Preparation and research of W-doped α-MoO3 as anode materials for proton battery

doi:10.19799/j.cnki.2095-4239.2024.0248

Abstract

Abstract:

Protons carry one positive charge with the smallest ionic radius and mass. Hydrogen is a ubiquitous element on earth, this makes rechargeable proton battery systems the next generation of energy storage batteries. To date, anode materials for proton batteries, such as WO₃, TiO_2, and MXenes, still suffer from low discharge capacity and poor rate performance. α-MoO₃, one of the layered crystalline compounds composed of [MoO]₆ octahedra double sublayers connected by van der Waals interaction. α-MoO₃ possesses a high theoretical specific capacity of 558 mAh/g because of three electron reactions and low proton insertion potential, is recognized as one of the most promising anode materials for proton batteries. Unfortunately, α-MoO₃ suffers severe lattice distortion and damage in aqueous electrolytes during the discharge process, causing rapid decay of the reversible capacity. In this study, we report the synthesis of W-doped α-MoO₃for the first time. The XRD and RAMAN results show that the substitution of Mo with W results in a stronger W—O bond and enhances the inlayer Mo=O bond. Additionally, the interlayer spacing of α-MoO₃ increases from 13.84 to 13.87 Å after W-doping because the W⁶⁺ has a larger radius (0.60 Å) than Mo⁶⁺(0.59 Å). Moreover, the CV results showed that the redox reactions of the W-doped material were mainly controlled by charge transfer between the electrode surface atoms rather than proton diffusion mass transfer. The reversible discharge capacities of the α-MoO₃ and W_0.035Mo_0.965O₃ were 202.4 and 189.2 mAh/g at 5 C (1 A/g), respectively. After 600 cycles, the capacity retention is 83.0% for W_0.035Mo_0.965O₃ is higher than that of α-MoO₃(69.6%). Even at 125 C (25 A/g), W_0.035Mo_0.965O₃ delivers a discharge capacity of 144.2 mAh/g which is higher than that of α-MoO₃ (90.7 mAh/g). Subsequently, the full Swagelok cell was assembled using MnO₂ as the cathode, W_0.035Mo_0.965O₃ as the anode, glass-fiber filter paper as the separator, and 2 mol/L H₂SO₄ + 1 mol/L MnSO₄ as the electrolyte. At 15 C (3 A/g), the full cell exhibited a reversible capacity of 177.0 mAh/g and a capacity retention of 83.8% after 400 cycles. These results show that W doping effectively improves the cycling stability and rate performance of α-MoO₃ materials.

Key words: aqueous proton battery, α-MoO₃, tungsten doping, anode

CLC Number:

TM 911.1

Xiaofeng MA, Qinjun SHAO, Jian CHEN. Preparation and research of W-doped α-MoO₃ as anode materials for proton battery[J]. Energy Storage Science and Technology, 2024, 13(10): 3319-3333.

Figures/Tables 15

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样品	a/Å	b/Å	c/Å	Rwp
α-MoO₃	13.84496	3.697078	3.965169	8.01
WMoO-0.01	13.86930	3.696709	3.962225	8.33
WMoO-0.05	13.87088	3.696015	3.957191	9.33
WMoO-0.1	13.88168	3.695780	3.956262	8.45

样品	理论质量分数/%	实际质量分数/%
WMoO-0.01	0.91	0.91
WMoO-0.05	4.35	4.26
WMoO-0.1	8.24	8.08

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Preparation and research of W-doped α-MoO₃ as anode materials for proton battery

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