skip to main content


The NSF Public Access Repository (NSF-PAR) system and access will be unavailable from 5:00 PM ET until 11:00 PM ET on Friday, June 21 due to maintenance. We apologize for the inconvenience.

This content will become publicly available on March 27, 2025

Title: Rechargeable Manganese Dioxide||Hard Carbon Lithium Batteries in an Ether Electrolyte

Earth-abundant, cost-effective electrode materials are essential for sustainable rechargeable batteries and global decarbonization. Manganese dioxide (MnO2) and hard carbon both exhibit high structural and chemical tunability, making them excellent electrode candidates for batteries. Herein, we elucidate the impact of electrolytes on the cycling performance of commercial electrolytic manganese dioxide in Li chemistry. We leverage synchrotron X-ray analysis to discern the chemical state and local structural characteristics of Mn during cycling, as well as to quantify the Mn deposition on the counter electrode. By using an ether-based electrolyte instead of conventional carbonate electrolytes, we circumvent the formation of a surface Mn(II)-layer and Mn dissolution from LixMnO2. Consequently, we achieved an impressive ∼100% capacity retention for MnO2after 300 cycles at C/3. To create a lithium metal-lean full cell, we introduce hard carbon as the anode which is compatible with ether-based electrolytes. Commercial hard carbon delivers a specific capacity of ∼230 mAh g−1at 0.1 A g−1without plateau, indicating a surface-adsorption mechanism. The resulting manganese dioxide||hard carbon full cell exhibits stable cycling and high Coulombic efficiency. Our research provides a promising solution to develop cost-effective, scalable, and safe energy storage solutions using widely available manganese oxide and hard carbon materials.

more » « less
Award ID(s):
Author(s) / Creator(s):
; ; ; ; ; ; ; ; ;
Publisher / Repository:
The Electrochemical Society
Date Published:
Journal Name:
Journal of The Electrochemical Society
Page Range / eLocation ID:
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    A low‐carbon future demands more affordable batteries utilizing abundant elements with sustainable end‐of‐life battery management. Despite the economic and environmental advantages of Li‐MnO2batteries, their application so far has been largely constrained to primary batteries. Here, we demonstrate that one of the major limiting factors preventing the stable cycling of Li‐MnO2batteries, Mn dissolution, can be effectively mitigated by employing a common ether electrolyte, 1 mol/L lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in 1,3‐dioxane (DOL)/1,2‐dimethoxyethane (DME). We discover that the suppression of this dissolution enables highly reversible cycling of the MnO2cathode regardless of the synthesized phase and morphology. Moreover, we find that both the LiPF6salt and carbonate solvents present in conventional electrolytes are responsible for previous cycling challenges. The ether electrolyte, paired with MnO2cathodes is able to demonstrate stable cycling performance at various rates, even at elevated temperature such as 60°C. Our discovery not only represents a defining step in Li‐MnO2batteries with extended life but provides design criteria of electrolytes for vast manganese‐based cathodes in rechargeable batteries.

    more » « less
  2. Abstract

    Rechargeable aqueous zinc‐ion batteries (ZIBs) have emerged as an alternative to lithium‐ion batteries due to their affordability and high level of safety. However, their commercialization is hindered by the low mass loading and irreversible structural changes of the cathode materials during cycling. Here, a disordered phase of a manganese nickel cobalt dioxide cathode material derived from wastewater via a coprecipitation process is reported. When used as the cathode for aqueous ZIBs , the developed electrode delivers 98% capacity retention at a current density of 0.1 A g−1and 72% capacity retention at 1 A g−1while maintaining high mass loading (15 mg cm−2). The high performance is attributed to the structural stability of the Co and Ni codoped phase; the dopants effectively suppress Jahn–Teller distortion of the manganese dioxide during cycling, as revealed by operando X‐ray absorption spectroscopy. Also, it is found that the Co and Ni co‐doped phase effectively inhibits the dissolution of Mn2+, resulting in enhanced durability without capacity decay at first 20 cycles. Further, it is found that the performance of the electrode is sensitive to the ratio of Ni to Co, providing important insight into rational design of more efficient cathode materials for low‐cost, sustainable, rechargeable aqueous ZIBs.

    more » « less
  3. Abstract

    A new concentrated ternary salt ether‐based electrolyte enables stable cycling of lithium metal battery (LMB) cells with high‐mass‐loading (13.8 mg cm−2, 2.5 mAh cm−2) NMC622 (LiNi0.6Co0.2Mn0.2O2) cathodes and 50 μm Li anodes. Termed “CETHER‐3,” this electrolyte is based on LiTFSI, LiDFOB, and LiBF4with 5 vol% fluorinated ethylene carbonate in 1,2‐dimethoxyethane. Commercial carbonate and state‐of‐the‐art binary salt ether electrolytes were also tested as baselines. With CETHER‐3, the electrochemical performance of the full‐cell battery is among the most favorably reported in terms of high‐voltage cycling stability. For example, LiNixMnyCo1–xyO2(NMC)‐Li metal cells retain 80% capacity at 430 cycles with a 4.4 V cut‐off and 83% capacity at 100 cycles with a 4.5 V cut‐off (charge at C/5, discharge at C/2). According to simulation by density functional theory and molecular dynamics, this favorable performance is an outcome of enhanced coordination between Li+and the solvent/salt molecules. Combining advanced microscopy (high‐resolution transmission electron microscopy, scanning electron microscopy) and surface science (X‐ray photoelectron spectroscopy, time‐of‐fight secondary ion mass spectroscopy, Fourier‐transform infrared spectroscopy, Raman spectroscopy), it is demonstrated that a thinner and more stable cathode electrolyte interphase (CEI) and solid electrolyte interphase (SEI) are formed. The CEI is rich in lithium sulfide (Li2SO3), while the SEI is rich in Li3N and LiF. During cycling, the CEI/SEI suppresses both the deleterious transformation of the cathode R‐3m layered near‐surface structure into disordered rock salt and the growth of lithium metal dendrites.

    more » « less
  4. Manganese dioxide (MnO 2 ) with different crystal structures has been widely investigated as the cathode material for Zn-ion batteries, among which spinel λ -MnO 2 is yet rarely reported because Zn-ion intercalation in spinel lattice is speculated to be limited by the narrow three-dimensional tunnels. In this work, we demonstrate that Zn-ion insertion in spinel lattice can be enhanced by reducing particle size and elucidate an intriguing electrochemical reaction mechanism dependent on particle size. Specifically, λ -MnO 2 nanoparticles (NPs, ~80 nm) deliver a high capacity of 250 mAh/g at 20 mA/g due to large surface area and solid-solution type phase transition pathway. Meanwhile, severe water-induced Mn dissolution leads to the poor cycling stability of NPs. In contrast, micron-sized λ -MnO 2 particles (MPs, ~0.9  μ m) unexpectedly undergo an activation process with the capacity continuously increasing over the first 50 cycles, which can be attributed to the formation of amorphous MnO x nanosheets in the open interstitial space of the MP electrode. By adding MnSO 4 to the electrolyte, Mn dissolution can be suppressed, leading to significant improvement in the cycling performance of NPs, with a capacity of 115 mAh/g retained at 1 A/g for over 500 cycles. This work pinpoints the distinctive impacts of the particle size on the reaction mechanism and cathode performance in aqueous Zn-ion batteries. 
    more » « less
  5. Abstract

    Benefiting from abundant resource reserves and considerable theoretical capacity, sodium (Na) metal is a strong anode candidate for low‐cost, large‐scale energy storage applications. However, extensive volume change and mossy/dendritic growth during Na electrodeposition have impeded the practical application of Na metal batteries. Herein, a self‐sodiophilic carbon host, lignin‐derived carbon nanofiber (LCNF), is reported to accommodate Na metal through an infiltration method. Na metal is completely encapsulated in the 3D space of the LCNF host, where the strong interaction between LCNF and Na metal is mediated by the self‐sodiophilic sites. The resulting LCNF@Na electrode delivers good cycling stability with a low voltage hysteresis and a dendrite‐free morphology in commercial carbonate‐based electrolytes. When interfaced with O3‐NaNi0.33Mn0.33Fe0.33O2and P2‐Na0.7Ni0.33Mn0.55Fe0.1Ti0.02O2cathodes in full cell Na metal batteries, the LCNF@Na electrode enables high capacity retentions, long cycle life, and good rate capability. Even in a “lean” Na anode environment, the full cells can still deliver good electrochemical performance. The overall stable battery performance, based on a self‐sodiophilic, biomass‐derived carbon host, illuminates a promising path towards enabling low‐cost Na metal batteries.

    more » « less