daohang fenxiangbox searchbox qikanlogonew daohangnew searchboxnew navrightzone footerzone paper

Electrochemical Properties of Pb-Lignin Composite Anodes for Zinc Electrowinning AITranslate

1.School of Metallurgical and Energy Engineering,Kunming University of Science and Technology,Kunming 650093,China
2.School of Materials and Chemical Engineering,Tongren University,Tongren 554300,China
AITranslate
Publisher: Youke Publishing Co., Ltd
Share Citation Information Add to Favorites Download PDF

    Scan to share on WeChat or Moments

Use WeChat scan.
Share with WeChat friends or Moments

Abstract AITranslate

Zinc metal has an active chemistry and is widely used in industries such as galvanised protective film and battery manufacturing. Eighty-five percent of zinc metal is produced by hydrometallurgy. Zinc electrowinning,as a vital part of hydrometallurgy,accounts for 80% of the total energy consumption of the hydrometallurgical process. During the electrowinning of zinc,the anodic oxygen evolution reaction has a high charge transfer energy barrier,which results in the anode generating a large overpotential of oxygen evolution potential. This leads to an increase in tank voltage and energy consumption. Concurrently,the anode material must be used in an environment with high acidity,high oxidation,high current density,and the co-existence of halogen ions. This results in corrosion of the anodes,which consequently reduces their service life. The anode sludge also has an impact on the quality of the zinc cathode. Currently,lead-based anodes are predominant in the wet zinc refining industry. However,lead-based anodes still have problems with high oxygen evolution potential and poor corrosion resistance. Lead-based anodes can be modified by doping functional metal elements. For instance,the incorporation of silver,a noble metal with electrocatalytic properties,can diminish the oxygen evolution potential of lead-based anodes. Nevertheless,silver is unable to enhance the mechanical strength of lead-based anodes,and the introduction of the precious metal silver will also considerably elevate the production cost of the anodes. It is therefore of great significance to identify a renewable and low-cost reinforcing phase that can be used as an effective substitute for silver in order to enhance the oxygen precipitation catalytic activity and corrosion resistance of conventional lead-based anodes. In this study,the sodium lignosulfonate,a byproduct of the paper industry,was employed as the primary raw material. The purified lignin was obtained following desulfurisation and purification. Pb-Lignin composite anodes were prepared by incorporating lignin into Pb-based anodes through the use of powder metallurgy technology. The impact of lignin on the electrochemical performance and corrosion resistance of Pb-xLignin composite anodes (x=0,0.2,0.4,0.6,0.8,1.0,%,mass fraction) was investigated. The prepared lignin was micron-sized spherical,with the benzene ring structure preserved intact. Lignin is rich in oxygen-containing active functional groups and is an excellent electrode active material with high electrochemical reactivity and stability. The doped lignin exhibited a varying degree of modification effect on the lead-based anode. The enhancement of the electrochemical performance and corrosion resistance of the lead-based composite anode by lignin exhibited an initial increase and subsequent decrease with increasing lignin doping under simulated zinc electrowinning conditions. This phenomenon could be attributed to the structural composition of the prepared lignin,which comprised lilac-based and p-hydroxyphenyl structural units,rendering it more prone to accelerate the oxygen precipitation electrocatalytic reaction on the anode surface. When the doping amount exceeded 0.8%,π-π interactions and hydrogen bonding between lignin molecules led to severe agglomeration,resulting in an uneven distribution of lignin on the surface of the lead anode and a weakening of the enhancement effect on the lead-based anode. The optimal modification of the lead-based composite anode was achieved when the doping amount of lignin was 0.8%. At this juncture,the Pb-0.8%Lignin composite anode exhibited a 1.25 and 1.23-fold increase in voltammetric charge,a 1.94 and 1.50-fold enhancement in bilayer capacitance (Cdl),and a higher apparent exchange current density than the pure Pb and Pb-Ag-Ca composite anodes. The oxygen evolution potential steady-state potential was 1.528 V at a current density of 500 A·m−2,which was 125 mV lower than that of the pure Pb electrode. Furthermore,the corrosion rate was reduced by 31.6%,which provided excellent oxygen evolution catalytic activity and corrosion resistance.

KeyWords AITranslate

lignin composite anode oxygen evolutionreaction zinc electrowinning

[1]Yang D H,Wang K P,Zhou H W,Zhang X,Zhang B,Lu B Z,Wang F. Microstructure and properties of galvannealed coatings at different galvannealed time [J]. Materials Letters,2023,345:134489.

[2]Yi Z H,Chen G,Hou F,Wang L Q,Liang J. Zinc-ion batteries:strategies for the stabilization of Zn metal anodes for Zn-ion batteries [J]. Advanced Energy Materials,2021,11(1):2170001.

[3](丁丹阳,李天恩,赵荣艳,贾东方,张栋栋. 金精矿综合回收铅锌工艺试验研究 [J]. 黄金,2023,44(11):48.)

D Y Ding,T E Li,R Y Zhao,D F Jia,D D Zhang. Experimental research on the comprehensive recovery process of lead and zinc from gold concentrates [J]. Gold,2023,44(11):48.

[4](许晗宇,黄龙,匡玲瑶,古兴兴. 一种新型生物质聚合物人工SEI膜稳定锌阳极的研究 [J]. 稀有金属,2025,49(5):695.)

H Y Xu,L Huang,L Y Kuang,X X Gu. A novel artificial biomass polymer SEI film for highly stable Zn anode [J]. Chinese Journal of Rare Metals,2025,49(5):695.

[5](裴启飞,郭孟伟,邵伟春,王恩泽,高明远,张启波. 锌电积体系Zn-MnO2同槽电解电化学分析 [J]. 有色金属科学与工程,2024,15(3):322.)

Q F Pei,M W Guo,W C Shao,E Z Wang,M Y Gao,Q B Zhang. Electrochemical analysis of the simultaneous electrolysis of zinc and manganese dioxide in zinc electrowinning system [J]. Nonferrous Metals Science and Engineering,2024,15(3):322.

[6]He S W,Xu R D,Sun L,Fan Y Q,Zhao Z,Liu H,Lv H H. Electrochemical characteristics of Co3O4-doped β-PbO2 composite anodes used in long-period zinc electrowinning [J]. Hydrometallurgy,2020,194:105357.

[7](陶毅,陈步明,黄惠,郭忠诚,何亚鹏. 锌电积用新型阳极的研究进展 [J]. 材料保护,2023,56(6):142.)

Y Tao,B M Chen,H Huang,Z C Guo,Y P He. Research progress of new anodes for zinc electrodeposition [J]. Materials Protection,2023,56(6):142.

[8](赵菁. 锌电积体系中的电极电催化反应过程研究 [D]. 郑州:郑州大学,2021. 9.)

J Zhao. Study of Electrocatalytic Reaction for the Electrode in Zinc Electrowinning System [D]. Zhengzhou:Zhengzhou University,2021. 9.

[9](荆晓生,郭思远,李欣圆,王雪,徐浩,延卫. Ti4O7阳极材料制备改性及其在电化学水处理中的应用研究进展 [J]. 稀有金属,2024,48(8):1163.)

X S Jing,S Y Guo,X Y Li,X Wang,H Xu,W Yan. Research progress in preparation and modification of Ti4O7 anode material and application in electrochemical water treatment [J]. Chinese Journal of Rare Metals,2024,48(8):1163.

[10](罗劲松,顾智辉,林晓坦,邓戈,张德超,胡一平,向成喜,李存兄. 湿法炼锌溶液中离子交换树脂静态吸附Cu2+行为及机理研究 [J]. 铜业工程,2024,(4):87.)

J S Luo,Z H Gu,X T Lin,G Deng,D C Zhang,Y P Hu,C X Xiang,C X Li. Static adsorption behavior and mechanism of Cu2+ by ion exchange resin in zinc hydrometallurgy solution [J]. Copper Engineering,2024,(4):87.

[11]Ye W Q,Xu F Y,Jiang L H,Duan N,Li J H,Zhang F L,Zhang G,Chen L J. A novel functional lead-based anode for efficient lead dissolution inhibition and slime generation reduction in zinc electrowinning [J]. Journal of Cleaner Production,2021,284:124767.

[12](杨四齐,夏先禹,张利华,白希为,姚浩. 亚铁离子对锌电积的影响 [J]. 有色金属工程,2023,13(7):54.)

S Q Yang,X Y Xia,L H Zhang,X W Bai,H Yao. Effect of ferrous ion on zinc electrowinning [J]. Nonferrous Metals Engineering,2023,13(7):54.

[13]Li Z P,Liu H Z. Study on electrochemical properties of lead calcium tin anode for hydrometallurgy [J]. Alexandria Engineering Journal,2023,82:389.

[14]Qiao Q C,Singh S,Lo S L,Li Y,Jin J R,Wang L Z. Electrochemical oxidation of acid orange 7 dye with Ce,Nd,and Co-modified PbO2 electrodes:preparation,characterization,optimization,and mineralization [J]. Journal of the Taiwan Institute of Chemical Engineers,2018,84:110.

[15]Zhang W Q,Li A J,Chen H Y,Lan B Y,Pan K,Zhang T R,Fang M X,Liu S Y,Zhang W. The effect of rare earth metals on the microstructure and electrochemical corrosion behavior of lead calcium grid alloys in sulfuric acid solution [J]. Journal of Power Sources,2012,203:145.

[16]Tao Y,Luo K L,Chang L H,Chen B M,Huang H,He Y P,Guo Z C. The influence of rare earth La on properties of lead-based alloy anode for zinc electrowinning [J]. Journal of Solid State Electrochemistry,2022,26(11):2555.

[17]Wang W J,Yuan T C,Li R D,Wang Z R,Li H H,Li L B,Zheng D. Electrochemical behaviors of powder-processed Pb-Ag anodes [J]. JOM,2019,71(8):2498.

[18]McGinnity J J,Nicol M J. The role of silver in enhancing the electrochemical activity of lead and lead-silver alloy anodes [J]. Hydrometallurgy,2014,144-145:133.

[19]Wang S,Zhou X Y,Ma C Y,Long B,Wang H,Yang J. Polarization behavior of Pb-Co powder-pressed alloy for electrowinning [J]. RSC Advances,2018,8(25):13910.

[20]Smith R A,Lu F C,Muro-Villanueva F,Cusumano J C,Chapple C,Ralph J. Manipulation of lignin monomer composition combined with the introduction of monolignol conjugate biosynthesis leads to synergistic changes in lignin structure [J]. Plant and Cell Physiology,2022,63(6):744.

[21]Matsushita Y,Hirano D,Aoki D,Yagami S,Takagi Y,Fukushima K. A biobased flame-retardant resin based on lignin [J]. Advanced Sustainable Systems,2017,1(10):1700073.

[22]Mikame K,Ohashi Y,Naito Y,Nishimura H,Katahira M,Sugawara S,Koike K,Watanabe T. Natural organic ultraviolet absorbers from lignin [J]. ACS Sustainable Chemistry & Engineering,2021,9(49):16651.

[23]Liu L L,Solin N,Inganäs O. Self-discharge study of lignin/graphite hybrid material electrodes [J]. Electrochimica Acta,2021,371:137836.

[24]Tong W X,Liang X X,Huang F,Chen L H,Wu H,Huang L L,Zhou X X. Preparation of activated carbon from paper black liquor lignin as high-performance electrode material [J]. European Journal of Wood and Wood Products,2024,82(3):861.

[25]Li P H,Wei Y M,Wu C W,Yang C,Jiang B,Wu W J. Lignin-based composites for high-performance supercapacitor electrode materials [J]. RSC Advances,2022,12(30):19485.

[26](薛阳. 木质素改性苯并噁嗪的制备、固化及性质研究 [D]. 武汉:华中农业大学,2011. 20.)

Y Xue. Study on Preparation,Solidification and Properties of Benzoxazine Modified with Lignin [D]. Wuhan:Huazhong Agricultural University,2011. 20.

[27](刘娣,张金,王亚娟,仇丹,邵双喜. 废弃竹笋壳中所提木质素的氧化性研究 [J]. 农产品加工,2019,(22):6.)

D Liu,J Zhang,Y J Wang,D Qiu,S X Shao. Study on the oxidation of lignin from waste bamboo shoots [J]. Farm Products Processing,2019,(22):6.

[28](赵斌元,胡克鳌,范永忠,竺品芳,吴人洁. 木质素磺酸及其衍生物红外光谱研究 [J]. 分析化学,2000,(6):716.)

B Y Zhao,K A Hu,Y Z Fan,P F Zhu,R J Wu. Infrared spectroscopic study on lignosulfonic acid and its derivatives [J]. Chinese Journal of Analytical Chemistry,2000,(6):716.

[29](朱莉,罗学刚. 对制浆废液脱磺以提取木质素 [J]. 化工进展,2007,(11):1645.)

L Zhu,X G Luo. Extraction of lignin from black liquor by desulfonation [J]. Chemical Industry and Engineering Progress,2007,(11):1645.

[30](赵雪冰,苏凤宜,邢新会. 过氧乙酸氧化木质素磺酸钠 [J]. 清华大学学报(自然科学版),2005,(9):1244.)

X B Zhao,F Y Su,X H Xing. Oxidation of sodium lignosulphonate by peracetic acid [J]. Journal of Tsinghua University(Science and Technology),2005,(9):1244.

[31](谭春枚. 木质素磺酸盐的层析分离研究 [D]. 广州:华南理工大学,2010. 46.)

C M Tan. Isolation of Lignosulfonate by Using Column Chromatography [D]. Guangzhou:South China University of Technology,2010. 46.

[32](王栋,夏俊美,张盈盈,吕家乐,袁铃,黄桂兰. 环境样品中痕量硫芥类化合物的核磁共振分析 [J]. 分析试验室,2023,42(5):689.)

D Wang,J M Xia,Y Y Zhang,J L Lv,L Yuan,G L Huang. Nuclear magnetic resonance analysis of trace sulfur mustard chemicals in the environmental samples [J]. Chinese Journal of Analysis Laboratory,2023,42(5):689.

[33](刘金科,杨桂花,齐乐天,薛玉,陈嘉川. 胆碱类低共熔溶剂选择性分离杨木中木质素的研究 [J]. 中国造纸,2020,39(4):1.)

J K Liu,G H Yang,L T Qi,Y Xue,J C Chen. Selective extraction of poplar lignin with choline-based deep eutectic solvents [J]. China Pulp & Pape,2020,39(4):1.

[34](辛莹莹. 木质素基酚醛树脂的绿色合成 [D]. 上海:华东师范大学,2021. 30.)

Y Y Xin. Green Synthesis of Lignin-Based Phenolic Resin [D]. Shanghai:East China Normal University,2021. 30.

[35](曾诚,宋国杰,孙海彦,郭书贤,孟超然,孙付保. 甘油预处理蔗渣的木质素分离提取及结构表征 [J]. 化工进展,2020,39(11):4418.)

C Zeng,G J Song,H Y Sun,S X Guo,C R Meng,F B Sun. Isolation and structural characterization of glycerol extracted sugarcanebagasse lignin [J]. Chemical Industry and Engineering Progress,2020,39(11):4418.

[36](李楠,周婷婷,耿莉莉,张宏喜. 棉杆有机溶剂型木质素的结构表征与分析 [J]. 广东化工,2015,42(15):45.)

N Li,T T Zhou,L L Geng,H X Zhang. Structure characterization and analysis of organic solvent lignins from cotton stalk [J]. Guangdong Chemical Industry,2015,42(15):45.

[37](胡强,王延云,龚卫华,王燕,唐梦劼. 低共熔溶剂预处理对笋壳木质素结构及物化性质的影响 [J]. 天然产物研究与开发,2023,35(3):365.)

Q Hu,Y Y Wang,W H Gong,Y Wang,M J Tang. Effect of deep eutectic solvent pretreatment on the structure and physicochemical properties of lignin from bamboo shoot shell [J]. Natural Product Research and Development,2023,35(3):365.

[38]Wang Q,Tu S Q,Wang W Y,Chen W,Duan X Y,Chang L M. Optimized indium modified Ti/PbO2 anode for electrochemical degradation of antibiotic cefalexin in aqueous solutions [J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects,2021,628:127244.

[39](张晨沛,杨长江,赵吕兴,李灿,李启坤,常军. 碳烟颗粒掺杂铅基复合阳极的制备及电化学性能研究 [J]. 稀有金属材料与工程,2024,53(2):483.)

C P Zhang,C J Yang,L X Zhao,C Li,Q K Li,J Chang. Preparation and electrochemical properties of soot-doped lead-based composite anodes [J]. Rare Metal Materials and Engineering,2024,53(2):483.

[40]Chen B M,Liu J H,Wang S C,Huang H,He Y P,Guo Z C. Preparation and electrochemical properties of a novel porous Ti/Sn-Sb-RuOx/β-PbO2/MnO2 anode for zinc electrowinning [J]. RSC Advances,2021,11(31):19136.

[41]Brug G J,van den Eeden A L G,Sluyters-Rehbach M,Sluyters J H. The analysis of electrode impedances complicated by the presence of a constant phase element [J]. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry,1984,176(1):275.

[42]Hu C Y,Liu J H,Zhang M,Zeng S,Guo S H,Xu L,Yu L F. A novel CF/Ti/β-PbO2 composite anode for zinc electrowinning:preparation,electrochemical properties and application [J]. Journal of Materials Chemistry A,2023,11(3):1403.

Basic Information:

DOI:10.13373/j.cnki.cjrm.XY24060025

Chinese Library Classification Number:TB333

Citation Information:

Zinc metal has an active chemistry and is widely used in industries such as galvanised protective film and battery manufacturing. Eighty-five percent of zinc metal is produced by hydrometallurgy. Zinc electrowinning,as a vital part of hydrometallurgy,accounts for 80% of the total energy consumption of the hydrometallurgical process. During the electrowinning of zinc,the anodic oxygen evolution reaction has a high charge transfer energy barrier,which results in the anode generating a large overpotential of oxygen evolution potential. This leads to an increase in tank voltage and energy consumption. Concurrently,the anode material must be used in an environment with high acidity,high oxidation,high current density,and the co-existence of halogen ions. This results in corrosion of the anodes,which consequently reduces their service life. The anode sludge also has an impact on the quality of the zinc cathode. Currently,lead-based anodes are predominant in the wet zinc refining industry. However,lead-based anodes still have problems with high oxygen evolution potential and poor corrosion resistance. Lead-based anodes can be modified by doping functional metal elements. For instance,the incorporation of silver,a noble metal with electrocatalytic properties,can diminish the oxygen evolution potential of lead-based anodes. Nevertheless,silver is unable to enhance the mechanical strength of lead-based anodes,and the introduction of the precious metal silver will also considerably elevate the production cost of the anodes. It is therefore of great significance to identify a renewable and low-cost reinforcing phase that can be used as an effective substitute for silver in order to enhance the oxygen precipitation catalytic activity and corrosion resistance of conventional lead-based anodes. In this study,the sodium lignosulfonate,a byproduct of the paper industry,was employed as the primary raw material. The purified lignin was obtained following desulfurisation and purification. Pb-Lignin composite anodes were prepared by incorporating lignin into Pb-based anodes through the use of powder metallurgy technology. The impact of lignin on the electrochemical performance and corrosion resistance of Pb-xLignin composite anodes (x=0,0.2,0.4,0.6,0.8,1.0,%,mass fraction) was investigated. The prepared lignin was micron-sized spherical,with the benzene ring structure preserved intact. Lignin is rich in oxygen-containing active functional groups and is an excellent electrode active material with high electrochemical reactivity and stability. The doped lignin exhibited a varying degree of modification effect on the lead-based anode. The enhancement of the electrochemical performance and corrosion resistance of the lead-based composite anode by lignin exhibited an initial increase and subsequent decrease with increasing lignin doping under simulated zinc electrowinning conditions. This phenomenon could be attributed to the structural composition of the prepared lignin,which comprised lilac-based and p-hydroxyphenyl structural units,rendering it more prone to accelerate the oxygen precipitation electrocatalytic reaction on the anode surface. When the doping amount exceeded 0.8%,π-π interactions and hydrogen bonding between lignin molecules led to severe agglomeration,resulting in an uneven distribution of lignin on the surface of the lead anode and a weakening of the enhancement effect on the lead-based anode. The optimal modification of the lead-based composite anode was achieved when the doping amount of lignin was 0.8%. At this juncture,the Pb-0.8%Lignin composite anode exhibited a 1.25 and 1.23-fold increase in voltammetric charge,a 1.94 and 1.50-fold enhancement in bilayer capacitance (Cdl),and a higher apparent exchange current density than the pure Pb and Pb-Ag-Ca composite anodes. The oxygen evolution potential steady-state potential was 1.528 V at a current density of 500 A·m−2,which was 125 mV lower than that of the pure Pb electrode. Furthermore,the corrosion rate was reduced by 31.6%,which provided excellent oxygen evolution catalytic activity and corrosion resistance.

quote

GB/T 7714-2015 [1] Can Li, Changjiang Yang, Chenpei Zhang, et al. Electrochemical Properties of Pb-Lignin Composite Anodes for Zinc Electrowinning[J]. Chinese Journal of Rare Metals, 2025, 49(10): 1541-1553. DOI:10.13373/j.cnki.cjrm.XY24060025.
MLA [1] Can Li, et al., "Electrochemical Properties of Pb-Lignin Composite Anodes for Zinc Electrowinning." Chinese Journal of Rare Metals, vol. 49, no. 10, 2025, pp. 1541-1553, https://doi.org/10.13373/j.cnki.cjrm.XY24060025.
APA [1] Can Li, Changjiang Yang, Chenpei Zhang, Jun Chang, Haijing Cui, & Yunlong Yin. (2025). Electrochemical Properties of Pb-Lignin Composite Anodes for Zinc Electrowinning. Chinese Journal of Rare Metals, 49(10), 1541-1553. https://doi.org/10.13373/j.cnki.cjrm.XY24060025
IEEE [1] Can Li, Changjiang Yang, Chenpei Zhang, Jun Chang, Haijing Cui, and Yunlong Yin, "Electrochemical Properties of Pb-Lignin Composite Anodes for Zinc Electrowinning," Chinese Journal of Rare Metals, vol. 49, no. 10, pp. 1541-1553, 2025, doi: 10.13373/j.cnki.cjrm.XY24060025. keywords: {lignin;composite anode;oxygen evolutionreaction;zinc electrowinning}