醇硫基丙烷磺酸钠对电解高性能锂电铜箔的影响

doi:10.13208/j.electrochem.210450

摘要/Abstract

摘要：

电解铜箔因其工艺简单、经济价值高,已广泛应用于印制线路板和锂离子电池领域。研究表明在电解制箔过程中,加入微量添加剂即可大幅度提高电解铜箔性能。因此, 在基础电解液（312.5 g·L^-1 CuSO₄·5H₂O,100 g·L^-1 H₂SO₄, 50 mg·L^-1 Cl^-）基础上,加入添加剂考察了电解液的电化学行为以及对铜箔表面形貌、结构以及性能的影响。实验选取了醇硫基丙烷磺酸钠（HP）、水解蛋白（HVP）和N,N-二甲基硫代甲酰胺丙烷磺酸钠（DPS）作为组合添加剂, 利用扫描电镜（SEM）、 X射线洐射（XRD）以及电化学分析等方法,重点考察了组合添加中HP对铜箔表面形貌和物理性能的影响。研究结果表明,在组合添加剂体系中HP具有较强的去极化作用,可以加速铜核的生长,且具有增强铜（200）晶面的择优生长取向。HP与DPS、 HVP的协同作用可以进一步减小电解铜箔的晶粒尺寸,降低表面粗糙,提高铜箔力学性能和耐腐蚀性能。所制备的电解铜箔均匀致密,平均晶粒尺寸为29.2 nm、平均粗糙度为 1.12 μm、平均抗拉强度为399.5 MPa且耐蚀性能优越, 是锂离子电池负极集流体的理想材料, 具有较高的商业价值。

关键词: 电解铜箔, 添加剂, 电化学, 抗拉强度, 耐腐蚀

Abstract:

Electrolytic copper foils have been widely used in printed circuit boards and lithium-ion batteries due to their simple production process and high economic value. In the process of electrolysis foil making, additives can greatly improve the performance of electrolytic copper foils. In this work, the copper foils were prepared in a self-designed plate electrodeposition device of which the operating principles were in accordance with those of actual industrial production. A series of the Virgin Make-up Solution (VMS: 312.5 g·L^-1 CuSO₄·5H₂O, 100 g·L^-1 H₂SO₄, 50 mg·L^-1 Cl^-) containing different additives was investigated to study the electrochemical behaviors of the electrolytes and their effects on the surface morphology, structure, and properties of the electrolytic copper foils. The results showed that HP had a strong depolarization effect in the combined additive system, which can accelerate the growth of copper nuclei, and had the optimal growth orientation of the enhanced copper (200) crystal surface. HVP had adsorption effect on the cathode surface and formed a barrier layer on the cathode active site, which inhibits the electrical deposition of copper. DPS had a strong depolarization effect at low concentration, with the high concentration, a polarization effect reduced the grain size. When HP and DPS coexisted, there was a competitive adsorption, showing certain polarization effect. The synergistic effect of HP with DPS and HVP could further reduce the grain size of electrolytic copper foils, reduce the surface roughness, and improve the mechanical properties and corrosion resistance of the coatings. The obtained electrolytic copper foils were uniformly dense, with an average grain size of 29.2 nm, an average roughness of 1.12 μm. and an average tensile strength of 399.5 MPa. The electrolytic copper foils obtained exhibited the superior corrosion resistance, became the ideal materials for lithium-ion battery anode fluid collection, and had high commercial value. Subsequently, the effects of DPS and HVP in the combined additive system on the surface morphology and physical properties of copper foil will be investigated to further explore the action mechanism of the combined additive and improve the electrodeposition model.

Key words: electrolytic copper foil, additives, electrochemical, tensile strength, corrosion resistant

杨森, 王文昌, 张然, 秦水平, 吴敏娴, 光崎尚利, 陈智栋. 醇硫基丙烷磺酸钠对电解高性能锂电铜箔的影响[J]. 电化学（中英文）, 2022, 28(6): 2104501.

Sen Yang, Wen-Chang Wang, Ran Zhang, Shui-Ping Qin, Min-Xian Wu, Naotoshi Mitsuzaki, Zhi-Dong Chen. Effect of Sodium Alcohol Thiyl Propane Sulfonate on Electrolysis of High Performance Copper Foil for Lithium Ion Batteries[J]. Journal of Electrochemistry, 2022, 28(6): 2104501.

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参考文献 29

[1]	Wang C B, Yin L W, Xiang D, Qi Y X. Uniform carbon layer coated Mn₃O₄ nanorod anodes with improved reversible capacity and cyclic stability for lithium ion batteries[J]. ACS Appl. Mater. Interfaces, 2012, 4(3): 1636-1642. doi: 10.1021/am2017909 URL
[2]	Varghese S P, Babu B, Prasannachandran R, Antony R, Shaijumon M M. Enhanced electrochemical properties of Mn₃O₄/graphene nanocomposite as efficient anode material for lithium ion batteries[J]. J. Alloy. Compd., 2019, 780: 588-596. doi: 10.1016/j.jallcom.2018.11.394
[3]	An C S, Zhang B, Tang L B, Xiao B, He Z J, Zheng J C. Binder-free carbon-coated TiO₂@graphene electrode by using copper foam as current collector as a high-performance anode for lithium ion batteries[J]. Ceram. Int., 2019, 45(10): 13144-13149. doi: 10.1016/j.ceramint.2019.03.249 URL
[4]	Zuo T T, Wu X W, Yang C P, Yin Y X, Ye H, Li N W, Guo Y G. Graphitized carbon fibers as multifunctional 3D current collectors for high areal capacity Li anodes[J]. Adv. Mater., 2017, 29(29): 1700389. doi: 10.1002/adma.201700389 URL
[5]	An G H, Cha S N, Ahn H J. Surface functionalization of the terraced surface-based current collector for a supercapacitor with an improved energy storage performance[J]. Appl. Surf. Sci., 2019, 478: 435-440. doi: 10.1016/j.apsusc.2019.01.280 URL
[6]	Shin D Y, Park D H, Ahn H J. Interface modification of an Al current collector for ultrafast lithium-ion batteries[J]. Appl. Surf. Sci., 2019, 475: 519-523. doi: 10.1016/j.apsusc.2019.01.016 URL
[7]	Lu L L, Ge J, Yang J N, Chen S M, Yao H B, Zhou F, Yu S H. Free-standing copper nanowire network current collector for improving lithium anode performance[J]. Nano Lett., 2016, 16(7): 4431-4437. doi: 10.1021/acs.nanolett.6b01581 URL
[8]	Park H, Um J H, Choi H, Yoon W S, Sung Y E, Choe H. Hierarchical micro-lamella-structured 3D porous copper current collector coated with tin for advanced lithium-ion batteries[J]. Appl. Surf. Sci., 2017, 399: 132-138. doi: 10.1016/j.apsusc.2016.12.043 URL
[9]	Cui Y, Fu Y Z. Enhanced cyclability of Li/polysulfide batteries by a polymer-modified carbon paper current collector[J]. ACS Appl. Mater. Interfaces, 2015, 7(36): 20369-20376. doi: 10.1021/acsami.5b06214 URL
[10]	Jin L(金磊), Yang J Q(杨家强), Yang F Z(杨防祖), Zhan D P(詹东平), Tian Z Q(田中群), Zhou S M(周绍民). Research progresses of copper interconnection in chips[J]. J. Electrochem.(电化学), 2020, 26(4): 521-530. doi: 10.13208/j.electrochem.200212
[11]	Yin L(殷列), Wang Z L(王增林). Behavior of copper electrodeposition in copper electroplating solution with different PEG molecular weight[J]. J. Electrochem.(电化学), 2008, 14(4): 431-435.
[12]	Meudre C, Ricq L, Hihn J Y, Moutarlier V, Monnin A, Heintz O. Adsorption of gelatin during electrodeposition of copper and tin-copper alloys from acid sulfate electrolyte[J]. Surf. Coat. Technol., 2014, 252: 93-101. doi: 10.1016/j.surfcoat.2014.04.050 URL
[13]	Dutra A J B, O'Keefe T J. Copper nucleation on titanium for thin film applications[J]. J. Appl. Electrochem., 1999, 29(10): 1217-1227. doi: 10.1023/A:1003537318303 URL
[14]	Lee Y K, O’Keefe T J. Evaluating and monitoring nucleation and growth in copper foil[J]. JOM-J. Miner. Met. Mater. Soc., 2002, 54(4): 37-41.
[15]	Zhong Q(钟琴). Effect of additives MPS, PEG, Cl^- on electrodeposition of copper[D]. Chongqing: Chongqing University, 2010.
[16]	Wang Y(王义). Study on the properties and mechanism of copper microvia filling additive[D]. Jiangxi: Jiangxi University of Science and Technology, 2018.
[17]	Dow W P, Li C C, Lin M W, Su G W, Huang C C. Copper fill of microvia using a thiol-modified Cu seed layer and various levelers[J]. J. Electrochem. Soc., 2009, 156(8): D314-D320. doi: 10.1149/1.3147273 URL
[18]	Tan M, Guymon C, Wheeler D R, Harb J N. The role of SPS, MPSA, and chloride in additive systems for copper electrodeposition[J]. J. Electrochem. Soc., 2007, 154(2): D78-D81. doi: 10.1149/1.2401057 URL
[19]	Zhang Q B, Hua Y X, Wang Y T, Lu H J, Zhang X Y. Effects of ionic liquid additive [BMIM] HSO₄ on copper electro-deposition from acidic sulfate electrolyte[J]. Hydrometallurgy, 2009, 98(3-4): 291-297. doi: 10.1016/j.hydromet.2009.05.017 URL
[20]	Wang X M, Wang K, Xu J, Li J, Lv J E, Zhao M, Wang L M. Quinacridone skeleton as a promising efficient leveler for smooth and conformal copper electrodeposition[J]. Dyes Pigment., 2020, 181: 108594. doi: 10.1016/j.dyepig.2020.108594 URL
[21]	Wang Z Q, Gong Y L, Jing C, Huang H J, Li H R, Zhang S T, Gao F. Synthesis of dibenzotriazole derivatives bearing alkylene linkers as corrosion inhibitors for copper in sodium chloride solution: A new thought for the design of organic inhibitors[J]. Corrosion Sci., 2016, 113: 64-77. doi: 10.1016/j.corsci.2016.10.005 URL
[22]	Li C C, Guo X Y, Shen S, Song P, Xu T, Wen Y, Yang H F. Adsorption and corrosion inhibition of phytic acid calcium on the copper surface in 3wt% NaCl solution[J]. Corrosion Sci., 2014, 83: 147-154. doi: 10.1016/j.corsci.2014.02.001 URL
[23]	Tang M X, Zhang S T, Qiang Y J, Chen S J, Luo L, Gao J Y, Feng L, Qin Z J. 4,6-Dimethyl-2-mercaptopyrimidine as a potential leveler for microvia filling with electroplating copper[J]. RSC Adv., 2017, 7(64): 40342-40353. doi: 10.1039/C7RA06857C URL
[24]	Varvara S, Muresan L, Popescu I C, Maurin G. Comparative study of copper electrodeposition from sulphate acidic electrolytes in the presence of IT-85 and of its components[J]. J. Appl. Electrochem., 2005, 35(1): 69-76. doi: 10.1007/s10800-004-2398-1 URL
[25]	Liu Y, Li S Y, Zhang J J, Liu J A, Han Z W, Ren L Q. Corrosion inhibition of biomimetic super-hydrophobic electrodeposition coatings on copper substrate[J]. Corrosion Sci., 2015, 94: 190-196. doi: 10.1016/j.corsci.2015.02.009 URL
[26]	Hernandez-Viezcas J A, Castillo-Michel H, Andrews J C, Cotte M, Rico C, Peralta-Videa J R, Ge Y, Priester J H, Holden P A, Gardea-Torresdey J L. In situ synchrotron X-ray fluorescence mapping and speciation of CeO₂ and ZnO nanoparticles in soil cultivated soybean (Glycine max)[J]. ACS Nano, 2013, 7(2): 1415-1423. doi: 10.1021/nn305196q pmid: 23320560
[27]	Mishra R, Balasubramaniam R. Effect of nanocrystalline grain size on the electrochemical and corrosion behavior of nickel[J]. Corrosion Sci., 2004, 46(12): 3019-3029. doi: 10.1016/j.corsci.2004.04.007 URL
[28]	Pang N, Chen L. Effect of substrate orientation on critical thickness of Cu thin films[J]. Electron. Mater. Lett., 2011, 7(4): 359-363. doi: 10.1007/s13391-011-0170-3 URL
[29]	Lu L, Chen X, Huang X, Lu K. Revealing the maximum strength in nanotwinned copper[J]. Science., 2009, 323(5914): 607-610. doi: 10.1126/science.1167641 pmid: 19179523

Additive	R_s(Ω·cm²)	R_f(Ω·cm²)	R_ct(Ω·cm²)	CPE		W (Ω^-1·cm^-2·s^-1)
Additive	R_s(Ω·cm²)	R_f(Ω·cm²)	R_ct(Ω·cm²)	Y₀（10^-6 Ω^-1·cm^-2·sⁿ）	n	W (Ω^-1·cm^-2·s^-1)
a	69.17	186.1	76.83	5.269	1.00	0.055
b	72.45	196.4	74.62	4.701	1.00	0.051
c	69.73	190.5	47.90	8.849	0.97	0.132
d	68.21	217.8	78.77	7.562	1.00	0.070
e	68.47	212.7	126.61	8.750	0.80	0.045

HP/(mg·L^-1)	E_corr/V	I_corr/(μA·cm^-2)	β_a /mV	β_c/mV	R_p/(kΩ·cm²)
0	-0.2732	3.55	66.512	51.148	3.464 × 10³
3	-0.2695	3.63	78.197	78.197	4.639 × 10³
5	-0.2235	1.80	108.536	61.214	9.187 × 10³
8	-0.1925	0.96	54.057	51.3	1.181 × 10⁴
10	-0.2919	12.61	230.413	57.134	1.627 × 10³
15	-0.3177	18.65	147.628	122.758	1.562 × 10³

HP/(mg·L^-1)	Cu	0	3	5	8	10	15
111/200	2.18	5.17	3.74	3.33	3.16	2.93	3.96
111/220	5.01	8.80	10.96	9.69	8.45	8.14	6.98