Preparation and electrochemical performance of Co Prussian blue analogue/ multi-walled carbon nanotubes nanocomposite for supercapacitors
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摘要: Co类普鲁士蓝(CoPBA)作为令人瞩目的超级电容器阳极材料拥有高比容量和优异的循环稳定性，但较差的电子导电性限制了其倍率性能。利用ZIF-67作为前驱体合成了Co类普鲁士蓝/多壁碳纳米管(CoPBA/MWCNT)复合材料，并使用XRD、SEM和TEM对材料的结构和形貌进行表征。在三电极体系中，测得CoPBA/MWCNT电极在电流密度为1 A·g−1时电容提高到312 F·g−1。制备的CoPBA/MWCNT电极有利于提高材料电导率和机械稳定性，从而获得更高的电化学性能。将CoPBA/MWCNT正极和活性炭(AC)负极组装为非对称电池，测得5000圈循环后容量保留率为83.1%，循环稳定性优异。Abstract: Co Prussian blue analogue (CoPBA) has attracted much attentions as a promising anode material of supercapacitors due to its high capacity and long cycle life. But CoPBA suffers from poor electrical conductivity, leading to unsatisfied rate performance. A nanocomposite of Co Prussian blue analogue/multi-walled carbon nano-tubes (CoPBA/MWCNT) composite was synthesized using ZIF-67 as a precursor. The structure and morphology of CoPBA/MWCNT were characterized by XRD, SEM and TEM. In a three-electrode system, the specific capacitance of the CoPBA/MWCNT electrode reaches up to 312 F·g−1 at a current density of 1 A·g−1. The fabrication of CoPBA/MWCNT is beneficial for improving electronic conductivity and mechanical stability, resulting in high electrochemical performance. An asymmetric supercapacitor cell is assembled with CoPBA/MWCNT as cathode and activated carbon (AC) as anode. Its capacity retention rate is 83.1% after 5000 cycles, exhibiting excellent cycling stability.
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图 1 Co类普鲁士蓝(CoPBA)/多壁碳纳米管(MWCNT)的合成过程
Figure 1. Synthesis process of Co Prussian blue analogue (CoPBA)/multiwalled carbon nanotube (MWCNT)
2-Mel—2-methylimidazole; CTABr—Cetyl trimethyl ammonium bromide
图 2 直接合成的CoPBA(D-CoPBA) (a)、D-CoPBA/MWCNT (b)、ZIF-67/MWCNT (c) 和CoPBA/MWCNT (d) 的SEM图像；CoPBA/MWCNT复合材料的EDS能谱 (e) 和TEM图像 ((f)~(h))
Figure 2. SEM images of direct synthetic CoPBA (D-CoPBA) (a), D-CoPBA/MWCNT (b), ZIF-67/MWCNT (c) and CoPBA/MWCNT (d); EDS mapping (e) and TEM images ((f)-(h)) of CoPBA/MWCNT composite material
图 3 CoPBA/MWCNT、MWCNT和D-CoPBA复合材料的XRD (a)和FTIR (b) 图谱
Figure 3. XRD patterns (a) and FTIR spectra (b) of CoPBA/MWCNT, MWCNT and D-CoPBA composites
图 4 D-CoPBA、CoPBA/MWCNT和D-CoPBA/MWCNT电极的CV曲线 (a)、EIS曲线 (c)；CoPBA/MWCNT电极扫描速度对比CV曲线 (b) 和赝电容 (d)
Figure 4. CV (a) and EIS (c) curves of D-CoPBA、CoPBA/MWCNT and D-CoPBA/MWCNT electrodes; Scan rates comparison CV curves (b) and pseudocapacitance properties (d) of CoPBA/MWCNT electrodes
ZCPE—Constant phase impedance; Rs—Liquid meet resistance; Zw—Diffusion impedance; Rct—Charge transfer resistance; b1-b4—Slope of lgIp–lgv for 1-4 peaks in Fig.4(a)
图 5 CoPBA/MWCNT电极在2~10 A·g−1下的恒电流充放电曲线 (a)，CoPBA/MWCNT (b)、D-CoPBA (c) 和D-CoPBA/MWCNT (d) 的放电电容与电流密度的点线图
Figure 5. Constant current charge and discharge curves of the CoPBA/MWCNT electrode recorded at 2-10 A·g−1 (a); Plots of discharge capacitance vs. current density diagrams for CoPBA/MWCNT (b), D-CoPBA (c) and D-CoPBA/MWCNT (d)
图 6 活性炭(AC)和CoPBA/MWCNT电极的CV曲线 (a)；CoPBA/MWCNT||AC非对称电池不同电压窗口下的CV (b)和GCD曲线(c)；CoPBA/MWCNT||AC非对称电池在不同扫描速度下的CV曲线 (d)
Figure 6. CV curves of activated carbon (AC) and CoPBA/MWCNT electrodes (a); CV curves (b) and GCD curves (c) of CoPBA/MWCNT||AC hybrid capacitor; CV curves of CoPBA/MWCNT||AC hybrid capacitor recorded at various scan rates (d)
图 7 不同电流密度下的CoPBA/MWCNT||AC的GCD曲线 ((a)、(b))；功率密度P和能量密度E对比的Gagone曲线 (c)；放电容量保留率和库伦效率随循环圈数的点线图 (d)
Figure 7. GCD curves of CoPBA/MWCNT||AC of different current densities ((a), (b)); Gagone plot showing energy density E vs. power density P (c);Plot of discharge capacitance retention and coulombic efficiency vs. cycle number (d)
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