Synergistically coupling of graphene quantum dots with Zn-intercalated MnO₂ cathode for high-performance aqueous Zn-ion batteries

Abstract

Cost-effective, safe, and highly performing energy storage devices require rechargeable batteries, and among various options, aqueous zinc-ion batteries (ZIBs) have shown high promise in this regard. As a cathode material for the aqueous ZIBs, manganese dioxide (MnO₂) has been found to be promising, but certain drawbacks of this cathode material are slow charge-transfer capability and poor cycling performance. Herein, a novel design of graphene quantum dots (GQDs) integrated with Zn-intercalated MnO₂ nanosheets is put forward to construct a 3D nanoflower-like GQDs@Zn _xMnO₂ composite cathode for aqueous ZIBs. The synergistic coupling of GQDs modification with Zn intercalation provides abundant active sites and conductive medium to facilitate the ion/electron transmission, as well as ensure the GQDs@Zn _xMnO₂ composite cathode with enhanced charge-transfer capability and high electrochemical reversibility, which are elucidated by experiment results and in-situ Raman investigation. These impressive properties endow the GQDs@Zn _xMnO₂ composite cathode with superior aqueous Zn²⁺ storage capacity (∼403.6 mAh·g⁻¹), excellent electrochemical kinetics, and good structural stability. For actual applications, the fabricated aqueous ZIBs can deliver a substantial energy density (226.8 W·h·kg⁻¹), a remarkable power density (650 W·kg⁻¹), and long-term cycle performance, further stimulating their potential application as efficient electrochemical storage devices for various energy-related fields.

Keywords

synergistically coupling / intercalation engineering / graphene quantum dots / manganese oxides / aqueous batteries

References

[1] Wang F, Borodin O, Gao T, Fan XL, Sun W, Han FD, Faraone A, Dura JA, Xu K, Wang CS. Highly reversible zinc metal anode for aqueous batteries. Nat. Mater., 2018, 17(6): 543.

[2] Liang GJ, Mo FN, Ji XL, Zhi CY. Non-metallic charge carriers for aqueous batteries. Nat. Rev. Mater., 2021, 6(2): 109.

[3] Y. Zhang, F. Wan, S. Huang, S. Wang, Z.Q. Niu, and J. Chen, A chemically self-charging aqueous zinc-ion battery, Nat. Commun., 11(2020), art. No. 2199.

[4] Small Methods, 2019, 3(1) art. No. 1800272

[5] Qin XH, Du YH, Zhang PC, Wang XY, Lu QQ, Yang AK, Sun JC. Layered Barium vanadate nanobelts for high-performance aqueous zinc-ion batteries. Int. J. Miner. Metall. Mater., 2021, 28(10): 1684.

[6] Tang BY, Shan LT, Liang SQ, Zhou J. Issues and opportunities facing aqueous zinc-ion batteries. Energy Environ. Sci., 2019, 12(11): 3288.

[7] Small, 2020, 16(5) art. No. 1905842

[8] Small, 2018, 14(13) art. No. 1703850

[9] Adv. Funct. Mater., 2018, 28(41) art. No. 1802564

[10] Yadav GG, Turney D, Huang JC, Wei X, Banerjee S. Breaking the 2 V barrier in aqueous zinc chemistry: Creating 2.45 and 2.8 V MnO₂—Zn aqueous batteries. ACS Energy Lett., 2019, 4(9): 2144.

[11] Chao DL, Zhou WH, Ye C, Zhang QH, Chen YG, Gu L, Davey K, Qiao SZ. An electrolytic Zn-MnO₂ battery for high-voltage and scalable energy storage. Angew. Chem. Int. Ed., 2019, 58(23): 7823.

[12] Adv. Mater., 2020, 32(50) art. No. 2002450

[13] Zhang HZ, Liu QY, Wang J, Chen KF, Xue DF, Liu J, Lu XH. Boosting the Zn-ion storage capability of birnessite manganese oxide nanoflorets by La³+ intercalation. J. Mater. Chem. A, 2019, 7(38): 22079.

[14] Zhao Y, Wang B, Shi MJ, An SB, Zhao LP, Yan C. Mg-intercalation engineering of MnO₂ electrode for high-performance aqueous magnesium-ion batteries. Int. J. Miner. Metall. Mater., 2022, 29(11): 1954.

[15] Adv. Energy Mater., 2020, 10(29) art. No. 2001275

[16] Bak S, Kim D, Lee H. Graphene quantum dots and their possible energy applications: A review. Curr. Appl. Phys., 2016, 16(9): 1192.

[17] Zahir N, Magri P, Luo W, Gaumet JJ, Pierrat P. Recent advances on graphene quantum dots for electrochemical energy storage devices. Energy Environ. Mater., 2022, 5(1): 201.

[18] Liu QW, Sun JH, Gao K, Chen N, Sun XT, Ti D, Bai CC, Cui RR, Qu LT. Graphene quantum dots for energy storage and conversion: From fabrication to applications. Mater. Chem. Front., 2020, 4(2): 421.

[19] Han Y, Liu SY, Cui L, Xu L, Xie J, Xia XK, Hao WK, Wang B, Li H, Gao J. Graphene-immobilized flower-like Ni₃S₂ nanoflakes as a stable binder-free anode material for sodium-ion batteries. Int. J. Miner. Metall. Mater., 2018, 25(1): 88.

[20] Zhang WY, Yang YN, Xia RQ, Li YC, Zhao JQ, Lin L, Cao JM, Wang QH, Liu Y, Guo HW. Graphene-quantum-dots-induced MnO₂ with needle-like nanostructure grown on carbonized wood as advanced electrode for supercapacitors. Carbon, 2020, 162, 114.

[21] Lv HP, Yuan Y, Xu QJ, Liu HM, Wang YG, Xia YY. Carbon quantum dots anchoring MnO₂/graphene aerogel exhibits excellent performance as electrode materials for supercapacitor. J. Power Sources, 2018, 398, 167.

[22] Li GZ, Huang ZX, Chen JB, Yao F, Liu JP, Li OL, Sun SH, Shi ZC. Rechargeable Zn-ion batteries with high power and energy densities: A two-electron reaction pathway in birnessite MnO₂ cathode materials. J. Mater. Chem. A, 2020, 8(4): 1975.

[23] Xu J, Hou KX, Ju ZW, Ma CJ, Wang WC, Wang C, Cao JY, Chen ZD. Synthesis and electrochemical properties of carbon dots/manganese dioxide (CQDs/MnO₂) nanoflowers for supercapacitor applications. J. Electrochem. Soc., 2017, 164(2): A430.

[24] Nguyen VH, Huynh LTN, Nguyen TH, Vu TP, Le MLP, Grag A, Tran VM. Promising electrode material using Ni-doped layered manganese dioxide for sodium-ion batteries. J. Appl. Electrochem., 2018, 48(7): 793.

[25] Liu GX, Huang HW, Bi R, Xiao X, Ma TY, Zhang L. K+ pre-intercalated manganese dioxide with enhanced Zn²⁺ diffusion for high rate and durable aqueous zinc-ion batteries. J. Mater. Chem. A, 2019, 7(36): 20806.

[26] X.L. Zeng, B. Li, R.Q. Liu, X. Li, and T.L. Zhu, Investigation of promotion effect of Cu doped MnO₂ catalysts on ketone-type VOCs degradation in a one-stage plasma-catalysis system, Chem. Eng. J., 384(2020), art. No. 123362.

[27] Adv. Sci., 2018, 5(5) art. No. 1700887

[28] Wang JJ, Wang JG, Liu HY, Wei CG, Kang FY. Zinc ion stabilized MnO₂ nanospheres for high capacity and long lifespan aqueous zinc-ion batteries. J. Mater. Chem. A, 2019, 7(22): 13727.

[29] Small, 2020, 16(14) art. No. 2000091

[30] C. Chen, M.J. Shi, Y. Zhao, C. Yang, L.P. Zhao, and C. Yan, Al-intercalated MnO₂ cathode with reversible phase transition for aqueous Zn-ion batteries, Chem. Eng. J., 422(2021), art. No. 130375.

[31] J.Q. Zheng, C.F. Liu, M. Tian, X.X. Jia, E.P. Jahrman, G.T. Seidler, S.Q. Zhang, Y.Y. Liu, Y.F. Zhang, C.G. Meng, and G.Z. Cao, Fast and reversible zinc ion intercalation in Al-ion modified hydrated vanadate, Nano Energy, 70(2020), art. No. 104519.

[32] Nano-micro Lett., 2019, 11(1) art. No. 25

[33] Guo C, Liu HM, Li JF, Hou ZG, Liang JW, Zhou J, Zhu YC, Qian YT. Ultrathin S-MnO₂ nanosheets as cathode for aqueous rechargeable zinc ion battery. Electrochim. Acta, 2019, 304, 370.

[34] Yang LF, Cheng S, Wang JH, Ji X, Jiang Y, Yao MH, Wu P, Wang MK, Zhou J, Liu ML. Investigation into the origin of high stability of S-MnO₂ pseudo-capacitive electrode using operando Raman spectroscopy. Nano Energy, 2016, 30, 293.

[35] Adv. Energy Mater., 2019, 9(3) art. No. 1802707

[36] Boyd S, Ganeshan K, Tsai WY, Wu T, Saeed S, Jiang DE, Balke N, van Duin ACT, Augustyn V. Effects of inter-layer confinement and hydration on capacitive charge storage in birnessite. Nat. Mater., 2021, 20(12): 1689.

[37] Adv. Funct. Mater., 2019, 29(8) art. No. 1806778

[38] Wang C, Zeng YX, Xiao X, Wu SJ, Zhong GB, Xu KQ, Wei ZF, Su W, Lu XH. γ-MnO₂ nanorods/graphene composite as efficient cathode for advanced rechargeable aqueous zinc-ion battery. J. Energy Chem., 2020, 43, 182.

[39] Shi MJ, Zhu HT, Yang C, Xu J, Yan C. Chemical reduction-induced fabrication of graphene hybrid fibers for energy-dense wire-shaped supercapacitors. Chin. J. Chem. Eng., 2022, 47, 1.

[40] Wang XH, Mathis TS, Li K, Lin ZF, Vlcek L, Torita T, Osti NC, Hatter C, Urbankowski P, Sarycheva A, Tyagi M, Mamontov E, Simon P, Gogotsi Y. Influences from solvents on charge storage in titanium carbide MXenes. Nat. Energy, 2019, 4(3): 241.

[41] L. Zhang, X.H. Zhang, G.Y. Tian, Q.H. Zhang, M. Knapp, H. Ehrenberg, G. Chen, Z.X. Shen, G.C. Yang, L. Gu, and F. Du, Lithium lanthanum titanate perovskite as an anode for lithium ion batteries, Nat. Commun., 11(2020), art. No. 3490.

[42] R.Y. Wang, M.J. Shi, L.Y. Li, Y. Zhao, L.P. Zhao, and C. Yan, In-situ investigation and application of cyano-substituted organic electrode for rechargeable aqueous Na-ion batteries, Chem. Eng. J., 451(2023), art. No. 138652.

[43] Ahmad R, Khan UA, Iqbal N, Noor T. Zeolitic imidazolate framework (ZIF)-derived porous carbon materials for supercapacitors: An overview. RSC Adv., 2020, 10(71): 43733.