Two-electron redox chemistry enables potassium-free copper hexacyanoferrate as high-capacity cathode for aqueous Mg-ion battery

Abstract

Prussian blue analogs (PBAs) are potential contestants for aqueous Mg-ion batteries (AMIBs) on account of their high discharge voltage and three-dimensional open frameworks. However, the low capacity arising from single reaction site severely restricts PBAs' practical applications in high-energy-density AMIBs. Here, an organic acid co-coordination combined with etching method is reported to fabricate defect-rich potassium-free copper hexacyanoferrate with structural water on carbon nanotube fiber (D-CuHCF@CNTF). Benefiting from the high-valence-state reactive sites, arrayed structure and defect effect, the well-designed D-CuHCF@CNTF exhibits an extraordinary reversible capacity of 146.6 mAh g⁻¹ with two-electron reaction, nearly close to its theoretical capacity. It is interesting to unlock the reaction mechanism of the Fe²⁺/Fe³⁺ and Cu⁺/Cu²⁺ redox couples via x-ray photoelectron spectroscopy. Furthermore, density functional theory calculations reveal that Fe and Cu in potassium-free D-CuHCF participate in charge transfer during the Mg²⁺ insertion/extraction process. As a proof-of-concept demonstration, a rocking-chair fiber-shaped AMIBs was constructed via coupling with the NaTi₂(PO₄)₃/CNTF anode, achieving high energy density and impressive mechanical flexibility. This work provides new possibilities to develop potassium-free PBAs with dual-active sites as high-capacity cathodes for wearable AMIBs.

Keywords

aqueous Mg-ion battery / energy-storage fiber / high capacity / Prussian blue analogs / two-electron reaction

References

[1] Guan C, Liu X, Ren W, Li X, Cheng C, Wang J. Rational design of metal-organic framework derived hollow NiCo₂O₄ arrays for flexible supercapacitor and electrocatalysis. Adv Energy Mater. 2017;7(12):1602391.

[2] Yan Y, Liu X, Yan J, Guan C, Wang J. Electrospun nanofibers for new generation flexible energy storage. Energy Environ Mater. 2021;4(4):502-521.

[3] Li X, Chen L, Yuan S, et al. Stretchable luminescent perovskite-polymer hydrogels for visual-digital wearable strain sensor textiles. Adv Fiber Mater. 2023;5(5):1671-1684.

[4] Wang M, Wang Q, Ding X, et al. The prospect and challenges of sodium-ion batteries for low-temperature conditions. Interdiscip Mater. 2022;1(3):373-395.

[5] Luo Q, Ming L, Zhang D, et al. Constructing Br-doped Li₁₀SnP₂S₁₂-based all-solid-state batteries with superior performances. Energy Mater Adv. 2023;4:0065.

[6] Rashad M, Asif M, Wang Y, He Z, Ahmed I. Recent advances in electrolytes and cathode materials for magnesium and hybrid-ion batteries. Energy Storage Mater. 2020;25(3):342-375.

[7] Yang Z, Liu X-H, He X-X, et al. Rechargeable sodium-based hybrid metal-ion batteries toward advanced energy storage. Adv Funct Mater. 2021;31(8):2006457.

[8] Hou Z, Zhang T, Liu X, et al. A solid-to-solid metallic conversion electrochemistry toward 91% zinc utilization for sustainable aqueous batteries. Sci Adv. 2022;8(41):eabp8960.

[9] Wu N, Yang Y-J, Zhang Q-Y, Zhang X, du XN. A layered titanium-based transition metal oxide as stable anode material for magnesium-ion batteries. J Mater Sci. 2020;55(35):16674-16682.

[10] Koketsu T, Ma J, Morgan BJ, et al. Reversible magnesium and aluminium ions insertion in cation-deficient anatase TiO₂. Nat Mater. 2017;16(11):1142-1148.

[11] Su H, Jaffer S, Yu H. Transition metal oxides for sodium-ion batteries. Energy Storage Mater. 2016;5(10):116-131.

[12] Xu Y, Deng X, Li Q, et al. Vanadium oxide pillared by interlayer Mg²⁺ ions and water as ultralong-life cathodes for magnesium-ion batteries. Chem. 2019;5(5):1194-1209.

[13] Zhu Y-F, Xiao Y, Dou S-X, Kang YM, Chou SL. Spinel/post-spinel engineering on layered oxide cathodes for sodium-ion batteries. eScience. 2021;1(1):13-27.

[14] Truong QD, Devaraju MK, Honma I. Nanocrystalline MgMnSiO₄ and MgCoSiO₄ particles for rechargeable Mg-ion batteries. J Power Sources. 2017;361(9):195-202.

[15] Feng Z, Yang J, NuLi Y, Wang J. Sol–gel synthesis of Mg_1.03Mn_0.97SiO₄ and its electrochemical intercalation behavior. J Power Sources. 2008;184(2):604-609.

[16] Chen L, Bao J, Dong X, et al. Aqueous Mg-ion battery based on polyimide anode and Prussian blue cathode. ACS Energy Lett. 2017;2(5):1115-1121.

[17] Komayko AI, Ryazantsev SV, Trussov IA, et al. The misconception of Mg²⁺ insertion into Prussian blue analogue structures from aqueous solution. ChemSusChem. 2021;14(6):1574-1585.

[18] Yang Y, Zhou J, Wang L, et al. Prussian blue and its analogues as cathode materials for Na-, K-, Mg-, Ca-, Zn- and Al-ion batteries. Nano Energy. 2022;99:107424.

[19] Sun X, Duffort V, Nazar LF. Prussian blue Mg-Li hybrid batteries. Adv Sci. 2016;3(8):1600044.

[20] Dong X, Chen L, Su X, Wang Y, Xia Y. Flexible aqueous lithium-ion battery with high safety and large volumetric energy density. Angew Chem Int Ed. 2016;55(26):7474-7477.

[21] Liu Q, Hu Z, Chen M, et al. The cathode choice for commercialization of sodium-ion batteries: layered transition metal oxides versus Prussian blue analogs. Adv Funct Mater. 2020;30(14):1909530.

[22] Hu Y, Guan C, Feng G, Ke Q, Huang X, Wang J. Flexible asymmetric supercapacitor based on structure-optimized Mn₃O₄/reduced graphene oxide nanohybrid paper with high energy and power density. Adv Funct Mater. 2015;25(47):7291-7299.

[23] Wang Q, Li J, Jin H, Xin S, Gao H. Prussian-blue materials: revealing new opportunities for rechargeable batteries. InfoMat. 2022;4(6):e12311.

[24] Ma L, Cui H, Chen S, Li X, Dong B, Zhi C. Accommodating diverse ions in Prussian blue analogs frameworks for rechargeable batteries: the electrochemical redox reactions. Nano Energy. 2021;81:105632.

[25] Zheng R, Li Y, Yu H, et al. Ammonium ion batteries: material, electrochemistry and strategy. Angew Chem Int Ed. 2023;62(23):e202301629.

[26] Xu C, Yang Z, Zhang X, et al. Prussian blue analogues in aqueous batteries and desalination batteries. Nano-Micro Lett. 2021;13(1):166.

[27] He H, Huang D, Tang Y, et al. Tuning nitrogen species in three-dimensional porous carbon via phosphorus doping for ultra-fast potassium storage. Nano Energy. 2019;57(3):728-736.

[28] Wang K, Fan X, Chen S, et al. 3D Co-doping α-Ni(OH)₂ nanosheets for ultrastable, high-rate Ni-Zn battery. Small. 2022;19(8):e2206287.

[29] Zhang Y, Li J, Zhao W, et al. Defect-free metal–organic framework membrane for precise ion/solvent separation toward highly stable magnesium metal anode. Adv Mater. 2022;34(6):2108114.

[30] Shimokawa K, Atsumi T, Okamoto NL, et al. Structure design of long-life spinel-oxide cathode materials for magnesium rechargeable batteries. Adv Mater. 2021;33(7):2007539.

[31] Bae J, Park H, Guo X, Zhang X, Warner JH, Yu G. High-performance magnesium metal batteries via switching the passivation film into a solid electrolyte interphase. Energ Environ Sci. 2021;14(8):4391-4399.

[32] Liu F, Wang T, Liu X, Fan LZ. Challenges and recent progress on key materials for rechargeable magnesium batteries. Adv Energy Mater. 2021;11(2):2000787.

[33] Zhu F, Zhang H, Lu Z, Kang D, Han L. Controlled defective engineering of MoS₂ nanosheets for rechargeable Mg batteries. J Energy Storage. 2021;42:103046.

[34] Liang G, Mo F, Li H, et al. A universal principle to design reversible aqueous batteries based on deposition-dissolution mechanism. Adv Energy Mater. 2019;9(32):1901838.

[35] Ma L, Chen S, Long C, et al. Achieving high-voltage and high-capacity aqueous rechargeable zinc ion battery by incorporating two-species redox reaction. Adv Energy Mater. 2019;9(45):1902446.

[36] Fu Q, Wu X, Luo X, et al. High-voltage aqueous Mg-ion batteries enabled by solvation structure reorganization. Adv Funct Mater. 2022;32(16):2110674.

[37] Shen Y, Zhang Q, Wang Y, Gu L, Zhao X, Shen X. A pyrite iron disulfide cathode with a copper current collector for high-energy reversible magnesium-ion storage. Adv Mater. 2021;33(41):2103881.

[38] Tang Y, Li X, Lv H, et al. High-energy aqueous magnesium hybrid full batteries enabled by carrier-hosting potential compensation. Angew Chem Int Ed. 2021;60(10):5443-5452.

[39] Leong KW, Pan W, Wang Y, Luo S, Zhao X, Leung DYC. Reversibility of a high-voltage, Cl⁻-regulated, aqueous Mg metal battery enabled by a water-in-salt electrolyte. ACS Energy Lett. 2022;7(8):2657-2666.

[40] Du A, Zhang H, Zhang Z, et al. A crosslinked polytetrahydrofuran-borate-based polymer electrolyte enabling wide-working-temperature-range rechargeable magnesium batteries. Adv Mater. 2019;31(11):1805930.

[41] Xu Y, Liu Z, Zheng X, et al. Solid electrolyte Interface regulated by solvent-in-water electrolyte enables high-voltage and stable aqueous Mg-MnO₂ batteries. Adv Energy Mater. 2022;12(22):2103352.

[42] Mizuno Y, Okubo M, Hosono E, et al. Electrochemical Mg²⁺ intercalation into a bimetallic CuFe Prussian blue analog in aqueous electrolytes. J Mater Chem A. 2013;1(42):13055-13059.

[43] Liu Y, He G, Jiang H, Parkin IP, Shearing PR, Brett DJL. Cathode design for aqueous rechargeable multivalent ion batteries: challenges and opportunities. Adv Funct Mater. 2021;31(13):2010445.

[44] Zeng Y, Lu XF, Zhang SL, Luan D, Li S, Lou XW(D). Construction of Co-Mn Prussian blue analog hollow spheres for efficient aqueous Zn-ion batteries. Angew Chem Int Ed. 2021;60(41):22189-22194.

[45] Li H, Okamoto NL, Hatakeyama T, Kumagai Y, Oba F, Ichitsubo T. Fast diffusion of multivalent ions facilitated by concerted interactions in dual-ion battery systems. Adv Energy Mater. 2018;8(27):1801475.

[46] Sun D, Zhu X, Luo B, et al. New binder-free metal phosphide-carbon felt composite anodes for sodium-ion battery. Adv Energy Mater. 2018;8(26):1801197.

[47] Xie B, Zuo P, Wang L, et al. Achieving long-life Prussian blue analogue cathode for Na-ion batteries via triple-cation lattice substitution and coordinated water capture. Nano Energy. 2019;61(7):201-210.

[48] Zhang X, Xia M, Yu H, et al. Hydrogen bond-assisted ultra-stable and fast aqueous NH₄⁺ storage. Nano-Micro Lett. 2021;13(1):139.

[49] Li J, Luo N, Kang L, et al. Hydrogen-bond reinforced superstructural manganese oxide as the cathode for ultra-stable aqueous zinc ion batteries. Adv Energy Mater. 2022;12(44):2201840.

[50] Zeng Y, Xu J, Wang Y, Li S, Luan D, Lou XW(D). Formation of CuMn Prussian blue analog double-shelled nanoboxes toward long-life Zn-ion batteries. Angew Chem Int ed. 2022;61(48):e202212031.

[51] Wang RY, Shyam B, Stone KH, et al. Reversible multivalent (monovalent, divalent, trivalent) ion insertion in open framework materials. Adv Energy Mater. 2015;5(12):1401869.

[52] Gao X, Wu H, Su C, et al. Recent advances in carbon-based nanomaterials for multivalent-ion hybrid capacitors: a review. Energy Environ Sci. 2023;16(4):1364-1383.

[53] Liu L, Niu Z, Chen J. Unconventional supercapacitors from nanocarbon-based electrode materials to device configurations. Chem Soc Rev. 2016;45(15):4340-4363.

[54] Nam KW, Kim S, Lee S, et al. The high performance of crystal water containing manganese birnessite cathodes for magnesium batteries. Nano Lett. 2015;15(6):4071-4079.

[55] Wang L, Zhu Y, Wen Y, et al. Regulating the local charge distribution of Ni active sites for the urea oxidation reaction. Angew Chem Int ed. 2021;60(19):10577-10582.

[56] Zhang Q, Man P, He B, et al. Binder-free NaTi₂(PO₄)₃ anodes for high-performance coaxial-fiber aqueous rechargeable sodium-ion batteries. Nano Energy. 2020;67:104212.

[57] Shi X, Zuo Y, Zhai P, et al. Large-area display textiles integrated with functional systems. Nature. 2021;591(7849):240-245.

[58] Sun H, You X, Deng J, et al. Novel graphene/carbon nanotube composite fibers for efficient wire-shaped miniature energy devices. Adv Mater. 2014;26(18):2868-2873.

[59] Shen Y, Zou J, Lan H, et al. Unlocking Prussian blue analogues inert-site to achieve high-capacity ammonium storage. Adv Funct Mater. 2024;2400598.

[60] Li Z, Shao M, Zhou L, et al. A flexible all-solid-state micro-supercapacitor based on hierarchical CuO@layered double hydroxide core–shell nanoarrays. Nano Energy. 2016;20(2):294-304.

[61] Yu D, Goh K, Wang H, et al. Scalable synthesis of hierarchically structured carbon nanotube-graphene fibres for capacitive energy storage. Nat Nanotechnol. 2014;9(7):555-562.

[62] Guo Z, Zhao Y, Ding Y, et al. Multi-functional flexible aqueous sodium-ion batteries with high safety. Chem. 2017;3(2):348-362.

[63] Huang Y, Ip WS, Lau YY, et al. Weavable, conductive yarn-based NiCo//Zn textile battery with high energy density and rate capability. ACS Nano. 2017;11(9):8953-8961.

[64] Li M, Meng J, Li Q, et al. Finely crafted 3D electrodes for dendrite-free and high-performance flexible fiber-shaped Zn-Co batteries. Adv Funct Mater. 2018;28(32):1802016.

[65] Zeng Y, Meng Y, Lai Z, et al. An ultrastable and high-performance flexible fiber-shaped Ni–Zn battery based on a Ni–NiO heterostructured nanosheet cathode. Adv Mater. 2017;29(44):1702698.

RIGHTS & PERMISSIONS

2024 The Authors. InfoMat published by UESTC and John Wiley & Sons Australia, Ltd.