錳基三元化合物作無粘結(jié)劑電極的制備與性能研究
發(fā)布時間：2018-10-09 14:11
【摘要】：電化學(xué)電容器作為一種具有高能量密度、可大電流充放電、對環(huán)境友好的儲能元件而備受關(guān)注。電極材料作為儲能元件的核心組成部分，決定了電化學(xué)電容器的性能。近年來，，三元及多元化合物電極材料的開發(fā)引起人們的廣泛關(guān)注，它綜合了多種過渡金屬的優(yōu)良性能，具有更高的比電容和良好的循環(huán)壽命。另一方面，電極的制備工藝從粘結(jié)劑型向無粘結(jié)劑型電極轉(zhuǎn)變，讓電化學(xué)活性材料直接生長于集流體表面，具有簡化工藝、提高活性材料利用率的優(yōu)點。 本論文采用水熱法，以Mn(CH3COO)2·4H2O、Co(CH3COO)2·4H2O、脲作為原料，在泡沫鎳表面一步沉積得到CoMn2O4、MnCo2O4兩種電極材料，設(shè)計了一種無粘結(jié)劑型電極。利用掃描電鏡（SEM）、X射線衍射儀（XRD）、X射線能譜儀（EDS），循環(huán)伏安法（CV）、恒電流充放電（CP）和電化學(xué)阻抗譜（EIS）對電極材料進(jìn)行結(jié)構(gòu)表征和電化學(xué)性能測試。 （1）CoMn2O4作為尖晶石結(jié)構(gòu)的過渡金屬復(fù)合氧化物，作為電極材料有較大的潛在價值。通過調(diào)控有機(jī)添加劑脲的比例、水熱反應(yīng)時間、水熱溫度等因素，得到最佳參數(shù)：n(Mn):n(Co):n(脲)比例為2:1:1，n(Mn)=20mmol，水熱60°C反應(yīng)20h。在泡沫鎳表面沉積了無定形CoMn2O4納米片，尺寸在200nm左右。比較無粘結(jié)劑電極與粉末涂敷電極的電化學(xué)性能，無粘結(jié)劑比電容可達(dá)625.00F·g-1，循環(huán)500次后，比電容保持率為65.50％。相同條件下，涂敷電極比電容為252.00F·g-1，比電容保持率為60.54％。 （2）MnCo2O4作為尖晶石（AB2O4）的一種，與CoMn2O4相比，A、B位置發(fā)生替換、兩者價態(tài)改變。以鈷鹽Co(CH3COO)2·4H2O為主體，當(dāng)n(Co):n(Mn):n(脲)比例為2:1:1，n(Co)=10mmol，水熱60°C反應(yīng)20h后泡沫鎳表面生長了300nm左右似花瓣狀的MnCo2O4納米片。通過電化學(xué)測試，無粘結(jié)劑電極與涂敷電極比電容分別為740.00F·g-1、251.66F·g-1。循環(huán)500次后，無粘結(jié)劑電極比電容保持率為71.00％，而涂敷電極僅為37.26％。 本論文通過簡單的水熱反應(yīng)制備了具有良好電化學(xué)性能的CoMn2O4和MnCo2O4無粘結(jié)劑型電極。通過性能測試比較，無粘結(jié)劑型電極在活性材料的利用率以及電化學(xué)性能方面要遠(yuǎn)高于涂敷電極，在簡化電極制備工藝的同時提高了活性材料的電化學(xué)性能。
[Abstract]:Electrochemical capacitors as a kind of high energy density, high current charge and discharge, environmentally friendly energy storage components have attracted much attention. As a core component of energy storage elements, electrode materials determine the performance of electrochemical capacitors. In recent years, the development of ternary and multicomponent compound electrode materials has attracted wide attention. It integrates the excellent properties of many transition metals, and has higher specific capacitance and better cycle life. On the other hand, the preparation process of electrode is changed from binder form to unbonded form electrode, which makes electrochemical active materials grow directly on the surface of collecting fluid, which has the advantages of simplifying the process and improving the utilization ratio of active materials. In this paper, Mn (CH3COO) 24 H 2O Co (CH3COO) 24 H 2O and urea were used as raw materials to prepare two kinds of CoMn2O4,MnCo2O4 electrode materials by one step deposition on the surface of nickel foam, and an unbonded electrode was designed. The structure and electrochemical properties of the electrode materials were characterized by (EDS), cyclic voltammetry, (CV), constant current charge-discharge (CP) and electrochemical impedance spectroscopy (EIS) by scanning electron microscope (SEM) X-ray diffractometer (XRD) and X-ray energy spectrometer (EDS),). The results are as follows: (1) CoMn2O4, as a spinel structure transition metal composite oxide, has great potential value as electrode material. By adjusting the proportion of organic additive urea, hydrothermal reaction time and hydrothermal temperature, the optimum reaction parameters were obtained: the ratio of 2: 1 (Mn): n (Co): n (urea) was 2: 1: 1: n (Mn) = 20 mmol, and the hydrothermal reaction time was 60 擄C for 20 h. Amorphous CoMn2O4 nanocrystals were deposited on the surface of nickel foam, and the size was about 200nm. The electrochemical performance of the unbonded electrode was compared with that of the powder coated electrode. The specific capacitance of the binder was 625.00 F g-1, and the specific capacitance retention rate was 65.50 after 500 cycles. Under the same conditions, the specific capacitance of the coated electrode is 252.00F g-1 and the retention rate of the specific capacitance is 60.54. (2) as a kind of spinel (AB2O4), MnCo2O4 is replaced by CoMn2O4, and their valence states change. With cobalt salt Co (CH3COO) 2 4H2O as the main body, when the ratio of n (Co): n (Mn): n (urea) is 2: 1: 1n (Co) 10 mmol / mol, 300nm like petal-like MnCo2O4 nanocrystals were grown on the surface of nickel foam after hydrothermal reaction for 20 h at 60 擄C. The specific capacitance of unbonded electrode and coated electrode was 740.00F g-1251.66F g-1, respectively. After 500 cycles, the specific capacitance retention rate of the binder electrode is 71.00, while the coated electrode is 37.26. In this paper, CoMn2O4 and MnCo2O4 unbonded electrodes with good electrochemical properties were prepared by simple hydrothermal reaction. The results show that the utilization ratio and electrochemical performance of the unbonded electrode are much higher than that of the coated electrode. The electrochemical performance of the active material is improved while the preparation process of the electrode is simplified.
【學(xué)位授予單位】：浙江理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：TM53;TQ137.12
本文編號：2259634
[Abstract]:Electrochemical capacitors as a kind of high energy density, high current charge and discharge, environmentally friendly energy storage components have attracted much attention. As a core component of energy storage elements, electrode materials determine the performance of electrochemical capacitors. In recent years, the development of ternary and multicomponent compound electrode materials has attracted wide attention. It integrates the excellent properties of many transition metals, and has higher specific capacitance and better cycle life. On the other hand, the preparation process of electrode is changed from binder form to unbonded form electrode, which makes electrochemical active materials grow directly on the surface of collecting fluid, which has the advantages of simplifying the process and improving the utilization ratio of active materials. In this paper, Mn (CH3COO) 24 H 2O Co (CH3COO) 24 H 2O and urea were used as raw materials to prepare two kinds of CoMn2O4,MnCo2O4 electrode materials by one step deposition on the surface of nickel foam, and an unbonded electrode was designed. The structure and electrochemical properties of the electrode materials were characterized by (EDS), cyclic voltammetry, (CV), constant current charge-discharge (CP) and electrochemical impedance spectroscopy (EIS) by scanning electron microscope (SEM) X-ray diffractometer (XRD) and X-ray energy spectrometer (EDS),). The results are as follows: (1) CoMn2O4, as a spinel structure transition metal composite oxide, has great potential value as electrode material. By adjusting the proportion of organic additive urea, hydrothermal reaction time and hydrothermal temperature, the optimum reaction parameters were obtained: the ratio of 2: 1 (Mn): n (Co): n (urea) was 2: 1: 1: n (Mn) = 20 mmol, and the hydrothermal reaction time was 60 擄C for 20 h. Amorphous CoMn2O4 nanocrystals were deposited on the surface of nickel foam, and the size was about 200nm. The electrochemical performance of the unbonded electrode was compared with that of the powder coated electrode. The specific capacitance of the binder was 625.00 F g-1, and the specific capacitance retention rate was 65.50 after 500 cycles. Under the same conditions, the specific capacitance of the coated electrode is 252.00F g-1 and the retention rate of the specific capacitance is 60.54. (2) as a kind of spinel (AB2O4), MnCo2O4 is replaced by CoMn2O4, and their valence states change. With cobalt salt Co (CH3COO) 2 4H2O as the main body, when the ratio of n (Co): n (Mn): n (urea) is 2: 1: 1n (Co) 10 mmol / mol, 300nm like petal-like MnCo2O4 nanocrystals were grown on the surface of nickel foam after hydrothermal reaction for 20 h at 60 擄C. The specific capacitance of unbonded electrode and coated electrode was 740.00F g-1251.66F g-1, respectively. After 500 cycles, the specific capacitance retention rate of the binder electrode is 71.00, while the coated electrode is 37.26. In this paper, CoMn2O4 and MnCo2O4 unbonded electrodes with good electrochemical properties were prepared by simple hydrothermal reaction. The results show that the utilization ratio and electrochemical performance of the unbonded electrode are much higher than that of the coated electrode. The electrochemical performance of the active material is improved while the preparation process of the electrode is simplified.
【學(xué)位授予單位】：浙江理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：TM53;TQ137.12
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