Development of Quasi-solid-state Na-ion Battery Based on Water-minimal Prussian Blue Cathode

doi:10.15541/jim20240063

Abstract

Abstract:

In comparison to Li-ion batteries, Na-ion batteries offer the benefits of low cost, good low-temperature performance, and safety, attracting great attention in the cost- and reliability-sensitive applications. With high capacity and low cost, Prussian blue-like materials (PBAs) stand as promising cathode materials for Na-ion batteries. However, the presence of crystalline water within their structure induces fast performance decay of the battery, serving as a critical bottleneck limiting their application. This work reports a facile thermal treatment strategy to effectively remove crystalline water from PBAs cathode materials, improving capacity retention from 73% to 88% after 340 cycles. The in-situ analysis uncovers that the initial loss of Coulombic efficiency of PBAs cathode is a result of its irreversible transformation from a trigonal form to cubic phase during the charging and discharging process. This issue can be addressed by introducing of Na₂C₂O₄ to compensate the irreversible Na loss in the cathode. On this basis, a high-performance quasi-solid-state Na-ion battery is built by pairing a low-water-content PBAs cathode with Na₂C₂O₄ additive and a hard carbon (HC) anode within a poly(ethylene glycol) diacrylate (PEGDA)-based quasi-solid-state electrolyte with high ionic conductivity and electrochemical stability. This battery exhibits the specific capacities ranging from 58 to 105 mAh·g^-1 at current densities from 20 to 500 mA·g^-1, capable of sustaining stable cycling for over 200 cycles. This study underscores the significant improvement in stability and capacity of PBAs cathode materials by the efficient removal of crystalline water in them.

Key words: Na-ion battery, quasi-solid-state battery, Prussian blue cathode, in-situ analysis

CLC Number:

TQ152

WANG Kunpeng, LIU Zhaolin, LIN Cunsheng, WANG Zhiyu. Development of Quasi-solid-state Na-ion Battery Based on Water-minimal Prussian Blue Cathode[J]. Journal of Inorganic Materials, 2024, 39(9): 1005-1012.

Figures/Tables 6

Fig. 1 TGA, morphology and structure analyses of PBAs cathode (a) TGA curves and (b) XRD patterns of Hw-PBAs and Lw-PBAs; (c-f) SEM images of (c, d) Hw-PBAs and (e, f) Lw-PBAs

Fig. 2 Chemical composition of PBAs cathode (a, b) Fe2p XPS spectra of (a) Hw-PBAs and (b) Lw-PBAs; (c, d) O1s XPS spectra of (c) Hw-PBAs and (d) Lw-PBAs

Fig. 3 Electrochemical performance of PBAs cathode in Na-ion half cell (a) Cycling performance of Lw-PBAs and Hw-PBAs cathodes at a current density of 100 mA·g-1; (b) Charge-discharge curves of Lw-PBAs cathode at 100 mA·g-1; (c) Rate capability of Lw-PBAs and Hw-PBAs cathodes at various current densities from 10 mA·g-1 to 500 mA·g-1; The voltage window is 2.0-3.8 V (vs. Na/Na+) for all half-cell tests; Colorful figures are available on website

Fig. 4 In-situ analysis of Na storage mechanism for Lw-PBAs cathode and HC anode (a) Charge-discharge curves of Lw-PBAs|LE|HC full cell; (b) In-situ XRD pattern of Lw-PBAs cathode during the operation of full cell; (c) Charge-discharge curves for the first cycle and (d) cycling stability of HC anode at a current density of 300 mA·g-1; (e) In-situ XRD pattern and (f) in-situ Raman spectra of HC anode during the operation of full cell; Colorful figures are available on website

Fig. 5 Effect of Na2C2O4 on the electrochemical performance of Lw-PBAs cathode (a) SEM image and (b) charge-discharge curves of Na2C2O4 with micrometer size at a current density of 180 mA·g-1; (c) Charge-discharge curves of Lw-PBAs|LE|HC full cells with or without adopting Na2C2O4 at a current density of 100 mA·g-1; (d) Rate performance of Lw-PBAs|LE|HC full cell with Na2C2O4 at various current densities from 10 to 500 mA·g-1; (e) Cycling stability of Lw-PBAs|LE|HC full cell with or without using Na2C2O4 at large current density of 500 mA·g-1; The voltage window is 1.5-3.8 V for all full-cell tests; Colorful figures are available on website

Fig. 6 Electrochemical performance of quasi-solid-state full cell based on Lw-PBAs cathode and PEGDA-based GPE (a) LSV curve at a scan rate of 5 mV·s-1; (b) EIS spectrum; (c) Charge-discharge curves at a current density of 100 mA·g-1; (d) Rate performance at current densities of 20-500 mA·g-1; (e) Cycling performance at 100 mA·g-1; The voltage window is 1.5-3.8 V for all full-cell tests

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