金属有机框架化合物Zn_4O(BDC)_3材料的制备、结构及电容性能
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摘要
采用循环伏安和交流阻抗测试技术,在6 mol·L~(-1)KOH溶液中研究了溶剂热法合成的次级结构单元Zn_4O(BDC)_3的比电容性能及储能机理。结果表明,Zn_4O(BDC)_3晶体呈立方六面体形貌,颗粒均匀,尺寸为0.5～1μm。Zn_4O(BDC)_3作为电极材料,在扫速为5 mV·s~(-1)时,比电容可达217.39 F·g~(-1);当扫速增至200 mV·s~(-1)时,比电容值维持在82.58 F·g~(-1)左右,循环伏安曲线仍保持初始的氧化还原峰形状,表明其储能机理遵从赝电容机理,具有较高倍率的充放电性能。Nyquist图在高频区为直径很小的容抗弧,说明该电极材料内阻小,导电性良好;中低频区域为一段较大的不完整容抗弧,说明活性物种锌离子在充放电过程中传荷电阻大,该电极材料具有良好的电容特性。
Specific capacitance and energy storage mechanism of Zinc-based metal-organic frameworks in 6 mol·L~(-1) KOH aqueous solutions, consisting of the secondary building units Zn_4O(BDC)_3 synthesized in a solvothermal process, were studied by cyclic voltammetry and electrochemical impedance spectroscopy analysis. The results demonstrated that the prepared Zn_4O(BDC)_3 grains with cubic hexahedron structure were 0.5—1 μm in size. The results for the capacitive performance from cyclic voltammetry revealed that Zn_4O(BDC)_3 samples had gravimetric capacitance up to 217.39 F·g~(-1) at a scan rate of 5 mV·s~(-1). The electrode materials retained about 82.58 F·g~(-1) capacitance, and CV curves kept their initial redox shape unchanged even at high scan rate of 200 mV·s~(-1), indicating pseudocapacitor energy storage mechanism and excellent rate capability for Zn_4O(BDC)_3 electrode. From Nyquist plot of Zn_4O(BDC)_3 materials, the smaller semicircle in the high-frequency region revealed the lower internal resistance of electrode materials, and the incomplete larger semicircle in the middle-and low-frequency region represented the higher charge-transfer resistance values during the charge-discharge process of active Zn~(2+) species, both of which implied that Zn_4O(BDC)_3 materials produced a better capacitance property.
Specific capacitance and energy storage mechanism of Zinc-based metal-organic frameworks in 6 mol·L~(-1) KOH aqueous solutions, consisting of the secondary building units Zn_4O(BDC)_3 synthesized in a solvothermal process, were studied by cyclic voltammetry and electrochemical impedance spectroscopy analysis. The results demonstrated that the prepared Zn_4O(BDC)_3 grains with cubic hexahedron structure were 0.5—1 μm in size. The results for the capacitive performance from cyclic voltammetry revealed that Zn_4O(BDC)_3 samples had gravimetric capacitance up to 217.39 F·g~(-1) at a scan rate of 5 mV·s~(-1). The electrode materials retained about 82.58 F·g~(-1) capacitance, and CV curves kept their initial redox shape unchanged even at high scan rate of 200 mV·s~(-1), indicating pseudocapacitor energy storage mechanism and excellent rate capability for Zn_4O(BDC)_3 electrode. From Nyquist plot of Zn_4O(BDC)_3 materials, the smaller semicircle in the high-frequency region revealed the lower internal resistance of electrode materials, and the incomplete larger semicircle in the middle-and low-frequency region represented the higher charge-transfer resistance values during the charge-discharge process of active Zn~(2+) species, both of which implied that Zn_4O(BDC)_3 materials produced a better capacitance property.
引文
1 Li Y S,Liang F Y,Bux H,et al.Journal of Membrane Science,2010,354,48.
2 Wang G D,Li J H,Pan J,et al.Dalton Transactions,2017,46(3),808.
3 Li J H,Han S D,Pan J,et al.CrystEngComm,2017,19,1160.
4 Ma Y J,Han S D,Mu Y,et al.Dalton Transactions,2018,47,1650.
5 Zhang D,Xue Z Z,Pan J,et al.Crystal Growth & Design,2018,18 (3),1882.
6 Qiu L G,Li Z Q,Wu Y,et al.Chemical Communications,2008,31,3642.
7 Zhang Y,Niu Y B,Liu T,et al.Materials Letters,2015,161,712.
8 Ke F S,Wu Y S,Deng H X.Journal of Solid State Chemistry,2015,223,109.
9 Kim A Y,Kim M K,Cho K,et al.ACS Applied Materials & Interfaces,2016,8,19514.
10 Inayat A K,Amin B,Muhammad A N,et al.International Jounal of Hydrogen Energy,2014,39,19609.
11 Li H,Yue F,Yang C,et al.Ceramics International,2016,42,3121.
12 Díaz R,Orcajo M G,Botas J A,et al.Materials Letters,2012,68,126.
13 Yaghi O M,Li G,Li H.Nature,1995,378,703.
14 Rosi N L,Eckert J,Eddaoudi M,et al.Science,2003,300,1127.
15 Choi K M,Jeong H M,Park J H,et al.ACS Nano,2014,8,7451.
16 Zhao Z X,Li Z,Li Y S.CIESC Journal,2011,62(2),507 (in Chinese).赵祯霞,李忠,李跃生.化工学报,2011,62(2),507.
17 Yoo Y,Jeong H K.Chemical Communications,2008,21,2441.
18 Son W J,Kim J,Kim J,et al.Chemical Communications,2008,47,6336.
19 Yoo Y,Lai Z,Jeong H K.Micropor Mesoporous and Materials,2009,123,100.
20 Biemmi E,Christian S,Stock N,et al.Microporous and Mesoporous Materials,2009,117(1/2),111.
21 Zhang L,Hu Y H.Applied Surface Science,2011,257(8),3392.
22 Wu Z,Zhang X B.Acta Physico-Chimica Sinica,2017,33(2),305 (in Chinese).吴中,张新波.物理化学学报,2017,33(2),305.
23 Dai X J,Wang K,Zhou X M,et al.Scientia Sinica Physica,Mechanica & Astronomica,2014,41(9),1046 (in Chinese).戴晓军,王凯,周小沫,等.中国科学:物理学力学天文学,2011,41(9),1046.
24 Ning G,Li T,Xu C,et al.Carbon,2013,5,241.
25 Jia Z,Dai C S,Chen L.Electrochemistry measurement methods,Chemical Industry Press,China,2006 (in Chinese).贾铮,戴长松,陈玲.电化学测量方法,化学工业出版社,2006.
26 Wang Y F,Zuo S L.Acta Physico-Chimica Sinica,2016,33(2),481 (in Chinese).王永芳,左松林.物理化学学报,2016,32(2),481.
2 Wang G D,Li J H,Pan J,et al.Dalton Transactions,2017,46(3),808.
3 Li J H,Han S D,Pan J,et al.CrystEngComm,2017,19,1160.
4 Ma Y J,Han S D,Mu Y,et al.Dalton Transactions,2018,47,1650.
5 Zhang D,Xue Z Z,Pan J,et al.Crystal Growth & Design,2018,18 (3),1882.
6 Qiu L G,Li Z Q,Wu Y,et al.Chemical Communications,2008,31,3642.
7 Zhang Y,Niu Y B,Liu T,et al.Materials Letters,2015,161,712.
8 Ke F S,Wu Y S,Deng H X.Journal of Solid State Chemistry,2015,223,109.
9 Kim A Y,Kim M K,Cho K,et al.ACS Applied Materials & Interfaces,2016,8,19514.
10 Inayat A K,Amin B,Muhammad A N,et al.International Jounal of Hydrogen Energy,2014,39,19609.
11 Li H,Yue F,Yang C,et al.Ceramics International,2016,42,3121.
12 Díaz R,Orcajo M G,Botas J A,et al.Materials Letters,2012,68,126.
13 Yaghi O M,Li G,Li H.Nature,1995,378,703.
14 Rosi N L,Eckert J,Eddaoudi M,et al.Science,2003,300,1127.
15 Choi K M,Jeong H M,Park J H,et al.ACS Nano,2014,8,7451.
16 Zhao Z X,Li Z,Li Y S.CIESC Journal,2011,62(2),507 (in Chinese).赵祯霞,李忠,李跃生.化工学报,2011,62(2),507.
17 Yoo Y,Jeong H K.Chemical Communications,2008,21,2441.
18 Son W J,Kim J,Kim J,et al.Chemical Communications,2008,47,6336.
19 Yoo Y,Lai Z,Jeong H K.Micropor Mesoporous and Materials,2009,123,100.
20 Biemmi E,Christian S,Stock N,et al.Microporous and Mesoporous Materials,2009,117(1/2),111.
21 Zhang L,Hu Y H.Applied Surface Science,2011,257(8),3392.
22 Wu Z,Zhang X B.Acta Physico-Chimica Sinica,2017,33(2),305 (in Chinese).吴中,张新波.物理化学学报,2017,33(2),305.
23 Dai X J,Wang K,Zhou X M,et al.Scientia Sinica Physica,Mechanica & Astronomica,2014,41(9),1046 (in Chinese).戴晓军,王凯,周小沫,等.中国科学:物理学力学天文学,2011,41(9),1046.
24 Ning G,Li T,Xu C,et al.Carbon,2013,5,241.
25 Jia Z,Dai C S,Chen L.Electrochemistry measurement methods,Chemical Industry Press,China,2006 (in Chinese).贾铮,戴长松,陈玲.电化学测量方法,化学工业出版社,2006.
26 Wang Y F,Zuo S L.Acta Physico-Chimica Sinica,2016,33(2),481 (in Chinese).王永芳,左松林.物理化学学报,2016,32(2),481.