N, P co-doped porous carbon /MnO2 composites for zinc-ion hybrid capacitors
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摘要: 使用化石燃料导致的环境问题日益严重，清洁能源装置与可再生能源的发展已经成为必然趋势。本文以咖啡渣为碳源，通过简单的一步活化法制备出咖啡渣炭/MnO2复合材料，并探讨了其在锌离子混合电容器(ZHSC)领域的应用。BET测试表明：咖啡渣炭/MnO2复合材料的比表面积为550.25 m2/g，总孔体积为0.6284 cm3/g。电化学测试结果表明，电极材料在电流密度为0.5 A/g时其比电容为401.5 F/g，在20 A/g的大电流密度下比电容达到264 F/g，具有良好的倍率性能。组装的ZHSC在0.5 A/g的电流密度下达到74.2 mA·h/g，能量密度为39.1 W·h/kg，功率密度为4264 W/kg；在10 A/g电流密度下，5000次充放电循环测试后其电容保持率为98%，库伦效率为98.7%，表明其有良好的循环稳定性和可逆性。因此，咖啡渣炭/MnO2复合材料为生物质炭与MnO2复合材料的探索提供了新思路。Abstract: Environmental problems caused by the use of fossil fuels have become increasingly serious, and the development of clean energy devices and renewable energy has become an inevitable trend. In this paper, coffee grounds carbon/MnO2 composite was prepared by a simple one-step activation method, and its application in zinc-ion hybrid capacitors (ZHSC) field was discussed. BET test showed that the specific surface area of coffee grounds carbon /MnO2 composite was 550.25 m2/g, and the total pore volume was 0.6284 cm3/g. Electrochemical tests showed that electrode displayed excellent specific capacitance of 401.5 F/g at a current density of 0.5 A/g and 264 F/g at a current density of 20 A/g, which revealed good rate capability. Meanwhile, ZHSC reaches 74.2 mA·h/g, energy density is 39.1 W·h/kg and power density is 4264 W/kg at 0.5A/g current density. Furthermore, the capacitance retention rate is 98% and the Coulomb efficiency is 98.7% after 5000 charge-discharge cycles, at the current density of 10 A/g, which indicating it has good cyclic stability and reversibility. Therefore, coffee grounds carbon/MnO2 composites provide a new idea for the exploration of biomass carbon and MnO2 composites.
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图 1 不同炭材料的SEM图片(a) NP/MnO2, (b) K-WCG, (c) KNP/MnO2-1.38, (d) KNP/MnO2-2.38
Figure 1. SEM images of NP/MnO2 (a), K-WCG (b), KNP/MnO2-1.38 (c) and KNP/MnO2-2.38(d)
NP/MnO2 is a coffee grounds carbon/MnO2 composite with only hexaldehyde-phenoxy-cyclotriphosphonitrile (HAPCP) and KMnO4 activation. K-WCG is a pure KOH activated carbon material. KNP/MnO2-2.38 is a composite material activated by 2.38 g KMnO4 and 2 g KOH. KNP/MnO2-2.38 is a composite material activated by 2.38 g KMnO4 and 2 g KOH.
图 2 KNP/MnO2-1.38-2的元素映射图(a) N, (b) P, (c) Mn
Figure 2. KNP/MnO2-1.38-2 of elemental mappings of N(a), P(b) and Mn(c)
图 3 不同炭材料的N2吸附/脱附等温线(a)和BJH介孔孔径分布图(插图为HK微孔孔径分布图) (b)
Figure 3. N2 adsorption/desorption isotherms of different carbon materials (a) and BJH mesoporous pore size distribution maps (illustrated as HK pore size distribution maps) (b)
图 4 不同炭材料的(a)XRD曲线和(b)拉曼光谱
Figure 4. (a) XRD and (b) Raman spectra of different carbon materials
图 5 (a)不同炭材料的XPS谱图; KNP/MnO2-1.38的XPS高分辨率谱图, (b) N 1s拟合谱图, (c) P 2p拟合谱图, (d) Mn 2p拟合谱图
Figure 5. XPS survey spectra of carbon materials (a) and N 1s (b), P 2p (c) and Mn 2p (d) spectra of KNP/MnO2-1.38
图 6 不同炭材料在三电极体系中的电化学性能：(a) 20 mV/s时的CV曲线, (b)1 A/g时的GCD曲线, (c)倍率性能图, (d) Nyquist图, (e) KNP/MnO2-1.38在不同扫速下的CV图, (f) KNP/MnO2-1.38在不同电流密度下的GCD图
Figure 6. CV of carbon materials at a scan rate of 20 mV/s (a), GCD of arbon materials at a current density of 1 A/g (b), specific capacitance of carbon materials at different current densities (c), Nyquist plots of carbon materials (d), CV of KNP/MnO2-1.38 at different scan rates (e) and GCD of KNP/MnO2-1.38 at different current densities (f)
图 7 KNP/MnO2-1.38//Zn的(a)不同电流密度下CV曲线; (b)不同电流密度下GCD曲线; (c) Ragone图; (d) 10 A/g电流密度下循环5000次的电容保持率
Figure 7. KNP/MnO2-1.38 //Zn of (a) CV curves at different current densities; (b) GCD curves at different current densities; (c) the Ragone plot; (d) cycling stability at current density of 10 A/g
表 1 表１ 咖啡渣炭/MnO2复合材料的孔结构参数
Table 1. Pore structure parameters of coffee grounds based porous carbon materials
Sample SBET/(m2·g−1) VTotal/(cm3·g−1) Vmeso/(cm3·g−1) Vmico/(cm3·g−1) NP/MnO2 133.45 0.1402 0.0970 0.0512 KNP/MnO2-1.38 550.35 0.6284 0.2256 0.4028 KNP/MnO2-2.38 526.78 0.4214 0.1710 0.2504 K-WCG 851.87 0.3752 0.0712 0.3040 Notes：SBET is surface area; VTotal is total pore volume; Vmeso is mesopore volume obtained by subtracting Vmicro from Vt; Vmico is micropore volume determined by using the t-plot methods. 
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表 2 不同复合材料的元素含量表
Table 2. Element content table of different composite materials
Sample N/at% O/at% P/at% Mn/at% NP/MnO2 1.46 11.72 1.09 0.6 KNP/MnO2-1.38 4.67 15.05 1.28 1.77 KNP/MnO2-2.38 3.75 16.39 1.25 1.65 K-WCG 1.54 12.58 0.23 －
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