Ni@PdNiO_x Bimetallic Synergism and Oxide Site Modulation to Boost Oxygen Electrocatalysis in Highly Durable Zn-Air Batteries

Abstract

Recently, zinc-air batteries have been of great interest due to their high theoretical specific energy that plays an important role in renewable energy conversion, while the sluggish kinetics of their half-reactions of oxygen reduction and oxygen evolution (ORR/OER) limit their widespread applications. Herein, we report the synthesis of self-assembly Ni@PdNiO_x seashell-like nanostructures (Ni@PdNiO_x NSs) with low Pd content through a novel one-step wet chemical method for the first time. The optimized self-assembly Ni@PdNiO_x NSs with a thickness of 2.06 nm are connected self-assembled to form a network structure, which exhibits a large surface area and unprecedented ORR/OER with a positive half-wave potential of 0.892 V vs. RHE and an overpotential of 230 mV at 10 mA/cm² in alkaline solution, outperforming most of the PdNi catalysts. When the self-assembly Ni@PdNiO_x NSs are applied as electrodes for zinc-air batteries, they deliver a high power density of 88.9 mW/cm² and an impressive energy density of 714 mA·h·g⁻¹. This work opens up a new strategy for generating superior oxygen electrocatalysis and provides new insight into the correlation of low Pd content and Ni in the improvement of alkaline oxygen electrocatalysis.

Keywords

Low content precious metal / Rechargeable Zn-air battery / Seashell-like nanostructure / Network structure / Bifunctional oxygen electrocatalyst

References

[1] Luo M, Zhao Z, Zhang Y, Sun Y, Xing Y, Lv F, Yang Y, Zhang X, Hwang S, Qin Y, Ma J Y, Lin F, Su D, Lu G, Guo SNature, 2019, 574: 81.

[2] Fu G, Wang Y, Tang Y, Zhou K, Goodenough J B, Lee J-MACS Mater. Lett., 2019, 1: 123.

[3] Yin J, Li Y, Lv F, Fan Q, Zhao Y-Q, Zhang Q, Wang W, Cheng F, Xi P, Guo SACS Nano, 2017, 11: 2275.

[4] Amiinu I S, Pu Z, Liu X, Owusu K A, Monestel H G R, Boakye F O, Zhang H, Mu SAdv. Funct. Mater., 2017, 27: 1702300.

[5] Hu S-N, Tian N, Li M-Y, Xiao C, Lou Y-Y, Zhou Z-Y, Sun S-GChem. Synth., 2023, 3: 4.

[6] Zeng H, Liu X, Chen F, Chen Z, Fan X, Lau WACS Appl. Mater. Interfaces, 2020, 12: 52549.

[7] Chen D, Zhu J, Mu X, Cheng R, Li W, Liu S, Pu Z, Lin C, Mu SAppl. Catal. B: Environ. Energy, 2020, 268: 118729.

[8] Lu X, Yang P, Wan Y, Zhang H, Xu H, Xiao L, Li R, Li Y, Zhang J, An MCoord. Chem. Rev., 2023, 495: 215400.

[9] Zhang M, Liu Q, Sun W, Sun K, Shen Y, An W, Zhang L, Chen H, Zou XChem. Synth., 2023, 3: 28.

[10] Wang H, Gong G, Sun G, Qi J, Yu R, Wang DChem. Res. Chinese Universities, 2024, 40: 475.

[11] Guo H, Feng Q, Zhu J, Xu J, Li Q, Liu S, Xu K, Zhang C, Liu TJ. Mater. Chem. A, 2019, 7: 3664.

[12] Diao J, Qiu Y, Liu S, Wang W, Chen K, Li H, Yuan W, Qu Y, Guo XAdv. Mater., 2020, 32: e1905679.

[13] Amiinu I S, Liu X, Pu Z, Li W, Li Q, Zhang J, Tang H, Zhang H, Mu SAdv. Funct. Mater., 2018, 28: 1704638.

[14] Wei X, Cao S, Xu H, Jiang C, Wang Z, Ouyang Y, Lu X, Dai F, Sun DACS Mater. Lett., 2022, 4: 1991.

[15] Li R, Li Y, Yang P, Ren P, Wang D, Lu X, Zhang H, Zhang Z, Yan P, Zhang J, An M, Wang B, Liu H, Dou SSmall, 2023, 19: 2302151.

[16] Xia T, Ren Q, Yang J, Li Z, Shao M, Duan XChem. Res. Chinese Universities, 2024, 40: 577.

[17] Nguyen D C, Luyen Doan T L, Prabhakaran S, Tran D T, Kim D H, Lee J H, Kim N HNano Energy, 2021, 82: 105750.

[18] Liu Y, Jiang Z, Jiang Z JAdv. Funct. Mater., 2023, 33: 2302883.

[19] Zhang W, Chang J, Wang G, Li Z, Wang M, Zhu Y, Li B, Zhou H, Wang G, Gu M, Feng Z, Yang YEnergy Environ. Sci., 2022, 15: 1573.

[20] Yi M, Li N, Lu B, Li L, Zhu Z, Zhang JEnergy Storage Mater., 2021, 42: 418.

[21] Zhang H, Guang H, Li R, Lu X, Xu H, Wang D, Xiao L, Zhang J, An M, Yang PJ. Mater. Chem. A, 2022, 10: 21797.

[22] Ding D, Shen K, Chen X, Chen H, Chen J, Fan T, Wu R, Li YACS Catal., 2018, 8: 7879.

[23] Jiang H, Gu J, Zheng X, Liu M, Qiu X, Wang L, Li W, Chen Z, Ji X, Li JEnergy Environ. Sci., 2019, 12: 322.

[24] Lu W, Zhao XChem. Res. Chinese Universities, 2025, 41: 432.

[25] Aljabour A, Awada H, Song L, Sun H, Offenthaler S, Yari F, Bechmann M, Scharber M C, Schöfberger WAngew. Chem. Int. Ed., 2023, 62: e202302208.

[26] Chang J, Zhang Q, Yu J, Jing W, Wang S, Yin G, Waterhouse G I N, Lu SAdv. Sci., 2023, 10: 2301656.

[27] Quílez-Bermejo J, García-Dalí S, Daouli A, Zitolo A, Canevesi R L S, Emo M, Izquierdo M T, Badawi M, Celzard A, Fierro VAdv. Funct. Mater., 2023, 33: 2300405.

[28] Lim J, Jung J-W, Kim N-Y, Lee G Y, Lee H J, Lee Y, Choi D S, Yoon K R, Kim Y-H, Kim I-D, Kim S OEnergy Storage Mater., 2020, 32: 517.

[29] Zhong H-L, Ze H, Zhang X-G, Zhang H, Dong J-C, Shen T, Zhang Y-J, Sun J-J, Li J-FACS Catal., 2023, 13: 6781.

[30] Liu Q, He Y M, Weng X, Wang A J, Yuan P X, Fang K M, Feng J JJ. Colloid Interface Sci., 2018, 513: 455.

[31] Hu T, Wang Y, Zhang L, Tang T, Xiao H, Chen W, Zhao M, Jia J, Zhu HAppl. Catal. B: Environ. Energy, 2019, 243: 175.

[32] Wang Y, Hall A SACS Energy Lett., 2019, 5: 17.

[33] Li Z, Li H, Li M, Hu J, Liu Y, Sun D, Fu G, Tang YEnergy Storage Mater., 2021, 42: 118.

[34] Wang S, Lin Z, Li M, Yu Z, Zhang M, Gong M, Tang Y, Qiu XJ. Mater. Chem. A, 2022, 10: 6086.

[35] Fu Z, Ling C, Wang JJ. Mater. Chem. A, 2020, 8: 7801.

[36] Manjunatha R, Dong L, Zhai Z, Wang J, Fu Q, Yan W, Zhang JGreen Energy Environ., 2022, 7: 933.

[37] Liu P, Li X, Min P, Chang X, Shu C, Ding Y, Yu Z-ZNano-Micro Letters, 2020, 13: 22.

[38] Seo M H, Park M G, Lee D U, Wang X, Ahn W, Noh S H, Choi S M, Cano Z P, Han B, Chen ZAppl. Catal. B: Environ. Energy, 2018, 239: 677.

[39] Liu K, Huang H, Zhu Y, Wang S, Lyu Z, Han X, Kuang Q, Xie SJ. Mater. Chem. A, 2022, 10: 3808.

[40] Hafner JJ. Comput. Chem., 2008, 29: 2044.

[41] Mortensen J J, Hansen L B, Jacobsen K WPhys. Rev. B, 2005, 71: 035109.

[42] Perdew J P, Burke K, Ernzerhof MPhys. Rev. Lett., 1996, 77: 3865.

[43] Grimme SJ. Comput. Chem., 2006, 27: 1787.

[44] Fan J, Wu J, Cui X, Gu L, Zhang Q, Meng F, Lei B H, Singh D J, Zheng WJ. Am. Chem. Soc., 2020, 142: 3645.

[45] Liu H, Tang H, Fang M, Si W, Zhang Q, Huang Z, Gu L, Pan W, Yao J, Nan C, Wu HAdv. Mater., 2016, 28: 8170.

[46] Sun Z, Yang X, Yu X-F, Xia L, Peng Y, Li Z, Zhang Y, Cheng J, Zhang K, Yu JAppl. Catal. B: Environ. Energy, 2021, 285: 119790.

[47] Lin X X, Zhang X F, Wang A J, Fang K M, Yuan J, Feng J JJ. Colloid Interface Sci., 2017, 499: 128.

[48] Wang P, Qin R, Ji P, Pu Z, Zhu J, Lin C, Zhao Y, Tang H, Li W, Mu SSmall, 2020, 16: e2001642.

[49] Zhou P, Lv X, Tao S, Wu J, Wang H, Wei X, Wang T, Zhou B, Lu Y, Frauenheim T, Fu X, Wang S, Zou YAdv. Mater., 2022, 34: 2204089.

[50] Hu Y, Luo X, Wu G, Chao T, Li Z, Qu Y, Li H, Wu Y, Jiang B, Hong XACS Appl. Mater. Interfaces, 2019, 11: 42298.

[51] Li Y, Yuan M, Yang H, Shi K, Sun Z, Li H, Nan C, Sun GAppl. Catal. B: Environ. Energy, 2023, 323: 122167.

[52] Tian J, Rao Y, Shi W, Yang J, Ning W, Li H, Yao Y, Zhou H, Guo SAngew. Chem. Int. Ed., 2023, 62: e202310894.

[53] Wang X., Kang Z., Wang D., Zhao Y., Xiang X., Shang H., Zhang B., Nano Energy, 2024, 121.

[54] Li C, Zhang Z, Liu RSmall, 2020, 16: e2003777.

[55] Xu X, Liao H, Huang L, Chen S, Wang R, Wu S, Wu Y, Sun Z, Huang HAppl. Catal. B: Environ. Energy, 2024, 341: 123312.

[56] Yan L, Zhang B, Wu S, Yu JJ. Mater. Chem. A, 2020, 8: 14234.

[57] Choi S, Do H W, Jin D, Kim S, Lee J, Soon A, Moon J, Shim WAdv. Funct. Mater., 2021, 31: 2101720.

[58] Wu D, Chen D, Zhu J, Mu SSmall, 2021, 17: e2102777.

[59] Han J, Bao H, Wang J-Q, Zheng L, Sun S, Wang Z L, Sun CAppl. Catal. B: Environ. Energy, 2021, 280: 119411.

RIGHTS & PERMISSIONS

Jilin University, The Editorial Department of Chemical Research in Chinese Universities and Springer-Verlag GmbH

Just Accepted

This article has successfully passed peer review and final editorial review, and will soon enter typesetting, proofreading and other publishing processes. The currently displayed version is the accepted final manuscript. The officially published version will be updated with format, DOI and citation information upon launch. We recommend that you pay attention to subsequent journal notifications and preferentially cite the officially published version. Thank you for your support and cooperation.