性能最好的材料,但其有限的资源和昂贵的价格限制了它更广泛的使用。本文通过在二氧化钌中掺入其它材料和利用微波法改良二氧化钌性能两种方法达到提高二氧化钌的性能和利用率、减少其用量的目的。根据国际研究前沿,选择了二氧化钌、二氧化锰和活性炭材料,制成不同比例的复合电极,并对其性能进行了测试和分析。结果表明当电极材料中二氧化钌、二氧化锰和活性炭的质量比各占20%、20%和60%时,其性能价格比最合适。通过微波加热的方法改进了Sol-gel法制取RuO2·xH2O,制取了具有良好性能的RuO2·xH2O电极材料,并通过实验确定微波加热时间的工艺参数。实验表明,当微波炉中档输出(功率为972W)、微波加热时间为8分钟时,制取的RuO2·xH2O性能最佳。该电极的比电容可达806F／g,内阻为0.41Ω,最大功率密度和能量密度分别为1.785kW/kg、29.09Wh/kg。
为了满足超级电容器大电流充放电的实验研究,设计并制作了基于PIC单片机控制的恒流测试系统,通过实际混合型超级电容器单元的充放电实验,进一步验证了测试系统的可操作性和恒流输出的稳定性,可用于超级电容器的大电流循环充放电测试。
本论文的研究工作得到国家自然科学基金资助(No.50577075)。
Supercapacitor has been developed as a new type of energy-storage component following the development of material science. It has the ability both of fast charging-discharging as traditional capacitor, and of high energy-storage density as battery. It has got many applications, such as in electric vehicles, pulse power system, electromagnetism arms, UPS and forklift, and becomes a hotspot in energy technology.
Hybrid supercapacitor has appeared in USA in recent years. Based on this new kind of supercapacitor, the relevant research for its modeling, preparation and testing are accomplished in deep. The first, a model of the composite electrodes with RuO2·xH2O/active carbon is set up based on the Conway model and electrode physical construction, the discharge characteristic at constant current is specially analyzed, and the regularity for change of the impedance and capacitance for composite electrodes at different mass ratios is explored. At the same time, the model for the typical pressed electrode is modified and improved, the characteristics of supercapacitor composed by pressed electrodes are analyzed, and the effect factors of inner resistance, capacitance and phase angle are discussed in theory.
The key technology of supercapacitors is the preparation of their electrodes, the physical characteristics of porous electrodes determines the electrochemistry behaviors of the electrodes directly. The electrostatic fields of different apertures and shapes are simulated by finite element method to obtain the electrostatic fields distribution of the porous electrodes. The simulation results show that the electrostatic field and capacitance of porous electrodes will be improved by changing the apertures and shapes of the electrodes.
In order to raise the working voltage of supercapacitor for pulse power system, a hybrid super-capacitor unit, which is composed of the anode of electrolytic capacitor and the cathode of supercapacitor, has been designed and studies. It has the merits of the electrolytic capacitor and supercapacitor, and enhances the working voltage of supercapacitor to improve energy density. The experiment results indicate the working voltage of the hybrid supercapacitor unit can achieve to 100V, energy density is 0.37J/g and power density is 8250W/g. Based on the hybrid supercapacitor unit, the hybrid supercapacitor module that has 100 parallel units is designed, and the simulation results validate that the module can satisfy the demand of fast charging and discharging at large current. When the load of 0.38 mΩ/10 mH inductance is discharged, the discharging current can be achieved to 2kA and the discharging power 200kW. Based on this simulated results, the hybrid super-capacitor module of 0.06F/3mΩ/0.3kJ is designed and studied on the experiments. The test results show that the hybrid super-capacitor module can fulfill the needs of pulse power system.
At present, the performance of RuO2 is the best in the all materials, but the finite resource and dear price limit its more extended usage. In this work, two methods that mixed other material into RuO2·xH2O and prepared RuO2·xH2O by microwave have been used to improve the performance and usage of RuO2. According to the international foreland research, the composite electrodes of RuO2·xH2O, MnO2 and active carbon with different mass ratios were prepared and tested. The results show that the performance of composite electrodes is the best, when the mass ratio of RuO2·xH2O, MnO2 and active carbon is 20%:20%:60%. RuO2-xH2O which exhibits the super performance is prepared by the Sol-gel method improved by microwave and tested their electrochemical performances to make sure the process parameter, such as heating times. The experiment results exhibit that the performance of RuO2·xH2O is the best when the power is the mid-range output (power of 972W) and the heating time is 8min. The specific capacitance of this electrode is 806F/g, the inner impedance is 0.41Ω, and the maximum power density and energy density are 1.785kW/kg and 29.09Wh/kg, respectively.
In order to research the charge and discharge performance of supercapacitors, in this paper, the constant current test system based on PIC microcontroller as the controller is designed. The software and hardware tests make further proving the maneuverability and stability of the system. Through the charging and discharging experiment for the hybrid super-capacitor, the results show that the system can obtain good constant current to satisfy the charging and discharging experiments for super-capacitor at large current.
This work is supported by National Natural Science Foundation of China (No.50577075).
引文
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