Potassium ion pre-intercalated MnO₂ for aqueous multivalent ion batteries

Abstract

Manganese dioxide (MnO₂), as a cathode material for multivalent ion (such as Mg²⁺ and Al³⁺) storage, is investigated due to its high initial capacity. However, during multivalent ion insertion/extraction, the crystal structure of MnO₂ partially collapses, leading to fast capacity decay in few charge/discharge cycles. Here, through pre-intercalating potassium-ion (K⁺) into δ-MnO₂, we synthesize a potassium ion pre-intercalated MnO₂, K_0.21MnO₂·0.31H₂O (KMO), as a reliable cathode material for multivalent ion batteries. The as-prepared KMO exhibits a high reversible capacity of 185 mAh/g at 1 A/g, with considerable rate performance and improved cycling stability in 1 mol/L MgSO₄ electrolyte. In addition, we observe that aluminum-ion (Al³⁺) can also insert into a KMO cathode. This work provides a valid method for modification of manganese-based oxides for aqueous multivalent ion batteries.

Graphical abstract

Keywords

Aqueous batteries / Multivalent ion batteries / Magnesium ion / Aluminum ion / MnO ₂

References

[1] Hu, S., Pillai, A.S., Liang, G., Pang, W.K., Wang, H., Li, Q., Guo, Z.: Li-rich layered oxides and their practical challenges: recent progress and perspectives. Electrochem. Energy Rev. 2(2), 277–311 (2019)

[2] Shao-Horn, Y., Croguennec, L., Delmas, C., Nelson, E.C., O’Keefe, M.A.: Atomic resolution of lithium ions in LiCoO₂. Nat. Mater. 2(7), 464–467 (2003)

[3] Tarascon, J.M., Armand, M.: Issues and challenges facing rechargeable lithium batteries. Nature 414(6861), 359–367 (2001)

[4] Whittingham, M.S.: Lithium batteries and cathode materials. Chem. Rev. 104(10), 4271–4302 (2004)

[5] Dong, S., Wu, Y., Lv, N., Ren, R., Huang, L.: Porous sodium titanate nanofibers for high energy quasi-solid-state sodium-ion hybrid capacitors. Rare Met. 41(7), 2453–2459 (2022)

[6] Kim, H., Hong, J., Park, K., Kim, H., Kim, S., Kang, K.: Aqueous rechargeable Li and Na ion batteries. Chem. Rev. 114(23), 11788–11827 (2014)

[7] Posada, J.O.G., Rennie, A.J.R., Villar, S.P., Martins, V.L., Marinaccio, J., Barnes, A., Glover, C.F., Worsley, D.A., Hall, P.J.: Aqueous batteries as grid scale energy storage solutions. Renewable Sustain. Energy Rev. 68, 1174–1182 (2017)

[8] Zhang, H., Liu, X., Li, H., Hasa, I., Passerini, S.: Challenges and strategies for high-energy aqueous electrolyte rechargeable batteries. Angew. Chem. Int. Ed. 60(2), 598–616 (2021)

[9] Tong, Y., Zhang, T., Sun, Y., Wang, X., Wu, X.: Co₃O₄@NiMoO₄ composite electrode materials for flexible hybrid capacitors. Front. Optoelectron. 15(1), 25 (2022)

[10] Chen, S., Zhang, M., Zou, P., Sun, B., Tao, S.: Historical development and novel concepts on electrolytes for aqueous rechargeable batteries. Energy Environ. Sci. 15(5), 1805–1839 (2022)

[11] Dong, S., Shin, W., Jiang, H., Wu, X., Li, Z., Holoubek, J., Stickle, W.F., Key, B., Liu, C., Lu, J., Greaney, P.A., Zhang, X., Ji, X.: Ultra-fast NH₄⁺ storage: strong H Bonding between NH₄⁺ and Bi-layered V₂O₅. Chem. 5(6), 1537–1551 (2019)

[12] Dong, S., Wang, Y., Chen, C., Shen, L., Zhang, X.: Niobium tungsten oxide in a green water-in-salt electrolyte enables ultrastable aqueous lithium-ion capacitors. Nano-Micro Lett. 12(1), 168 (2020)

[13] Liang, G., Mo, F., Yang, Q., Huang, Z., Li, X., Wang, D., Liu, Z., Li, H., Zhang, Q., Zhi, C.: Commencing an acidic battery based on a copper anode with ultrafast proton-regulated kinetics and superior dendrite-free property. Adv. Mater. 31(52), 1905873 (2019)

[14] Wang, H., Tan, R., Yang, Z., Feng, Y., Duan, X., Ma, J.: Stabilization perspective on metal anodes for aqueous batteries. Adv. Energy Mater. 11(2), 2000962 (2021)

[15] Yang, D., Zhou, Y., Geng, H., Liu, C., Lu, B., Rui, X., Yan, Q.: Pathways towards high energy aqueous rechargeable batteries. Coord. Chem. Rev. 424, 213521 (2020)

[16] Famprikis, T., Canepa, P., Dawson, J.A., Islam, M.S., Masquelier, C.: Fundamentals of inorganic solid-state electrolytes for batteries. Nat. Mater. 18(12), 1278–1291 (2019)

[17] Chen, D., Tao, D., Ren, X., Wen, F., Li, T., Chen, Z., Cao, Y., Xu, F.: A molybdenum polysulfide in-situ generated from ammonium tetrathiomolybdate for high-capacity and high-power rechargeable magnesium battery cathodes. ACS Nano 16(12), 20510–20520 (2022)

[18] Liu, Y., Qin, Z., Yang, X., Liu, J., Liu, X.-X., Sun, X.: High-volt-age manganese oxide cathode with two-electron transfer enabled by a phosphate proton reservoir for aqueous zinc batteries. ACS Energy Lett. 7(5), 1814–1819 (2022)

[19] Qin, X., Zhao, X., Zhang, G., Wei, Z., Li, L., Wang, X., Zhi, C., Li, H., Han, C., Li, B.: Highly reversible intercalation of calcium ions in layered vanadium compounds enabled by acetonitrile–water hybrid electrolyte. ACS Nano 17(13), 12040–12051 (2023)

[20] Yang, J., Gong, W., Geng, F.: Defect modulation in cobalt manganese oxide sheets for stable and high-energy aqueous aluminumion batteries. Adv. Funct. Mater. 33(27), 2301202 (2023)

[21] Peng, Z., Li, Y., Ruan, P., He, Z., Dai, L., Liu, S., Wang, L., Chan Jun, S., Lu, B., Zhou, J.: Metal-organic frameworks and beyond: the road toward zinc-based batteries. Coord. Chem. Rev. 488, 215190 (2023)

[22] Yi, R., Shi, X., Tang, Y., Yang, Y., Zhou, P., Lu, B., Zhou, J.: Carboxymethyl chitosan-modified zinc anode for high-performance zinc–iodine battery with narrow operating voltage. Small Struct. 4(9), 2300020 (2023)

[23] Xie, X., Li, J., Xing, Z., Lu, B., Liang, S., Zhou, J.: Biocompatible zinc battery with programmable electro-cross-linked electrolyte. Natl. Sci. Rev. 10(3), nwac281 (2023)

[24] You, C., Wu, X., Yuan, X., Chen, Y., Liu, L., Zhu, Y., Fu, L., Wu, Y., Guo, Y.-G., van Ree, T.: Advances in rechargeable Mg batteries. J. Mater. Chem. A. 8(48), 25601–25625 (2020)

[25] Zhang, J., Chang, Z., Zhang, Z., Du, A., Dong, S., Li, Z., Li, G., Cui, G.: Current design strategies for rechargeable magnesium-based batteries. ACS Nano 15(10), 15594–15624 (2021)

[26] Pei, C., Xiong, F., Yin, Y., Liu, Z., Tang, H., Sun, R., An, Q., Mai, L.: Recent progress and challenges in the optimization of electrode materials for rechargeable magnesium batteries. Small 17(3), 2004108 (2021)

[27] Song, J., Noked, M., Gillette, E., Duay, J., Rubloff, G., Lee, S.B.: Activation of a MnO₂ cathode by water-stimulated Mg²⁺ insertion for a magnesium ion battery. Phys. Chem. Chem. Phys. 17(7), 5256–5264 (2015)

[28] Nam, K.W., Kim, S., Lee, S., Salama, M., Shterenberg, I., Gofer, Y., Kim, J.S., Yang, E., Park, C.S., Kim, J.S., Lee, S.S., Chang, W.S., Doo, S.G., Jo, Y.N., Jung, Y., Aurbach, D., Choi, J.W.: The high performance of crystal water containing manganese birnessite cathodes for magnesium batteries. Nano Lett. 15(6), 4071–4079 (2015)

[29] Saha, P., Jampani, P.H., Datta, M.K., Hong, D., Gattu, B., Patel, P., Kadakia, K.S., Manivannan, A., Kumta, P.N.: A rapid solid-state synthesis of electrochemically active Chevrel phases (Mo₆T₈; T = S, Se) for rechargeable magnesium batteries. Nano Res. 10(12), 4415–4435 (2017)

[30] Canepa, P., Sai Gautam, G., Hannah, D.C., Malik, R., Liu, M., Gallagher, K.G., Persson, K.A., Ceder, G.: Odyssey of multivalent cathode materials: open questions and future challenges. Chem. Rev. 117(5), 4287–4341 (2017)

[31] Andrews, J.L., Mukherjee, A., Yoo, H.D., Parija, A., Marley, P.M., Fakra, S., Prendergast, D., Cabana, J., Klie, R.F., Banerjee, S.: Reversible Mg-ion insertion in a metastable one-dimensional polymorph of V₂O₅. Chem. 4(3), 564–585 (2018)

[32] Augustyn, V., Simon, P., Dunn, B.: Pseudocapacitive oxide materials for high-rate electrochemical energy storage. Energy Environ. Sci. 7(5), 1597–1614 (2014)

[33] Zhang, R., Yu, X., Nam, K.-W., Ling, C., Arthur, T.S., Song, W., Knapp, A.M., Ehrlich, S.N., Yang, X.-Q., Matsui, M.: α-MnO₂ as a cathode material for rechargeable Mg batteries. Electrochem. Commun. 23, 110–113 (2012)

[34] Kim, J.-S., Chang, W., Kim, R., Kim, D., Han, D., Lee, K., Lee, S., Doo, S.: High-capacity nanostructured manganese dioxide cathode for rechargeable magnesium ion batteries. J. Power. Sources 273, 210–215 (2015)

[35] Chen, W., Zhan, X., Luo, B., Ou, Z., Shih, P., Yao, L., Pidaparthy, S., Patra, A., An, H., Braun, P.V., Stephens, R.M., Yang, H., Zuo, J., Chen, Q.: Effects of particle size on Mg²⁺ ion intercalation into λ-MnO₂ cathode materials. Nano Lett. 19(7), 4712–4720 (2019)

[36] Zhang, C., Zhan, X., Al-Zoubi, T., Ma, Y., Shih, P., Wang, F., Chen, W., Pidaparthy, S., Stephens, R.M., Chen, Q., Zuo, J., Yang, H.: Electrochemical generation of birnessite MnO₂ nanoflowers for intercalation of Mg²⁺ ions. Nano Energy 102, 107696 (2022)

[37] Clites, M., Pomerantseva, E.: Bilayered vanadium oxides by chemical pre-intercalation of alkali and alkali-earth ions as battery electrodes. Energy Storage Mater. 11, 30–37 (2018)

[38] Tang, H., Xiong, F., Jiang, Y., Pei, C., Tan, S., Yang, W., Li, M., An, Q., Mai, L.: Alkali ions pre-intercalated layered vanadium oxide nanowires for stable magnesium ions storage. Nano Energy 58, 347–354 (2019)

[39] Rasul, S., Suzuki, S., Yamaguchi, S., Miyayama, M.: High capacity positive electrodes for secondary Mg-ion batteries. Electrochim. Acta 82, 243–249 (2012)

[40] Augustyn, V., Come, J., Lowe, M.A., Kim, J.W., Taberna, P., Tolbert, S.H., Abruña, H.D., Simon, P., Dunn, B.: High-rate electrochemical energy storage through Li⁺ intercalation pseudocapacitance. Nat. Mater. 12(6), 518–522 (2013)

[41] Choi, C., Ashby, D.S., Butts, D.M., DeBlock, R.H., Wei, Q., Lau, J., Dunn, B.: Achieving high energy density and high power density with pseudocapacitive materials. Nat. Rev. Mater. 5(1), 5–19 (2020)

[42] Koketsu, T., Ma, J., Morgan, B.J., Body, M., Legein, C., Dachraoui, W., Giannini, M., Demortière, A., Salanne, M., Dardoize, F., Groult, H., Borkiewicz, O.J., Chapman, K.W., Strasser, P., Dambournet, D.: Reversible magnesium and aluminium ions insertion in cation-deficient anatase TiO₂. Nat. Mater. 16(11), 1142–1148 (2017)

[43] Wu, D., Zhuang, Y., Wang, F., Yang, Y., Zeng, J., Zhao, J.: High-rate performance magnesium batteries achieved by direct growth of honeycomb-like V₂O₅ electrodes with rich oxygen vacancies. Nano Res. 16(4), 4880–4887 (2023)

[44] Yuan, C., Zhang, Y., Pan, Y., Liu, X., Wang, G., Cao, D.: Investigation of the intercalation of polyvalent cations (Mg²⁺, Zn²⁺) into λ-MnO₂ for rechargeable aqueous battery. Electrochim. Acta 116, 404–412 (2014)

[45] Liu, M., Rong, Z., Malik, R., Canepa, P., Jain, A., Ceder, G., Persson, K.A.: Spinel compounds as multivalent battery cathodes: a systematic evaluation based on ab initio calculations. Energy Environ. Sci. 8(3), 964–974 (2015)

[46] Wu, C., Gu, S., Zhang, Q., Bai, Y., Li, M., Yuan, Y., Wang, H., Liu, X., Yuan, Y., Zhu, N., Wu, F., Li, H., Gu, L., Lu, J.: Electrochemically activated spinel manganese oxide for rechargeable aqueous aluminum battery. Nat. Commun. 10(1), 73 (2019)

[47] Gu, S., Wang, H., Wu, C., Bai, Y., Li, H., Wu, F.: Confirming reversible Al³⁺ storage mechanism through intercalation of Al³⁺ into V₂O₅ nanowires in a rechargeable aluminum battery. Energy Storage Mater. 6, 9–17 (2017)

[48] Yang, H., Li, H., Li, J., Sun, Z., He, K., Cheng, H.-M., Li, F.: The rechargeable aluminum battery: opportunities and challenges. Angew. Chem. Int. Ed. 58(35), 11978–11996 (2019)

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