Layered Oxide Cathodes for Sodium-Ion Batteries: Storage Mechanism, Electrochemistry, and Techno-economics

Wenhua Zuo; Alessandro Innocenti; Maider Zarrabeitia; Dominic Bresser; Yong Yang; Stefano Passerini

doi:10.1021/acs.accounts.2c00690

Layered Oxide Cathodes for Sodium-Ion Batteries: Storage Mechanism, Electrochemistry, and Techno-economics

Acc Chem Res. 2023 Feb 7;56(3):284-296. doi: 10.1021/acs.accounts.2c00690. Epub 2023 Jan 25.

Authors

Wenhua Zuo^{1

2}, Alessandro Innocenti^{1

2}, Maider Zarrabeitia^{1

2}, Dominic Bresser^{1

2}, Yong Yang³, Stefano Passerini^{1

2

4}

Affiliations

¹ Helmholtz Institute Ulm (HIU), Helmholtzstrassse 11, D-89081 Ulm, Germany.
² Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe, Germany.
³ State Key Laboratory for Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Siming South Road 422, Xiamen 361005, People's Republic of China.
⁴ Chemistry Department, Sapienza University, Piazzale A. Moro 5, 00185 Rome, Italy.

Abstract

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 (Na_xTMO₂, 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 Na_xTMO₂ 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 Na_xTMO₂ 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 Na_xTMO₂. The favorable redox-active cations for Na_xTMO₂ are emphasized in terms of abundance, cost, supply, and energy density. Different working mechanisms related to Na_xTMO₂ 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 Na_xTMO₂, with an emphasis on the cost, large-scale fabrication capability, and electrochemical performance.