【摘要】：超級(jí)電容器作為一類新型能源存儲(chǔ)器件,具有功率密度高、充放電速度快、循環(huán)壽命長等優(yōu)點(diǎn),因而受到廣泛的關(guān)注。二氧化錳(MnO_2)因具有儲(chǔ)量豐富、價(jià)格低廉、理論比電容量高(達(dá)到1370 F g~(-1))以及電位窗口寬等特點(diǎn),是一種重要的超級(jí)電容器電極材料。然而,由于二氧化錳電極材料自身導(dǎo)電性差,從而限制了高電容性能二氧化錳基超級(jí)電容器的發(fā)展。本文以納米結(jié)構(gòu)的二氧化錳和高導(dǎo)電性材料復(fù)合來提高二氧化錳基超級(jí)電容器電化學(xué)性能作為研究內(nèi)容。利用電化學(xué)沉積技術(shù),成功制備了納米結(jié)構(gòu)的二氧化錳電極材料和三維MnO_2/AgNW復(fù)合材料,并利用循環(huán)伏安、恒流充放電、交流阻抗等測試手段對(duì)所制備電極材料的電化學(xué)性能進(jìn)行系統(tǒng)的研究。而且,將MnO_2/AgNW復(fù)合材料組裝成柔性對(duì)稱型超級(jí)電容器器件,并對(duì)其組裝工藝和充放電性能進(jìn)行了優(yōu)化探索。主要研究內(nèi)容和結(jié)果如下:1.利用串聯(lián)電阻計(jì)時(shí)電位法和恒流充放電過程中的二次生長技術(shù),制備了一種具有水鈉礦和斜方錳礦結(jié)構(gòu)的三維牡丹花狀MnO_2/FTO平板電極材料,展現(xiàn)了優(yōu)異的電容性能,比電容量在電流密度為10 A g~(-1)條件下能夠達(dá)到1260 F g~(-1),10000次恒流充放電循環(huán)后其電容保持率達(dá)到304%。不同于傳統(tǒng)的計(jì)時(shí)電流法,利用串聯(lián)電阻計(jì)時(shí)電流法制備的MnO_2電極材料在循環(huán)過程中能夠進(jìn)行二次生長,這種二次生長導(dǎo)致了MnO_2晶體結(jié)構(gòu)變化,從而明顯的提高了其表面/近表面及體內(nèi)贗電容性能。利用交流阻抗、循環(huán)伏安和恒流程放電測試,以及第一性原理計(jì)算研究了其儲(chǔ)能機(jī)理,發(fā)現(xiàn)表面電容和體電容的貢獻(xiàn)與掃描速率的有關(guān),主要是通過對(duì)不同掃描速率下的總電容的劃分和氧化還原峰得以證明。這種特殊結(jié)構(gòu)的MnO_2可用于微型超級(jí)電容器,同時(shí)其二次生長過程所展現(xiàn)的獨(dú)特自修復(fù)特性,特別適合應(yīng)用于免維修和長壽命的微型超級(jí)電容器領(lǐng)域。2.以銀納米線層作為導(dǎo)電集流體,利用電化學(xué)沉積技術(shù)將MnO_2直接生長在AgNW上,制備成三維MnO_2/AgNW復(fù)合電極材料,并對(duì)其電化學(xué)性能進(jìn)行系統(tǒng)的研究。為了避免電沉積過程中的AgNW層的脫落問題,利用快速退火工藝將AgNW層在300 oC條件下進(jìn)行焊接處理,促使相互交叉的AgNW之間形成焊接點(diǎn),這能夠明顯的提高電極材料的導(dǎo)電性和循環(huán)壽命。在恒流充放電過程中,這種三維MnO_2/AgNW復(fù)合電極材料的形貌由花狀結(jié)構(gòu)逐漸轉(zhuǎn)變?yōu)榉涓C狀,從而使比容量逐漸提高,從初始的423.5 F g~(-1)增加到663.4 F g~(-1),7000次恒流充放電后其比電容提高到初始值的156.6%。3.基于上述MnO_2/AgNW復(fù)合材料所展現(xiàn)的優(yōu)異的電化學(xué)性能,將這種電極材料制備成柔性對(duì)稱性濾紙基MnO_2/AgNW超級(jí)電容器器件。為了避免AgNW層在濾紙上的脫落問題,對(duì)AgNW層進(jìn)行加壓處理。當(dāng)掃速為10 mV/s,柔性超級(jí)電容器器件的電極材料的比電容為166.6 F g~(-1)。進(jìn)行10000次恒流充放電測試過程中,其仍能展現(xiàn)了較好的循環(huán)穩(wěn)定性。當(dāng)柔性器件進(jìn)行彎折處理,其比電容量仍能保持101.4 F g~(-1)的比容量。
[Abstract]:As a new type of energy storage device, supercapacitor is widely concerned because of its advantages of high power density, fast charging and discharging speed, long cycle life, and so on. Manganese dioxide (MnO_2) is an important supercapacitor because of its rich reserves, low price, high theoretical ratio (up to 1370 F g~ (-1)) and wide potential window. However, due to the poor self conductivity of the manganese dioxide electrode material, the development of the high capacitive manganese based supercapacitor is limited. This paper uses nanostructured manganese dioxide and high conductivity materials to improve the electrochemical performance of manganese based supercapacitors. The nanostructured manganese dioxide electrode materials and three dimensional MnO_2/AgNW composites were prepared successfully. The electrochemical performance of the prepared electrode materials was systematically studied by means of cyclic voltammetry, constant current charge discharge, and AC impedance, and the MnO_2/ AgNW composite was assembled into a flexible symmetric supercapacitor. The assembly process and charge discharge performance were optimized. The main contents and results were as follows: 1. a three dimensional peony shaped MnO_2/FTO plate electrode material with sodium ore and a trapezoid manganese ore structure was prepared by using the series resistance chronograph and two growth techniques in the constant current charge discharge process. With different capacitance, the specific capacitance can reach 1260 F g~ (-1) under the current density of 10 A g~ (-1). After 10000 constant current charging and discharging cycle, its capacitance retention rate is different from that of the traditional timing current method. The MnO_2 electrode material prepared by the series resistor timing current method can grow two times during the cycle process. The two growth results in the change of the MnO_2 crystal structure, which obviously improves the surface / near surface and the pseudo capacitance in the body. The energy storage mechanism is studied by the AC impedance, cyclic voltammetry and the constant flow discharge test, and the first principle calculation. It is found that the contribution of the surface capacitance and the volume capacitance is related to the scanning rate. The division of the total capacitance and the redox peak at different scanning rates are proved. The special structure of the MnO_2 can be used for micro supercapacitors, while the unique self repair characteristics presented in the secondary growth process are especially suitable for the micro supercapacitor field of the maintenance free and long life micro supercapacitor, which is guided by the silver nanowire layer as the guide. In order to avoid the loss of AgNW layer in the process of electrodeposition, the AgNW layer was welded under the condition of 300 oC to avoid the loss of AgNW layer in the process of electrodeposition, and the phase of the AgNW layer was welded on the condition of 300 oC in the process of electrodeposition. The intersecting AgNW forms the welding point, which can obviously improve the conductivity and the cycle life of the electrode material. In the constant current charge discharge process, the morphology of the three-dimensional MnO_2/AgNW composite electrode is gradually transformed from the flower structure to honeycomb, thus increasing the specific capacity gradually from the initial 423.5 F g~ (-1) to 663.4 F g~ (-1). After 7000 constant current charging and discharging, the 156.6%.3., whose specific capacitance is increased to the initial value, is based on the excellent electrochemical performance presented by the above MnO_2/AgNW composite. The electrode material is prepared into a flexible symmetric filter paper based MnO_2/AgNW supercapacitor device. In order to avoid the problem of falling off the AgNW layer on the filter paper, the AgNW layer is pressurized. When the scavenging speed is 10 mV/s, the specific capacitance of the electrode material of the flexible supercapacitor device is 166.6 F g~ (-1). During the 10000 constant current charge discharge test, it can still show good cyclic stability. When the flexible device is bent, the specific capacity of the flexible device can still maintain the specific capacity of 101.4 F g~ (-1).
【學(xué)位授予單位】：濟(jì)南大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TM53

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