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超级电容器电极材料氧化镍的改性及电解液的研究

Modification of Nickel Oxide Electrode Material and Electrolyte Investigation on Supercapacitor

【作者】 刘良

【导师】 陈野;

【作者基本信息】 哈尔滨工程大学 , 应用化学, 2008, 硕士

【摘要】 超级电容器是介于电池与传统电容器之间的一种新型的储能装置,由于其具有比功率高,循环性能好,可快速充电等优点,日益受到人们的重视。对于超级离子电容器的研究,主要集中在电极材料方面。本文选定氧化镍作为超级电容器的电极材料,研究了氧化镍的制备及其影响因素,以及其与活性碳的混合超级电容器的组装。本文研究了不同电解质溶液对NiO电极性能的影响。在KOH水溶液中能形成赝电容,最终确定KOH水溶液为最优电解液,并对KOH进行了添加剂的研究,得出在电解液KOH溶液中添加LiOH能够提高电容器的比容量,并且在4.5mol·L’KOH+0.5molLiOH·L’的混合电解液中比容量在5mA·cm-2下达369.75 F·g-1,且循环性能好。用沉淀法制备NiO。结果表明,以碳酸铵作为沉淀剂并流沉淀法制备的NiO,10mA·cm-2时,其放电比容量可达352.7 F·g-1,溶液电阻RL为0.5Ω,电极电阻RE为0.6Ω,经12mA·cm-2恒电流循环100次,表现出良好的循环稳定性能。以Ni(NO32·6H2O和(NH42CO3为起始原料,聚乙二醇400为表面活性剂,采用醇-水法合成团聚少的NiO。这样制备的氧化镍在10 mA·cm-2恒流充放电条件下,放电比容量可达395.5 F·g-1。应用醇-水法制备掺杂Al3+、Zn2+、CO2+的氧化镍复合材料。结果表明:在最佳工艺参数为Ni2+:Al3+:Zn2+:Co2+=0.88:0.05:0.02:0.05时制备的电极比容量为716.45 F·g-1,比容量远高于未掺杂时。由XRD和SEM图看出,掺杂的氧化镍电极材料的晶粒细化,形状不规则,且分散均匀。用活性炭电极和氧化镍电极组装超级电容器。电化学性能测试结果:其充放电电压可达1.45V,具有优良的大电流充放电性能较低的自放电率,负/正极质量比为2:1时得到最大比容量,达82.68 F·g-1,不同电流密度下的等效内阻数值基本相同,为0.45Ω,在恒流充放电5000次时容量仍然维持在初始容量的80%以上,由此可见复合电容器的性能良好。

【Abstract】 The supercapacitor is a new type of electrochemical energy storage devices between the typical rechargeable batteries and the typical dielectric capacitors and have advantages of high power densities and have very long cycle life, and have drawn more and more attention in recent years. The dissertation focus on the preparation, structure properties of electrode material and study on electrochemical hybrid supercapacitors composed with activated carbon and nickel oxide electrodes.The effects of different electrolytes on capacitor properties of NiO were investigated. Nickel oxide film electrodes be have pseudocapacitance in aqu eous KOH.The results showed that the KOH electrolyte ware feasible. LiO H additives were studied. On the condition of 5mA·cm-2 constant current, t he specific capacitance is 369.75F·g-1 in mixed electrolytes containing 4.5m ol KOH and 0.5mol LiOH every one litre. The cycle capability of NiO in mixed electrolytes is excellent.NiO was prepared by depositing methods. Taking (NH)2CO3 as precipit ator, the NiO was prepared by Parallel Flow Precipitation Process, The val ues of RL and RE by test of AC impedance are 0.5Ωand 0.6Ωrespectivel y.The specific discharge capacitance is 352.7 F·g-1 at 10mA·cm-2 current de nsity. Long cycle life was also demonstrated after charge/discharge 100 cyc les at 12 mA·cm-2.Taking Ni(NO32 and (NH)2CO3 as main raw materials, taking PEG-400 as surfactant, NiO was prepared by alcohol-water method. Compared with water solution method, the distribution of the NiO powder obtained by alcohol-water method is narrow. The addition of surfactant PE G-400 can reduce powder agglomeration. The specific capacitance of the re suiting NiO reached 395.5 F·g-1 at 10mA·cm-2. NiO was prepared that multi-ion instituted the Ni2+ by alcohol-water m ethod. By using orthogonal test method optimum technological conditions ar e Al3+:Zn2+:Co2+=0.88:0.05:0.02:0.05.The specific capacitance of the resultin g NiO reached 716.45 F·g-1 at 10mA·cm-2.XRD and SEM show that particl e size of the NiO is smaller and its distribution is narrow.Electrochemical hybrid supercapacitor composed with activated carbon and nickel oxide electrodes were studied in 5mol·L-1 KOH aqueous solutions.The result: The maximum charge-discharge voltage was about 1.45V and excellent characteristic of high power discharge was attained in this way. This type of hybrid supercapacitor exhibited much lower self-discharge rate than capacitor composed of two identical activated carbon electrodes. The specific capacitance of electrochemical hybrid supercapacitor reached 82.68F·g-1 at 10mA·cm-2 on quality proportion of anodexathode is 4:1, its inner resistance is 0.45Ωat different current density. Long cycle life was also demonstrated after charge/discharge 5000 cycles, and its specific capacitance is above 80% initiatory capacitance. The high performance obtained indicates that the AC/NiO hybrid supercapacitorsare promising.

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