Electrochemical Behavior of Copper Electrodeposition in BMIMPF6 Ionic Liquid

doi:10.7503/cjcu20170816

Abstract

Abstract:

The ionic liquid(IL) 1-butyl-3-methylimidazolium hexafluorophosphate(BMIMPF₆) was synthesized by methylimidazol, chlorobutane and potassium hexafluorophosphate through two-step process. Then the electrochemical behavior of copper electrodeposition in BMIMPF₆ IL was studied. The electrochemical oxidation and reduction process of copper ions were analyzed by cyclic voltammetry(CV) method, and the kinetic parameters and reversibility were also discussed. The nucleation and growth mechanism of copper on the substrate were investigated by chronoamperometry test. The micro-morphology and composition of the layer were characterized by scanning electron microscope(SEM), energy dispersire spectrometer(EDS) and X-ray diffractoneter(XRD). The results show that the redox of copper in the system is an irreversible process. The first stage of reduction is a reversible process and the third step in the second stage is an irreversible process, and the diffusion coefficient of this step is 3.743×10^-6 cm²/s. The electrocrystallization mechanism of copper in this system is three dimensional instantaneous nucleation growth controlled by diffusion. The copper layer is deposited in the form of graniphyric after nucleation.

Key words: Ionic liquid, Copper, Electrodeposition, Cyclic voltammetry, Nucleation mechanism

CLC Number:

O646

TrendMD:

SUN Jie, MING Tingyun, QIAN Huixuan, ZHANG Manke, TAN Yong. Electrochemical Behavior of Copper Electrodeposition in BMIMPF₆ Ionic Liquid[J]. Chem. J. Chinese Universities, 2018, 39(7): 1497.

Figures/Tables 10

Fig.1 CV curves at different sweep rates in BMIMPF6-CuCl2·2H2O ionic liquids

Table 1 Data of reduction peak of CV curves under different sweep rates

ν/(mV·s^-1)	$E a pc$ /V	$E a p / 2$ /V	i_a/(mA·cm^-2)	$E pc b 3$ /V	$E p / 2 b 3$ /V	i_b3/(mA·cm^-2)	$α b 3 *$
50	0.587	0.709	-2.517	-1.451	-0.830	-5.906	0.088
100	0.573	0.681	-3.503	-1.488	-0.701	-8.108	0.069
150	0.572	0.694	-3.649	-1.612	-0.530	-10.700	0.050
200	0.609	0.729	-3.734	-1.664	-0.530	-12.710	0.048
250	0.615	0.723	-3.835	-1.689	-0.613	-14.160	0.051
300	0.622	0.735	-3.955	-1.720	-0.624	-15.130	0.050
350	0.583	0.716	-5.580	-1.739	-0.746	-16.380	0.055
Average	0.594	—	—	-1.623	—	—	0.059

Table 1 Data of reduction peak of CV curves under different sweep rates

ν/(mV·s^-1)	$E a pc$ /V	$E a p / 2$ /V	i_a/(mA·cm^-2)	$E pc b 3$ /V	$E p / 2 b 3$ /V	i_b3/(mA·cm^-2)	$α b 3 *$
50	0.587	0.709	-2.517	-1.451	-0.830	-5.906	0.088
100	0.573	0.681	-3.503	-1.488	-0.701	-8.108	0.069
150	0.572	0.694	-3.649	-1.612	-0.530	-10.700	0.050
200	0.609	0.729	-3.734	-1.664	-0.530	-12.710	0.048
250	0.615	0.723	-3.835	-1.689	-0.613	-14.160	0.051
300	0.622	0.735	-3.955	-1.720	-0.624	-15.130	0.050
350	0.583	0.716	-5.580	-1.739	-0.746	-16.380	0.055
Average	0.594	—	—	-1.623	—	—	0.059

Table 2 Data of oxidation peak of CV curves under different sweep rates

ν/(mV·s^-1)	$E pa 1$ /V	i₁/(mA·cm^-2)	$E 2 pa$ /V	i₂/(mA·cm^-2)	$E 3 pa$ /V	i₃/(μA·cm^-2)
50	-0.212	10.08	0.548	7.66	1.011	6.42
100	-0.207	10.67	0.637	9.04	1.014	8.77
150	-0.258	9.51	0.636	8.99	1.129	9.47
200	-0.283	8.29	0.641	9.20	1.154	8.13
250	-0.295	8.52	0.628	9.20	—	—
300	-0.302	7.55	0.628	9.58	—	—
350	-0.315	6.39	0.615	9.29	—	—
Average	-0.267	-	0.609	—	1.077	—

Table 2 Data of oxidation peak of CV curves under different sweep rates

ν/(mV·s^-1)	$E pa 1$ /V	i₁/(mA·cm^-2)	$E 2 pa$ /V	i₂/(mA·cm^-2)	$E 3 pa$ /V	i₃/(μA·cm^-2)
50	-0.212	10.08	0.548	7.66	1.011	6.42
100	-0.207	10.67	0.637	9.04	1.014	8.77
150	-0.258	9.51	0.636	8.99	1.129	9.47
200	-0.283	8.29	0.641	9.20	1.154	8.13
250	-0.295	8.52	0.628	9.20	—	—
300	-0.302	7.55	0.628	9.58	—	—
350	-0.315	6.39	0.615	9.29	—	—
Average	-0.267	-	0.609	—	1.077	—

Fig.2 Relationship between E and lgν

Fig.3 Relationgship between I and ν1/2

Fig.4 i-t Curves of Cu2+ at different potentials

Fig.5 (i/im)2-t/tm curves

Fig.6 Micro-morphologies of electrodeposition layer during growth process^ Electrodeposition time/s: (A) 30; (B) 60; (C) 300.

Fig.7 SEM image(A) and EDS spectrum(B) of electrodeposition layer for 300 s

Fig.8 XRD pattern of deposition layer formed after electrodeposition for 1 h

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Electrochemical Behavior of Copper Electrodeposition in BMIMPF₆ Ionic Liquid

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