Dilute Aqueous-Aprotic Electrolyte Towards Robust Zn-Ion Hybrid Supercapacitor with High Operation Voltage and Long Lifespan

doi:10.1007/s40820-024-01372-x

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Abstract

With the merits of the high energy density of batteries and power density of supercapacitors, the aqueous Zn-ion hybrid supercapacitors emerge as a promising candidate for applications where both rapid energy delivery and moderate energy storage are required. However, the narrow electrochemical window of aqueous electrolytes induces severe side reactions on the Zn metal anode and shortens its lifespan. It also limits the operation voltage and energy density of the Zn-ion hybrid supercapacitors. Using ‘water in salt’ electrolytes can effectively broaden their electrochemical windows, but this is at the expense of high cost, low ionic conductivity, and narrow temperature compatibility, compromising the electrochemical performance of the Zn-ion hybrid supercapacitors. Thus, designing a new electrolyte to balance these factors towards high-performance Zn-ion hybrid supercapacitors is urgent and necessary. We developed a dilute water/acetonitrile electrolyte (0.5 m Zn(CF₃SO₃)₂ + 1 m LiTFSI-H₂O/AN) for Zn-ion hybrid supercapacitors, which simultaneously exhibited expanded electrochemical window, decent ionic conductivity, and broad temperature compatibility. In this electrolyte, the hydration shells and hydrogen bonds are significantly modulated by the acetonitrile and TFSI⁻ anions. As a result, a Zn-ion hybrid supercapacitor with such an electrolyte demonstrates a high operating voltage up to 2.2 V and long lifespan beyond 120,000 cycles.

Key words： Zn-ion supercapacitors Zn metal anode Electrolyte engineering Hydrogen bonds Solvation structures

Received: 15 November 2023 Published: 25 March 2024

Corresponding Authors: Bolong Huang, Wenjun Zhang

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	Articles by authors
	Shuilin Wu
	Yibing Yang
	Mingzi Sun
	Tian Zhang
	Shaozhuan Huang
	Daohong Zhang
	Bolong Huang
	Pengfei Wang
	Wenjun Zhang

Cite this article:

Shuilin Wu,Yibing Yang,Mingzi Sun, et al. Dilute Aqueous-Aprotic Electrolyte Towards Robust Zn-Ion Hybrid Supercapacitor with High Operation Voltage and Long Lifespan[J]. Nano-Micro Letters, 2024, 16(1): 161-.

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https://www.qk.sjtu.edu.cn/nml/EN/10.1007/s40820-024-01372-x OR https://www.qk.sjtu.edu.cn/nml/EN/Y2024/V16/I1/161

Fig. 1 Evaluation of the stability of Zn metal anode in 0.5 m Zn(CF3SO3)2 + 1 m LiTFSI H2O/AN electrolyte. a Tafel plots of Zn plating/stripping in the 0.5 m + 1 m-H2O/AN and reference aqueous electrolytes. b The plots of current density versus time of the Zn-Ti galvanic cells in the 0.5 m + 1 m-H2O/AN and reference aqueous electrolytes. c Coulombic efficiencies of the Zn-Cu cells with the 0.5 m + 1 m-H2O/AN and reference aqueous electrolytes at various current densities (0.5-10 mA cm−2). d Voltage profiles of Zn-Zn symmetric cells in the 0.5 m + 1 m-H2O/AN at various current densities (0.5-10 mA cm−2). e Coulombic efficiency of the Zn-Cu cell with the 0.5 m + 1 m-H2O/AN electrolyte at 5 mA cm−2, inset is the charge-discharge curves at specific cycles (e.g., the 10th, 100th, 500th, 1000th, 2000th and 3000th cycle). f Voltage profiles of the Zn-Zn symmetric cells with the 0.5 m + 1 m-H2O/AN and reference aqueous electrolytes at 5 mA cm−2; the areal capacity of these tests is 0.5 mAh cm−2 for each cycle

Fig. 2 Electrochemical performance of the Zn-aMEGO hybrid supercapacitor with 0.5 m + 1 m-H2O/AN electrolyte. a Galvanostatic charge-discharge curves of the device with different voltage ranges at 0.5 A g−1. b Cyclic voltammetry curves of the device at various scan rates (5-100 mV s−1) within 0-2.2 V. c Rate capability of the device within a voltage range of 0-2.2 V. d Cycling stability of the device at 15 A g−1 within 0-2.2 V. e The galvanostatic charge-discharge curves of the device after specific cycles at 15 A g−1

Fig. 3 The electrochemical performance of 0.5 m + 1 m-H2O/AN electrolyte at low temperature (− 30 °C). a Charge-discharge curves of the Zn-Cu cells at different current densities. b Voltage profiles of the Zn-Zn cells at various current densities. c Coulombic efficiency of the Zn-Cu cells at 5 mA cm−2, inset is the charge-discharge curves at the specific cycles. The cyclic voltammetry curves of the Zn-aMEGO hybrid supercapacitors with d the 0.5 m + 1 m-H2O/AN electrolyte and e the 0.5 m + 1 m-H2O aqueous electrolyte under different temperatures at a scan rate of 100 mV s−1. f The capacitance retention of the Zn-aMEGO supercapacitors with 0.5 m + 1 m-H2O/AN electrolyte at 1 A g−1 within a voltage range of 0-2.2 V, inset is the charge-discharge curves of the device after specific cycles

Fig. 4 3D contour plots of the anti-bonding and bonding orbitals of a 0.5 m + 1 m-H2O electrolyte, b 0.5 m + 1 m-H2O/AN electrolyte, c 0.5 m + 3 m-H2O/AN electrolyte, and d 0.5 m + 5 m-H2O/AN electrolyte. Red balls = O, white balls = H, purple balls = Li, grey balls = Zn, yellow balls = S, dark blue balls = N, light blue balls = F; blue isosurface = bonding orbitals, green isosurface = anti-bonding orbitals. The PDOSs of e 0.5 m + 1 m-H2O electrolyte, f 0.5 m + 1 m-H2O/AN electrolyte, g 0.5 m + 3 m-H2O/AN electrolyte, and h 0.5 m + 5 m-H2O/AN electrolyte. The radial distribution function (RDF) comparison of i 0.5 m + 1 m-H2O electrolyte and j 0.5 m + 1 m-H2O/AN electrolyte. k Interaction energies comparison. l Mean square displacement (MSD) of different electrolytes at 298 K. (Color figure online)

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