Biomimetic composite architecture achieves ultrahigh rate capability and cycling life of sodium ion battery cathodes

Kang Ho Shin,Sul Ki Park,Min Sung Choi,Seong-Min Bak,Puritut Nakhanivej,Pengcheng Liu,David Mitlin,Ho Seok Park,Yixian Wang

doi:10.1063/5.0020805

Abstract

Sodium ion batteries are an emerging candidate to replace lithium ion batteries in large-scale electrical energy storage systems due to the abundance and widespread distribution of sodium. Despite the growing interest, the development of high-performance sodium cathode materials remains a challenge. In particular, polyanionic compounds are considered as a strong cathode candidate owing to their better cycling stability, a flatter voltage profile, and stronger thermal stability compared to other cathode materials. Here, we report the rational design of a biomimetic bone-inspired polyanionic Na3V2(PO4)3-reduced graphene oxide composite (BI-NVP) cathode that achieves ultrahigh rate charging and ultralong cycling life in a sodium ion battery. At a charging rate of 1 C, BI-NVP delivers 97% of its theoretical capacity and is able to retain a voltage plateau even at the ultra-high rate of 200 C. It also shows long cycling life with capacity retention of 91% after 10 000 cycles at 50 C. The sodium ion battery cells with a BI-NVP cathode and Na metal anode were able to deliver a maximum specific energy of 350 W h kg−1 and maximum specific power of 154 kW kg−1. In situ and postmortem analyses of cycled BI-NVP (including by Raman and XRD spectra) HRTEM, and STEM-EELS, indicate highly reversible dilation–contraction, negligible electrode pulverization, and a stable NVP-reduced graphene oxide layer interface. The results presented here provide a rational and biomimetic material design for the electrode architecture for ultrahigh power and ultralong cyclability of the sodium ion battery full cells when paired with a sodium metal anode.

Highlights

Polyanionic compounds are considered as a strong cathode candidate owing to their better cycling stability, a flatter voltage profile, and stronger thermal stability compared to other cathode materials
We report the rational design of a biomimetic bone-inspired polyanionic Na3V2(PO4)3-reduced graphene oxide composite (BI-NVP) cathode that achieves ultrahigh rate charging and ultralong cycling life in a sodium ion battery
The inner NVP granules are interconnected with the rGO, forming a porous composite structure, as shown in the scanning electron microscopy (SEM) image [Fig. 1(b)]

Summary

Introduction

The rapid development of cost-efficient large-scale electrical energy storage systems (ESSs) has led to remarkable progress on the exploitation of renewable energy resources, such as solar energy, wind energy, and tidal energy. Owing to the abundance and widespread distribution of sodium, sodium ion batteries (SIBs) are a strong candidate to replace lithium ion batteries (LIBs) for large-scale EESs. the development of high-performance sodium cathode materials remains challenging. Extensive efforts have been devoted to investigating cathode materials, especially sodium-layered oxides and polyanionic compounds. Despite the high specific capacity of layered compounds, they often lack structural stability in the highly charged state and require a low discharge cutoff voltage to achieve enough capacity. In a sharp contrast to oxides, most polyanionic compounds have a three-dimensional (3D) robust framework due to strong covalent bonding of the oxygen atom in the polyanion polyhedra. The development of high-performance sodium cathode materials remains challenging.. Extensive efforts have been devoted to investigating cathode materials, especially sodium-layered oxides and polyanionic compounds.. Despite the high specific capacity of layered compounds, they often lack structural stability in the highly charged state and require a low discharge cutoff voltage to achieve enough capacity.. In a sharp contrast to oxides, most polyanionic compounds have a three-dimensional (3D) robust framework due to strong covalent bonding of the oxygen atom in the polyanion polyhedra. This provides for better cycling stability, flatter voltage profile, stronger thermal stability, and higher safety. Owing to the inductive effect of the polyanion groups, a higher operating voltage can be achieved.

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Conclusion