Ni²⁺掺杂与纳米结构调控协同构筑高性能水系锌离子电池 MnO₂正极

Synergistic Modification of Ni²⁺ Doping and Nanostructure Regulation for High-performance Aqueous Zinc-ion Battery MnO₂ Cathodes

摘要

针对水系锌离子电池δ-MnO₂正极材料存在的反应动力学迟缓、结构不稳定及容量衰减快等问题, 提出一种结合Ni²⁺离子掺杂与纳米结构调控的协同改性策略, 制备了Ni²⁺掺杂的δ-MnO₂纳米花正极材料(NiMnO₂-n). 纳米结构调控使NiMnO₂-n具有纳米级片层尺寸和大的比表面积(142 m²/g), 能有效缩短离子扩散路径并增加电化学活性位点. 同时, Ni²⁺掺杂进一步减薄了纳米片厚度并扩大层间距, 在促进H⁺/Zn²⁺嵌入/脱出动力学的同时, 显著提升了材料的结构稳定性. 此外, Ni²⁺掺杂引入的丰富氧空位可削弱离子插层时的空间位阻, 降低离子扩散能垒, 从而加速反应动力学. 得益于上述结构优势, NiMnO₂-n表现出更快的H⁺和Zn²⁺扩散特性与嵌入/脱出动力学特性, 具备良好的倍率性能和循环稳定性: 在1.0 A/g电流密度下可提供150.7 mA·h/g的可逆容量, 循环900次后每次容量衰减率仅为0.040%. 机理研究初步证实, NiMnO₂-n的储能过程为H⁺与Zn²⁺嵌入/脱出和沉积-溶解共存的混合反应机制.

Abstract

The δ-MnO₂ cathode materials in aqueous zinc-ion batteries suffer from sluggish reaction kinetics, structural instability and rapid capacity degradation. To address these issues, this study proposes a synergistic modification strategy combining Ni²⁺ doping and nanostructure regulation, successfully preparing Ni²⁺-doped δ-MnO₂ nanoflower spheres (NiMnO₂-n). Nanostructure regulation endows NiMnO₂-n with nanosized sheet structures and a large specific surface area of 142 m²/g, effectively shortening ion diffusion paths and increasing electrochemical active sites. Besides, Ni²⁺ doping further reduces the thickness of nanosheet and expands the interlayer spacing, which not only promotes H⁺/Zn²⁺ intercalation/extraction kinetics but also significantly enhances the structural stability of NiMnO₂-n. Moreover, the abundant oxygen vacancies introduced by Ni²⁺ doping weaken the spatial potential resistance for ion intercalation and lower the ion diffusion barrier, thereby accelerating the reaction kinetics. Benefiting from these structural advantages, NiMnO₂-n exhibits faster H⁺ and Zn²⁺ diffusion characteristics and improved intercalation/extraction kinetics, leading to improved rate capability and cycling stability: it delivers a reversible capacity of 150.7 mA·h/g at a current density of 1.0 A/g with a decay rate as low as 0.040% per cycle over 900 cycles. Mechanistic studies preliminarily confirm that the energy storage process in NiMnO₂-n originates from the intercalation/extraction of H⁺ and Zn²⁺ and the dissolution-deposition of MnO₂.

关键词

水系锌离子电池 / 掺杂 / 结构调控 / 氧空位 / 动力学

Key words

Aqueous zinc-ion battery / Doping / Structural regulation / Oxygen vacancy / Kinetics

参考文献

[1] Khamsanga S., Pornprasertsuk R., Yonezawa T., Mohamad A. A., Kheawhom S., Sci. Rep., 2019, 9(1), 8441

[2] Chao D., Ye C., Xie F., Zhou W., Zhang Q., Gu Q., Davey K., Gu L., Qiao S. Z., Adv. Mater., 2020, 32(25), 2001894

[3] Chuai M., Yang J., Tan R., Liu Z., Yuan Y., Xu Y., Sun J., Wang M., Zheng X., Chen N., Chen W., Adv. Mater., 2022, 34(33), 2203249

[4] Gou L., Sun A. H., Liang K., Wang Y. J., Fan X. Y., Li D. L., Chem. J. Chinese Universities, 2025, 46(10), 20250105

[5] (苟蕾, 孙爱红, 梁凯, 王延静, 樊小勇, 李东林 . 高等学校化学学报, 2025, 46(10), 20250105)

[6] Zhang T., Li T., Shen Y., Ma H., Wei C., Cai J., Xu Y., Li Y., Dong X., Zhang S., Huang F., Lin T., Adv. Mater., 2025, 37(34), 2505082

[7] Blanc L. E., Kundu D., Nazar L. F., Joule, 2020, 4(4), 771-799

[8] Zhou M., Zheng Y., Bi J., Liu L., Sun W., Tian C., Cai Z., Zhao X., Niu C., Sun Y., Pan H., Angew. Chem. Int. Ed., 2025, 65(6), e23672

[9] Dong Y., Jia M., Wang Y., Xu J., Liu Y., Jiao L., Zhang N., ACS Appl. Energy Mater., 2020, 3(11), 11183-11192

[10] Hu P., Zhu T., Wang X., Wei X., Yan M., Li J., Luo W., Yang W., Zhang W., Zhou L., Zhou Z., Mai L., Nano Lett., 2018, 18(3), 1758-1763

[11] Deng W., Li Z., Ye Y., Zhou Z., Li Y., Zhang M., Yuan X., Hu J., Zhao W., Huang Z., Li C., Chen H., Zheng J., Li R., Adv. Energy Mater., 2021, 11(31), 2003639

[12] Ma L., Chen S., Long C., Li X., Zhao Y., Liu Z., Huang Z., Dong B., Zapien J. A., Zhi C., Adv. Energy Mater., 2019, 9(45), 1902446

[13] Wang Q., Xu X., Yang G., Liu Y., Yao X., Chem. Commun., 2020, 56(79), 11859-11862

[14] Cui H., Ma L., Huang Z., Chen Z., Zhi C., SmartMat, 2022, 3(4), 565-581

[15] Zhang J., Li W., Wang J., Pu X., Zhang G., Wang S., Wang N., Li X., Angew. Chem. Int. Ed., 2023, 62(8), e202215654

[16] Guo X., Zhou J., Bai C., Li X., Fang G., Liang S., Mater. Today Energy, 2020, 16, 100396

[17] Wei C., Xu C., Li B., Du H., Kang F., J. Phys. Chem. Solids, 2012, 73(12), 1487-1491

[18] Chacko B., Wuppulluri M., Mater. Renew. Sustain. Energy, 2025, 14(1), 10

[19] Zheng J., Zhao J., Ye J., Deng K., Liu P., Liao Q., Liu X., Lv X., Tan S., Tian W., Ji J., Appl. Surf. Sci., 2023, 635, 157665

[20] Cai Z., Zhou M., Sun W., Li Y., Pan H., ACS Appl. Mater. Interfaces, 2025, 17(46), 63861-63870

[21] Wang Y., Zhou H., Wei S., Chen S., Cao D., Zhou Q., Wu X., Song L., J. Am. Chem. Soc., 2025, 147(45), 41297-41307

[22] Liu X., Zheng J., Li J., Ming F., Zhu Y., Wei B., Qi Z., Makgwane P. R., Liang H., Nano Lett., 2025, 25(51), 17790-17796

[23] Cai Y., Chua R., Huang S., Ren H., Srinivasan M., Chem. Eng. J., 2020, 396, 125221

[24] Karbak M., Baazizi M., Sayah S., Autret—Lambert C., Tison Y., Martinez H., Chafik T., Ghamouss F., J. Mater. Chem. A, 2023, 11(6), 2634-2640

[25] Zhang X., Ma X., Bi H., Zhang Y., Mi P., Liu F., Jin X., Chen Y., Zhang K., Wang J., Dong Y., Adv. Funct. Mater., 2025, 35(1), 2411990

[26] Lin J., Wang Y., Chen M., Lu J., Mi H., Chen J., He C., Ma D., Zhang P., Adv. Energy Mater., 2024, 14(31), 2401275

[27] Ye J. J., Li P. H., Hou Z., Zhang W., Zhu W., Jin S., Ji H., Angew. Chem. Int. Ed., 2024, 63(43), e202410900

[28] Zhao Y., Zhang S., Zhang Y., Liang J., Ren L., Fan H. J., Liu W., Sun X., Energy Environ. Sci., 2024, 17(3), 1279-1290

[29] Chacón—Borrero J., Chang X., Min Z., Yu J., Montaña—Mora G., Mejia—Centeno K. V., Sun Y., Zhou X., Tunmee S., Kidkhunthod P., Li J., Llorca J., Arbiol J., Cabot A., Energy Storage Mater., 2025, 81, 104486

[30] Li T., Zhang N., Liu B., Wang P., Liu Z., Wang Y., Xu D., Tian H., Zhang Q., Yi T. F., Adv. Funct. Mater., 2025, 35(20), 2423755

[31] Xu Y., Zhang G., Wang X., Zhang J., Wen H., Wang D., Yuan Y., Jiang Q., Qian H., Xi Y., Zuo J., Li M., Liu J., Yang H., Luo Y., Wang J., Li W., Li X., Adv. Funct. Mater., 2025, 35(27), 2500137

[32] Xie D., Wang Y., Tian L., Huang H., Sun J., Kim D. W., Zhao J., Mao J., Adv. Funct. Mater., 2025, 35(4), 2413993

[33] Liang J., Zhao Y., Ren L., Li M., Zhang Q., Wang Y., Sun X., Chuai M., Wang X., Liu W., Adv. Funct. Mater., 2025, 35(25), 2501135

[34] Ge W., Chen X., Ma R., Zheng S., Shang N., Zhao X., Chem. Res. Chinese Universities, 2024, 40(3), 437-450

[35] Hou P., Yang N., Wang D., Chem. Res. Chinese Universities, 2024, 40(3), 394-412

[36] Meng D., Ran S., Gao L., Zhang Y., San X., Zhang L., Li R., Jin Q., Chem. Res. Chinese Universities, 2024, 40(3), 490-498

[37] Wang C. B., Li P., Chen D. H., Zhang R. L., Wang L., Zong L. B., Chem. Res. Chinese Universities, 2024, 40(3), 462-474

[38] Li L., Wang J., Chen Z., Dong J., Chang P., Zhang J., Yang T., Ding R., Chem. Eng. J., 2025, 507, 160760

[39] Chen Y., Lin C., Chen X., Lu Z., Zhang K., Liu Y., Wang J., Han G., Xu G., Adv. Energy Mater., 2024, 14, 2304303

[40] Wang Y., Zhang Y., Gao G., Fan Y., Wang R., Feng J., Yang L., Meng A., Zhao J., Li Z., Nano Micro Lett., 2023, 15(1), 219

[41] Liang X., Hart C., Pang Q., Garsuch A., Weiss T., Nazar L. F., Nat. Commun., 2015, 6(1), 5682

[42] Wu D., King S. T., Sadique N., Ma L., Ehrlich S. N., Ghose S., Bai J., Zhong H., Yan S., Bock D. C., Takeuchi E. S., Marschilok A. C., Housel L. M., Wang L., Takeuchi K. J., J. Mater. Chem. A, 2023, 11(30), 16279-16292

[43] Ren Y., Li H., Rao Y., Zhou H., Guo S., Energy Environ. Sci., 2024, 17(2), 425-441

[44] Geng L., Meng J., Wang X., Wu W., Han K., Huang M., Han C., Wu L., Li J., Zhou L., Mai L., Chem, 2025, 11(2), 102302

[45] Li Y. S., Geng L. S., Zhang B. M., Wei Z. H., Fan H., Li J. H., Feng W. C., Zhou L., Rare Met., 2025, 44(2), 950-960

基金资助

国家自然科学基金(21905061)

山西省基础研究计划项目(202403021212304)

优秀博士来晋科研专项(QZX-2023015)

2025年运城市科技计划项目(YCKJYD-202537)

运城学院应用研究计划项目(YY-202207)

运城学院应用研究计划项目(QZX-2023015)

运城学院应用研究计划项目(YQ-2023021)