【摘要】：超級電容器因?yàn)榫哂懈吖β拭芏?充放電速度快,循環(huán)使用壽命長,綠色安全等優(yōu)點(diǎn)受到研究學(xué)者的廣泛關(guān)注�；谶^渡族金屬氧化物的贗電容器電極材料因?yàn)榫哂懈叩哪芰棵芏瘸蔀橐环N非常具有應(yīng)用前景的電容器電極材料,但是金屬氧化物因?yàn)閷?dǎo)電性差成為其制約因素。當(dāng)前許多研究通過添加導(dǎo)電增強(qiáng)體可制備出納米結(jié)構(gòu)材料來提高金屬氧化物的導(dǎo)電性,但是采用此種方法同樣因?yàn)榻缑娼Y(jié)合力差以及活性物質(zhì)負(fù)載不均勻而影響其性能。通過在納米多孔金屬表面自生長一層氧化物可有效解決導(dǎo)電性差以及界面結(jié)合力差的缺點(diǎn),本論文在二元NiMn、二元NiCuMn的基礎(chǔ)上通過引入具有高穩(wěn)定性、高理論比電容的鈷氧化物成功制備出具有高電位窗口,高體積比電容的新型NiCoMn三元復(fù)合電極,同時(shí)考慮引入價(jià)格低廉的鐵、銅對不同體系進(jìn)行電化學(xué)綜合性能研究。研究主要內(nèi)容為：(1)根據(jù)相圖制備出不同體系的厚度為25um的合金條帶。EDX及XRD表征表明合金條帶成分均勻?qū)儆趩蜗喙倘荏w,有利于形成孔徑分布均勻的三維納米多孔結(jié)構(gòu)。(2)采用脫合金化法成功制備出孔徑分布均勻的納米多孔合金。XPS表征顯示不同體系中金屬元素均存在不同價(jià)態(tài)或者軌道的金屬陽離子,且分析氧元素也存在三種結(jié)合形式,其中金屬氧化物和氫氧化物的含量高有利于提高電化學(xué)性能。BET分析,其孔徑分布均為1～10nm之間,比表面積以Ni20C10Mn70電極最大為48m2/g有利于負(fù)載更多的活性物質(zhì)。TEM分析其孔徑分布與BET測試一致,對不同衍射斑點(diǎn)分析納米多孔金屬氧化物電極存在兩種不同的相。(3)對不同體系進(jìn)行電化學(xué)性能測試發(fā)現(xiàn),NiFeMn體系因?yàn)镕e和Cu的理論比電容低很難得到高比電容的電極材料,但是其體積比電容高達(dá)921F/cm~3。而對不同成分的NiCoMn體系研究發(fā)現(xiàn),合金體系為Ni20Co10Mn70制備的電極電化學(xué)性能最優(yōu),在有效工作電位窗口為1.5V下,比電容高達(dá)2012F/cm~3,其能量密度高達(dá)114mWh/cm~3,高于當(dāng)前實(shí)際應(yīng)用電容器近5倍以上,兩電極測試結(jié)果與三電極性能相近。
[Abstract]:Because of its high power density, high charge and discharge speed, long cycle life and green safety, supercapacitors have attracted much attention. Due to its high energy density, pseudo-capacitor electrode materials based on transition metal oxides have become a promising electrode material for capacitors, but metal oxides have become the limiting factors because of their poor conductivity. At present, many researches can improve the electrical conductivity of metal oxides by adding conductive reinforcements. However, this method also affects the properties of metal oxides because of poor interfacial adhesion and uneven loading of active substances. By self-growing a layer of oxide on the surface of nano-porous metal, the shortcomings of poor electrical conductivity and poor interfacial adhesion can be effectively solved. In this paper, the introduction of binary NiMn, binary NiCuMn has high stability. A novel NiCoMn ternary composite electrode with high potential window and high volume specific capacitance was successfully prepared by cobalt oxide with high theoretical specific capacitance. At the same time, the electrochemical comprehensive properties of different systems were studied by introducing low-cost iron and copper. The main contents of the study are as follows: (1) the alloy strips with different 25um thickness have been prepared according to the phase diagram. The results of EDX and XRD show that the alloy bands are homogeneous single-phase solid solution. (2) Nano-porous alloy with uniform pore size distribution was successfully prepared by dealloying method. XPS characterization showed that there were different valence of metal elements in different systems. Metal cations in states or orbits, There are also three kinds of binding forms for the analysis of oxygen elements, among which the high content of metal oxides and hydroxides is beneficial to the improvement of electrochemical performance. The pore size distribution in BET analysis is between 1~10nm and hydroxide. The maximum specific surface area of Ni20C10Mn70 electrode for 48m2/g is favorable for loading more active substances. The pore size distribution of TEM is consistent with that of BET. Different diffraction spots were used to analyze the existence of two different phases in nano-porous metal oxide electrodes. (3) the electrochemical properties of different systems were tested. It is difficult to obtain high specific capacitance electrode material in NiFeMn system because the theory of Fe and Cu is lower than that of capacitance, but its volume specific capacitance is as high as 921 F / cm ~ (3). On the other hand, the electrochemical properties of the electrode prepared by Ni20Co10Mn70 were found to be the best in the NiCoMn system with different composition. The specific capacitance of the electrode was up to 2012F / cm ~ (-1) and the energy density of the electrode was up to 114mWh/ cm ~ (3) under the effective working potential window of 1.5 V. The performance of the two electrodes is similar to that of the three electrodes.
【學(xué)位授予單位】：天津工業(yè)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2016
【分類號】：TB383.1;TM53

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