Citation: Qiuyang LUO, Xiaoning TANG, Shu XIA, Junnan LIU, Xingfu YANG, Jie LEI. Application of a densely hydrophobic copper metal layer in-situ prepared with organic solvents for protecting zinc anodes[J]. Chinese Journal of Inorganic Chemistry, ;2024, 40(7): 1243-1253. doi: 10.11862/CJIC.20240110 shu

Application of a densely hydrophobic copper metal layer in-situ prepared with organic solvents for protecting zinc anodes

School of Materials and Metallurgy, Guizhou University, Guiyang 550025, China

Corresponding author: Xiaoning TANG, xntang@gzu.edu.cn
Received Date: 3 April 2024
Revised Date: 30 May 2024

Figures(6)

Herein, a dense and hydrophobic Cu metal protective layer was constructed in-situ on the Zn electrode (Cu@Zn) through a displacement reaction in an organic solvent. Specifically, CuI powder was dissolved in N-methyl-2-pyrrolidone (NMP) and stirred for 12 h to obtain a uniform solution. Subsequently, the bare Zn was immersed in the solution at 80 ℃ for 6 h, and then washed with absolute ethanol three times to achieve the Cu@Zn electrode. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) analyses confirm a dense Cu protective layer on the surface of the Cu@Zn electrode. Additionally, the better hydrophobicity of the Cu@Zn electrode was demonstrated through contact angle measurements with a 2 mol·L^-1 ZnSO₄ electrolyte. The dense and hydrophobic Cu metal protective layer can effectively isolate the direct contact between the Zn electrode and electrolyte, suppressing side reactions such as hydrogen evolution and corrosion at the electrode/electrolyte interface. Furthermore, the Cu layer possesses zincophilicity, reduced interfacial resistance, and a lower nucleation energy barrier, thereby promoting uniform Zn deposition and effectively inhibiting dendritic growth. As a result, Cu@Zn symmetric cells exhibited continuous stable performance for 1 700 and 1 330 h at 1 mA·cm^-2, 1 mAh·cm^-2 and 3 mA·cm^-2, 1 mAh·cm^-2, respectively, which were higher than those of bare Zn symmetric cells (204 and 120 h). Furthermore, the Cu@Zn||MnO₂ full cell delivered a specific capacity of 168.5 mAh·g^-1 at 1 A·g^-1 respectively, maintaining stability for over 2 000 cycles.
- aqueous Zn-ion battery,
- Zn electrode,
- dense and hydrophobicity,
- zincophilicity,
- Cu metal layer
1. [1]
  Li C, Jin S, Archer L A, Nazar L F. Toward practical aqueous zinc-ion batteries for electrochemical energy storage[J]. Joule, 2022,6(8):1733-1738. doi: 10.1016/j.joule.2022.06.002
2. [2]
  Han D L, Cui C J, Zhang K Y, Wang Z X, Gao J C, Guo Y, Zhang Z C, Wu S C, Yin L C, Weng Z, Kang F Y, Yang Q H. A non-flammable hydrous organic electrolyte for sustainable zinc batteries[J]. Nat. Sustain., 2021,5(3)205. doi: 10.1038/s41893-021-00800-9
3. [3]
  Li Q, Chen A, Wang D H, Pe Z X, Zhi C Y. "Soft shorts" hidden in zinc metal anode research[J]. Joule, 2022,6(2):273-279. doi: 10.1016/j.joule.2021.12.009
4. [4]
  Han D L, Wang Z X, Lu H T, Li H, Cui C J, Zhang Z C, Sun R, Geng C N, Liang Q H, Guo X X, Mo Y B, Zhi X, Kang F Y, Weng Z, Yang Q H. A self-regulated interface toward highly reversible aqueous zinc batteries[J]. Adv. Energy Mater., 2022,12(9)2102982. doi: 10.1002/aenm.202102982
5. [5]
  JI H M, XIE C L, ZHANG Q, LI Y X, LI H H, WANG H Y. Anode current collector for aqueous zinc-ion batteries: Issues and design strategies[J]. Acta Chim. Sin., 2023,81(1):29-41.
6. [6]
  HAN D, MA T, SUN T J, ZHANG W J, TAO Z L. Zinc anode protection strategy for aqueous zinc-ion batteries[J]. Chinese J. Inorg. Chem., 2022,38(2):185-197. doi: 10.11862/CJIC.2022.031
7. [7]
  Liu M Y, Yuan W T, Ma G Q, Qiu K Y, Nie X Y, Liu Y C, Shen S G, Zhang N. In-situ integration of a hydrophobic and fast-Zn²⁺-conductive inorganic interphase to stabilize Zn metal anodes[J]. Angew. Chem. Int. Ed., 2023,62(27)e202304444. doi: 10.1002/anie.202304444
8. [8]
  Yan H B, Li S M, Nan Y, Yang S B, Li B. Ultrafast zinc-ion-conductor interface toward high-rate and stable zinc metal batteries[J]. Adv. Energy Mater., 2021,11(8)2100186.
9. [9]
  Xia S, Luo Q Y, Liu J N, Yang X F, Lei J, Shao J J, Tang X N. In situ spontaneous construction of zinc phosphate coating layer toward highly reversible zinc metal anodes[J]. Small, 2024e2310497. doi: 10.1002/smll.202310497
10. [10]
  LI S H, LI M L, CHI X W, YIN X, LUO Z D, YU J H. High-stable aqueous zinc metal anodes enabled by an oriented ZnQ zeolite protective layer with facile ion migration kinetics[J]. Acta Phys.-Chim. Sin., 2024,402309003.
11. [11]
  Li J J, Liu Z X, Han S H, Zhou P, Lu B A, Zhou J D, Zeng Z Y, Chen Z Z, Zhou J. Hetero nucleus growth stabilizing zinc anode for high-biosecurity zinc-ion batteries[J]. Nano-Micro Lett., 2023,15(1)237. doi: 10.1007/s40820-023-01206-2
12. [12]
  Chang N N, Li T Y, Li R, Wang S N, Yin Y B, Zhang H B, Li X F. An aqueous hybrid electrolyte for low-temperature zinc-based energy storage devices[J]. Energy Environ. Sci., 2020,13(10):3527-3535. doi: 10.1039/D0EE01538E
13. [13]
  Liu Y, An Y K, Wu L, Sun J G, Xiong F Y, Tang H, Chen S L, Guo Y, Zhang L, An Q Y, Mai L Q. Interfacial chemistry modulation via amphoteric glycine for a highly reversible zinc anode[J]. ACS Nano, 2022,17(1):552-560.
14. [14]
  Li X, Chen Z J, Ruan P C, Hu X T, Lu B G, Yuan X M, Tian S Y, Zhou J. Inducing preferential growth of the Zn (002) plane by using a multifunctional chelator for achieving highly reversible Zn anodes[J]. Nanoscale, 2024,16(6):2923-2930. doi: 10.1039/D3NR05699F
15. [15]
  Li Y, Peng X Y, Li X, Duan H, Xie S Y, Dong L B, Kang F Y. Functional ultrathin separators proactively stabilizing zinc anodes for zincbased energy storage[J]. Adv. Mater., 2023,35(18)2300019. doi: 10.1002/adma.202300019
16. [16]
  Zheng Z Y, Guo S J, Yan M Y, Luo Y Z, Cao F F. A functional janus Ag nanowires/bacterial cellulose separator for high-performance dendrite-free zinc anode under harsh conditions[J]. Adv. Mater., 2023,35(47)2304667. doi: 10.1002/adma.202304667
17. [17]
  Tian H J, Feng G X, Wang Q, Li Z, Zhang W, Lucero M, Feng Z X, Wang Z, Zhang Y, Zhen C, Gu M, Shan X N, Yang Y. Three-dimensional Zn-based alloys for dendrite-free aqueous Zn battery in dualcation electrolytes[J]. Nat. Commun., 2022,13(1)7922. doi: 10.1038/s41467-022-35618-2
18. [18]
  SONG R, ZHAO M Q, WANG S, LU Y, BAO X B, LUO Q M, GOU L, FAN X Y, LI D L. Three-dimensional porous structure and zincophile gradient enabling dendrite free zinc anode[J]. Acta Chim. Sinica, 2024,82(4):426-434.
19. [19]
  Hieu L T, So S, Kim I T, Hur J. Zn anode with flexible β-PVDF coating for aqueous Zn-ion batteries with long cycle life[J]. Chem. Eng. J., 2021,411128584. doi: 10.1016/j.cej.2021.128584
20. [20]
  Chen P, Yuan X H, Xia Y B, Zhang Y, Fu L J, Liu L L, Yu N F, Huang Q H, Wang B, Hu X W, Wu Y P, van Ree T. An artificial polyacrylonitrile coating layer confining zinc dendrite growth for highly reversible aqueous zinc-based batteries[J]. Adv. Sci., 2021,8(11)2100309. doi: 10.1002/advs.202100309
21. [21]
  Hao J N, Li X L, Zhang S L, Yang F F, Zeng X H, Zhang S, Bo G Y, Wang C S, Guo Z P. Designing dendrite-free zinc anodes for advanced aqueous zinc batteries[J]. Adv. Funct. Mater., 2020,30(30)2001263. doi: 10.1002/adfm.202001263
22. [22]
  Duan J W, Dong J M, Cao R R, Yang H, Fang K K, Liu Y, Shen Z T, Li F M, Liu R, Li H L, Chen C. Regulated Zn plating and stripping by a multifunctional polymer-alloy interphase layer for stable Zn metal anode[J]. Adv. Sci., 2023,10(29)2303343. doi: 10.1002/advs.202303343
23. [23]
  Chen J Y, Qiao X, Han X R, Zhang J H, Wu H B, He Q, Chen Z B, Shi L, Wang Y Z, Xie Y N, Ma Y W, Zhao J. Releasing plating-induced stress for highly reversible aqueous Zn metal anodes[J]. Nano Energy, 2022,103107814. doi: 10.1016/j.nanoen.2022.107814
24. [24]
  Kang L T, Cui M W, Jiang F Y, Gao Y F, Luo H J, Liu J J, Liang W, Zhi C Y. Nanoporous CaCO₃ coatings enabled uniform Zn stripping/plating for long-life zinc rechargeable aqueous batteries[J]. Adv. Funct. Mater., 2018,8(25)1801090.
25. [25]
  Li B, Xue J, Lv X, Zhang R C, Ma K X, Wu X W, Dai L, Wang L, He Z X. A facile coating strategy for high stability aqueous zinc ion batteries: Porous rutile nano-TiO₂ coating on zinc anode[J]. Surf. Coat. Tech., 2021,421127367. doi: 10.1016/j.surfcoat.2021.127367
26. [26]
  Yang Y, Liu C Y, Lv Z H, Yang H, Zhang Y F, Ye M H, Chen L B, Zhao J B, Li C C. Synergistic manipulation of Zn²⁺ ion flux and desolvation effect enabled by anodic growth of a 3D ZnF₂ matrix for long-lifespan and dendrite-free Zn metal anodes[J]. Adv. Mater., 2021,33(11)2007388. doi: 10.1002/adma.202007388
27. [27]
  Chen A S, Zhao C Y, Gao J Z, Guo Z K, Lu X Y, Zhang J C, Liu Z P, Wang M, Liu N N, Fan L S, Zhang Y, Zhang N Q. Multifunctional SEI-like structure coating stabilizing Zn anodes at a large current and capacity[J]. Energy Environ. Sci., 2023,16(1):275-284. doi: 10.1039/D2EE02931F
28. [28]
  Liu C C, Lu Q Q, Omar A, Mikhailova D. A facile chemical method enabling uniform Zn deposition for improved aqueous Zn-ion batteries[J]. Nanomaterials, 2021,11(3)764. doi: 10.3390/nano11030764
29. [29]
  Cai Z, Ou Y T, Wang J D, Xiao R, Fu L, Yuan Z, Zhan R M, Sun Y M. Chemically resistant Cu-Zn/Zn composite anode for long cycling aqueous batteries[J]. Energy Storage Mater., 2020,27:205-211. doi: 10.1016/j.ensm.2020.01.032
30. [30]
  Wang Y Y, Chen Y J, Liu W, Ni X Y, Qing P, Zhao Q W, Wei W F, Ji X B, Ma J M, Chen L B. Uniform and dendrite-free zinc deposition enabled by in situ formed AgZn₃ for the zinc metal anode[J]. J. Mater. Chem. A, 2021,9(13):8452-8461. doi: 10.1039/D0TA12177K
31. [31]
  Han D L, Wu S C, Zhang S W, Deng Y Q, Cui C J, Zhang L A, Long Y, Li H, Tao Y, Weng Z, Yang Q H, Kang F Y. A corrosion-resistant and dendrite-free zinc metal anode in aqueous systems[J]. Small, 2020,16(29)2001736. doi: 10.1002/smll.202001736
32. [32]
  Ren Q Q, Tang X Y, Zhao X C, Wang Y, Li C H, Wang S, Yuan Y F. A zincophilic interface coating for the suppression of dendrite growth in zinc anodes[J]. Nano Energy, 2023,109108306. doi: 10.1016/j.nanoen.2023.108306
33. [33]
  Wang M M, Wang W P, Meng Y H, Xu Y, Sun J F, Yuan Y, Chuai M, Chen N, Zheng X H, Luo R, Xu K, Chen W. Crystal facet correlated Zn growth on Cu for aqueous Zn metal batteries[J]. Energy Storage Mater., 2023,56424. doi: 10.1016/j.ensm.2023.01.026
34. [34]
  Zhu Y P, Cui Y, Alshareef H N. An anode-free Zn-MnO₂ battery[J]. Nano Lett., 2021,21(3):1446-1453. doi: 10.1021/acs.nanolett.0c04519
35. [35]
  Zhang Q, Luan J Y. Fu L, Wu S G, Tang Y G, Ji X B, Wang H Y[J]. Chem. Int. Ed., 2019,58(44):15841-15847. doi: 10.1002/anie.201907830
36. [36]
  Zhang Y, Yang S C, Deng J, Chen N X, Xie S D, Zhou J J, Wang Z H. Rational design of zincophilic Ag/permselective PEDOT: PSS heterogeneous interfaces for high-rate zinc electrodeposition[J]. Small, 2023,19(49)2303665. doi: 10.1002/smll.202303665
37. [37]
  Li C P, Shi X D, Liang S Q, Ma X M, Han M M, Wu X W, Zhou J. Spatially homogeneous copper foam as surface dendrite-free host for zinc metal anode[J]. Chem. Eng. J., 2020,379122248. doi: 10.1016/j.cej.2019.122248
38. [38]
  Xie S Y, Li Y, Li X, Zhou Y J, Dang Z Q, Rong J H, Dong L B. Stable zinc anodes enabled by zincophilic Cu nanowire networks[J]. Nano-Micro. Lett., 2021,14(1)39.
39. [39]
  Li G P, Wang X L, Lv S H, Wang J, Yu W S, Dong X T, Liu D T. In situ constructing a film-coated 3D porous Zn anode by iodine etching strategy toward horizontally arranged dendrite-free Zn deposition[J]. Adv. Funct. Mater., 2022,33(4)2208288.
40. [40]
  Miao Z Y, Du M, Li H Z, Zhang F, Jiang H C, Sang Y H, Li Q F, Liu H, Wang S H. Constructing nano-channeled tin layer on metal zinc for high-performance zinc-ion batteries anode[J]. EcoMat, 2021,3(4).
41. [41]
  Han L S, Guo Y M, Ning F H, Liu X Y, Yi J, Luo Q, Qu B H, Yue J L, Lu Y F, Li Q. Lotus effect inspired hydrophobic strategy for stable Zn metal anodes[J]. Adv. Mater., 2023,46(11)2308086.
42. [42]
  QIN D D, DING J Y, LIANG C, LIU Q, FENG L G, LUO Y, HU G Z, LUO J, LIU X J. Addressing challenges and enhancing performance of manganese-based cathode materials in aqueous zinc-ion batteries[J]. Acta Phys.-Chim. Sin., 2024,402310034. doi: 10.3866/PKU.WHXB202310034
43. [43]
  CHEN X H, RUAN P F, WU X W, LIANG S Q, ZHOU J. Crystal structures, reaction mechanisms, and optimization strategies of MnO 2 cathode for aqueous rechargeable zinc batteries[J]. Acta Phys.-Chim. Sin., 2022,38(11)2111003.
1. [1]
  Xiaoning TANG , Junnan LIU , Xingfu YANG , Jie LEI , Qiuyang LUO , Shu XIA , An XUE . Effect of sodium alginate-sodium carboxymethylcellulose gel layer on the stability of Zn anodes. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1452-1460. doi: 10.11862/CJIC.20240191
2. [2]
  Shanghua Li , Malin Li , Xiwen Chi , Xin Yin , Zhaodi Luo , Jihong Yu . 基于高离子迁移动力学的取向ZnQ分子筛保护层实现高稳定水系锌金属负极的构筑. Acta Physico-Chimica Sinica, 2025, 41(1): 2309003-. doi: 10.3866/PKU.WHXB202309003
3. [3]
  Doudou Qin , Junyang Ding , Chu Liang , Qian Liu , Ligang Feng , Yang Luo , Guangzhi Hu , Jun Luo , Xijun Liu . Addressing Challenges and Enhancing Performance of Manganese-based Cathode Materials in Aqueous Zinc-Ion Batteries. Acta Physico-Chimica Sinica, 2024, 40(10): 2310034-. doi: 10.3866/PKU.WHXB202310034
4. [4]
  Pengyang FAN , Shan FAN , Qinjin DAI , Xiaoying ZHENG , Wei DONG , Mengxue WANG , Xiaoxiao HUANG , Yong ZHANG . Preparation and performance of rich 1T-MoS₂ nanosheets for high-performance aqueous zinc ion battery cathode materials. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 675-682. doi: 10.11862/CJIC.20240339
5. [5]
  Xiaoning TANG , Shu XIA , Jie LEI , Xingfu YANG , Qiuyang LUO , Junnan LIU , An XUE . Fluorine-doped MnO₂ with oxygen vacancy for stabilizing Zn-ion batteries. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1671-1678. doi: 10.11862/CJIC.20240149
6. [6]
  Qinjin DAI , Shan FAN , Pengyang FAN , Xiaoying ZHENG , Wei DONG , Mengxue WANG , Yong ZHANG . Performance of oxygen vacancy-rich V-doped MnO₂ for high-performance aqueous zinc ion battery. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 453-460. doi: 10.11862/CJIC.20240326
7. [7]
  Wenqi Gao , Xiaoyan Fan , Feixiang Wang , Zhuojun Fu , Jing Zhang , Enlai Hu , Peijun Gong . Exploring Nernst Equation Factors and Applications of Solid Zinc-Air Battery. University Chemistry, 2024, 39(5): 98-107. doi: 10.3866/PKU.DXHX202310026
8. [8]
  Ping ZHANG , Chenchen ZHAO , Xiaoyun CUI , Bing XIE , Yihan LIU , Haiyu LIN , Jiale ZHANG , Yu'nan CHEN . Preparation and adsorption-photocatalytic performance of ZnAl@layered double oxides. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1965-1974. doi: 10.11862/CJIC.20240014
9. [9]
  Kun Xu , Xinxin Song , Zhilei Yin , Jian Yang , Qisheng Song . Comprehensive Experimental Design of Preferential Orientation of Zinc Metal by Heat Treatment for Enhanced Electrochemical Performance. University Chemistry, 2024, 39(4): 192-197. doi: 10.3866/PKU.DXHX202309050
10. [10]
  Fengqiao Bi , Jun Wang , Dongmei Yang . Specialized Experimental Design for Chemistry Majors in the Context of “Dual Carbon”: Taking the Assembly and Performance Evaluation of Zinc-Air Fuel Batteries as an Example. University Chemistry, 2024, 39(4): 198-205. doi: 10.3866/PKU.DXHX202311069
11. [11]
  Haihua Yang , Minjie Zhou , Binhong He , Wenyuan Xu , Bing Chen , Enxiang Liang . Synthesis and Electrocatalytic Performance of Iron Phosphide@Carbon Nanotubes as Cathode Material for Zinc-Air Battery: a Comprehensive Undergraduate Chemical Experiment. University Chemistry, 2024, 39(10): 426-432. doi: 10.12461/PKU.DXHX202405100
12. [12]
  Lu XU , Chengyu ZHANG , Wenjuan JI , Haiying YANG , Yunlong FU . Zinc metal-organic framework with high-density free carboxyl oxygen functionalized pore walls for targeted electrochemical sensing of paracetamol. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 907-918. doi: 10.11862/CJIC.20230431
13. [13]
  Hong CAI , Jiewen WU , Jingyun LI , Lixian CHEN , Siqi XIAO , Dan LI . Synthesis of a zinc-cobalt bimetallic adenine metal-organic framework for the recognition of sulfur-containing amino acids. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 114-122. doi: 10.11862/CJIC.20240382
14. [14]
  Xiaowei TANG , Shiquan XIAO , Jingwen SUN , Yu ZHU , Xiaoting CHEN , Haiyan ZHANG . A zinc complex for the detection of anthrax biomarker. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1850-1860. doi: 10.11862/CJIC.20240173
15. [15]
  Zijian Jiang , Yuang Liu , Yijian Zong , Yong Fan , Wanchun Zhu , Yupeng Guo . Preparation of Nano Zinc Oxide by Microemulsion Method and Study on Its Photocatalytic Activity. University Chemistry, 2024, 39(5): 266-273. doi: 10.3866/PKU.DXHX202311101
16. [16]
  Zhongxin YU , Wei SONG , Yang LIU , Yuxue DING , Fanhao MENG , Shuju WANG , Lixin YOU . Fluorescence sensing on chlortetracycline of a Zn-coordination polymer based on mixed ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2415-2421. doi: 10.11862/CJIC.20240304
17. [17]
  Yu Wang , Shoulei Zhang , Tianming Lv , Yan Su , Xianyu Liu , Fuping Tian , Changgong Meng . Introduce a Comprehensive Inorganic Synthesis Experiment: Synthesis of Nano Zinc Oxide via Microemulsion Using Waste Soybean Oil. University Chemistry, 2024, 39(7): 316-321. doi: 10.3866/PKU.DXHX202311035
18. [18]
  Qi Li , Pingan Li , Zetong Liu , Jiahui Zhang , Hao Zhang , Weilai Yu , Xianluo Hu . Fabricating Micro/Nanostructured Separators and Electrode Materials by Coaxial Electrospinning for Lithium-Ion Batteries: From Fundamentals to Applications. Acta Physico-Chimica Sinica, 2024, 40(10): 2311030-. doi: 10.3866/PKU.WHXB202311030
19. [19]
  Qianwen Han , Tenglong Zhu , Qiuqiu Lü , Mahong Yu , Qin Zhong . 氢电极支撑可逆固体氧化物电池性能及电化学不对称性优化. Acta Physico-Chimica Sinica, 2025, 41(1): 2309037-. doi: 10.3866/PKU.WHXB202309037
20. [20]
  Aoyu Huang , Jun Xu , Yu Huang , Gui Chu , Mao Wang , Lili Wang , Yongqi Sun , Zhen Jiang , Xiaobo Zhu . Tailoring Electrode-Electrolyte Interfaces via a Simple Slurry Additive for Stable High-Voltage Lithium-Ion Batteries. Acta Physico-Chimica Sinica, 2025, 41(4): 100037-. doi: 10.3866/PKU.WHXB202408007

Get Citation

PDF

XML

Metrics

PDF Downloads(8)
Abstract views(1139)
HTML views(187)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142