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Noninterference Revealing of "Layered to Layered" Zinc Storage Mechanism of ?-MnO2 toward Neutral Zn-Mn Batteries with Superior Performance.

ABSTRACT: MnO2 is one of the most studied cathodes for aqueous neutral zinc-ion batteries. However, the diverse reported crystal structures of MnO2 compared to ?-MnO2 inevitably suffer a structural phase transition from tunneled to layered Zn-buserite during the initial cycles, which is not as kinetically direct as the conventional intercalation electrochemistry in layered materials and thus poses great challenges to the performance and multifunctionality of devices. Here, a binder-free ?-MnO2 cathode is designed and a favorable "layered to layered" Zn2+ storage mechanism is revealed systematically using such a "noninterferencing" electrode platform in combination with ab initio calculation. A flexible quasi-solid-state Zn-Mn battery with an electrodeposited flexible Zn anode is further assembled, exhibiting high energy density (35.11 mWh cm-3; 432.05 Wh kg-1), high power density (676.92 mW cm-3; 8.33 kW kg-1), extremely low self-discharge rate, and ultralong stability up to 10 000 cycles. Even with a relatively high ?-MnO2 mass loading of 5 mg cm-2, significant energy and power densities are still achieved. The device also works well over a broad temperature range (0-40 °C) and can efficiently power different types of small electronics. This work provides an opportunity to develop high-performance multivalent-ion batteries via the design of a kinetically favorable host structure.

SUBMITTER: Jiang Y

PROVIDER: S-EPMC7080538 | biostudies-literature | 2020 Mar

REPOSITORIES: biostudies-literature

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Noninterference Revealing of "Layered to Layered" Zinc Storage Mechanism of δ-MnO2 toward Neutral Zn-Mn Batteries with Superior Performance.

Jiang Yuqi Y Ba Deliang D Li Yuanyuan Y Liu Jinping J

Advanced science (Weinheim, Baden-Wurttemberg, Germany) 20200116 6

MnO2 is one of the most studied cathodes for aqueous neutral zinc-ion batteries. However, the diverse reported crystal structures of MnO2 compared to δ-MnO2 inevitably suffer a structural phase transition from tunneled to layered Zn-buserite during the initial cycles, which is not as kinetically direct as the conventional intercalation electrochemistry in layered materials and thus poses great challenges to the performance and multifunctionality of devices. Here, ...[more]

PMID: 32195094

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Project description:Nanoparticles produced by bacteria, fungi, or plants generally have physicochemical properties such as size, shape, crystalline structure, magnetic properties, and stability which are difficult to obtain by chemical synthesis. For instance, Mn(II)-oxidizing organisms promote the biomineralization of manganese oxides with specific textures under ambient conditions. Controlling their crystallinity and texture may offer environmentally relevant routes of Mn oxide synthesis with potential technological applications, e.g., for energy storage. However, whereas the electrochemical activity of synthetic (abiotic) Mn oxides has been extensively studied, the electroactivity of Mn biominerals has been seldom investigated yet. Here we evaluated the electroactivity of biologically induced biominerals produced by the Mn(II)-oxidizer bacteria Pseudomonas putida strain MnB1. For this purpose, we explored the mechanisms of Mn biomineralization, including the kinetics of Mn(II) oxidation, under different conditions. Manganese speciation, biomineral structure, and texture as well as organic matter content were determined by a combination of X-ray diffraction, electron and X-ray microscopies, and thermogravimetric analyses coupled to mass spectrometry. Our results evidence the formation of an organic-inorganic composite material and a competition between the enzymatic (biotic) oxidation of Mn(II) to Mn(IV) yielding MnO2 birnessite and the abiotic formation of Mn(III), of which the ratio depends on oxygenation levels and activity of the bacteria. We reveal that a subtle control over the conditions of the microbial environment orients the birnessite to Mn(III)-phases ratio and the porosity of the assembly, which both strongly impact the bulk electroactivity of the composite biomineral. The electrochemical properties were tested in lithium battery configuration and exhibit very appealing performances (voltage, capacity, reversibility, and power capability), thanks to the specific texture resulting from the microbially driven synthesis route. Given that such electroactive Mn biominerals are widespread in the environment, our study opens an alternative route for the synthesis of performing electrode materials under environment-friendly conditions.

Dataset Information

Noninterference Revealing of "Layered to Layered" Zinc Storage Mechanism of ?-MnO2 toward Neutral Zn-Mn Batteries with Superior Performance.

Publications

Noninterference Revealing of "Layered to Layered" Zinc Storage Mechanism of δ-MnO<sub>2</sub> toward Neutral Zn-Mn Batteries with Superior Performance.

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