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Substantial Na-Ion Storage at High Current Rates: Redox-Pseudocapacitance through Sodium Oxide Formation.

ABSTRACT: Batteries and supercapacitors, both governed by electrochemical processes, operate by different electrochemical mechanisms which determine their characteristic energy and power densities. Battery materials store large amounts of energy by ion intercalation. Electrical double-layer capacitors store charge through surface-controlled ion adsorption which leads to high power and rapid charging, but much smaller amounts of energy stored. Pseudocapacitive materials offer the promise to combine these properties by storing charge through surface-controlled, battery-like redox reactions but at high rates approaching those of electrochemical double-layer capacitors. This work compares the pseudo-capacitive charge storage characteristics of self-organized titanium dioxide (TiO2-x) nanotubes (NTs) to flat TiO2-x surface films to further elucidate the proposed charge storage mechanism within the formed surface films. By comparing TiO2-x NTs to flat TiO2-x surface films, having distinctively different oxide mass and surface area ratios, it is shown that NaO2 and Na2O2 formation, which constitutes the active surface film material, is governed by the metal oxide bulk. Our results corroborate that oxygen diffusion from the lattice oxide is key to NaO2 and Na2O2 formation.

SUBMITTER: Portenkirchner E

PROVIDER: S-EPMC9737611 | biostudies-literature | 2022 Nov

REPOSITORIES: biostudies-literature

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Substantial Na-Ion Storage at High Current Rates: Redox-Pseudocapacitance through Sodium Oxide Formation.

Portenkirchner Engelbert E

Nanomaterials (Basel, Switzerland) 20221130 23

Batteries and supercapacitors, both governed by electrochemical processes, operate by different electrochemical mechanisms which determine their characteristic energy and power densities. Battery materials store large amounts of energy by ion intercalation. Electrical double-layer capacitors store charge through surface-controlled ion adsorption which leads to high power and rapid charging, but much smaller amounts of energy stored. Pseudocapacitive materials offer the promise to combine these p ...[more]

PMID: 36500888

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Project description:ConspectusLithium-ion batteries (LIBs) are ubiquitous in all modern portable electronic devices such as mobile phones and laptops as well as for powering hybrid electric vehicles and other large-scale devices. Sodium-ion batteries (NIBs), which possess a similar cell configuration and working mechanism, have already been proven as ideal alternatives for large-scale energy storage systems. The advantages of NIBs are as follows. First, sodium resources are abundantly distributed in the earth's crust. Second, high-performance NIB cathode materials can be fabricated by using solely inexpensive and noncritical transition metals such as manganese and iron, which further reduces the cost of the required raw materials. Recently, the unprecedented demand for lithium and other critical minerals has driven the cost of these primary raw materials (which are utilized in LIBs) to a historic high and thus triggered the commercialization of NIBs.Sodium layered transition metal oxides (NaxTMO2, TM = transition metal/s), such as Mn-based sodium layered oxides, represent an important family of cathode materials with the potential to reduce costs, increase energy density and cycling stability, and improve the safety of NIBs for large-scale energy storage. However, these layered oxides face several key challenges, including irreversible phase transformations during cycling, poor air stability, complex charge-compensation mechanisms, and relatively high cost of the full cell compared to LiFePO4-based LIBs. Our work has focused on the techno-economic analysis, the degradation mechanism of NaxTMO2 upon cycling and air exposure, and the development of effective strategies to improve their electrochemical performances and air stability. Correlating structure-performance relationships and establishing general design strategies of NaxTMO2 must be considered for the commercialization of NIBs.In this Account, we discuss the recent progress in the development of air-stable, electrochemically stable, and cost-effective NaxTMO2. The favorable redox-active cations for NaxTMO2 are emphasized in terms of abundance, cost, supply, and energy density. Different working mechanisms related to NaxTMO2 are summarized, including the electrochemical reversibility, the main structural transformations during the charge and discharge processes, and the charge-compensation mechanisms that accompany the (de)intercalation of Na+ ions, followed by discussions to improve the stability toward ambient air and upon cycling. Then the techno-economics are presented, with an emphasis on cathodes with different chemical compositions, cost breakdown of battery packs, and Na deficiency, factors that are critical to the large-scale implementation. Finally, this Account concludes with an overview of the remaining challenges and new opportunities concerning the practical applications of NaxTMO2, with an emphasis on the cost, large-scale fabrication capability, and electrochemical performance.

Dataset Information

Substantial Na-Ion Storage at High Current Rates: Redox-Pseudocapacitance through Sodium Oxide Formation.

Publications

Substantial Na-Ion Storage at High Current Rates: Redox-Pseudocapacitance through Sodium Oxide Formation.

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