Stable Cycling of Ultrahigh Mass Loaded MnO2 for Low-Cost Sodium-Ion Batteries

Abstract

Achieving cost-effective and sustainable solutions for large-scale energy storage is critical for advancing the global clean energy transition. The intermittent nature of green energy underscores the inadequacy of current large scale energy storage technologies like pumped hydroelectricity which is susceptible to geographic and water resource constraints, making batteries a prime candidate for this role. Although lithium-ion batteries (LIBs) with high energy and power density are a viable solution, the high cost and uneven distribution of lithium reserves limits the widespread application of LIBs for grid energy storage. Considering these developments and the challenges posed by limited lithium reserves, sustainable and low-cost sodium-ion batteries (SIBs) emerge as a promising alternative.Among the various battery electrode materials, manganese dioxide (MnO2) stands out as a promising choice for large-scale energy storage applications due to its earth abundance, cost-effectiveness and non-toxic nature. Although MnO2 is known as a pseudocapacitive material with superior cycling stability in aqueous electrolytes, its dissolution in non-aqueous electrolytes has restricted its widespread use in long lifetime batteries. In this study, we demonstrate that an ether-based electrolyte solution (1M NaClO4 in diglyme) is able to achieve stable cycling of electrodeposited ε-MnO2 as a cathode for SIBs, reaching a over 75% capacity retention over 1000 cycles. This response surpasses conventional ester-based electrolytes (58% of 1M NaClO4 in EC/PC). A comparative cycling stability study, coupled with electrochemical quartz crystal microbalance characterization, validates the efficacy of the ether-based electrolyte in mitigating MnO2 dissolution. Furthermore, the integration of 3D printed graphene aerogel (3D GA) as a scaffold for electrodeposited MnO2 leads to enhanced electrochemical performance of the MnO2 electrode (3D MnO2/GA), resulting in a high areal capacity of 4.4 mAh cm-2 at a current density of 10 mA cm-2. The 3D MnO2/GA electrode possesses scalable electrochemical performance with mass loadings from 20 mg cm-2 to 80 mg cm-2. Using this electrode, a high mass loaded sodium-ion battery (SIB) device was fabricated by using utilizing 58 mg cm-2 3D MnO2/GA as the cathode and 16 mg cm-2 dip-coated TiO2@Cu foam as the anode. This MnO2 | TiO2 device delivered a notable areal capacity of 6.2 mWh cm-2 and a high areal power density of 70.7 mW cm-2. Moreover, the SIB device demonstrates 85% capacity retention after 500 cycles, underscoring the stable cycling of this high-energy and power-density SIB device.