Rational design and demonstration of a high-performance flexible Zn/V2O5 battery with thin-film electrodes and para-polybenzimidazole electrolyte membrane

doi:10.1016/j.ensm.2020.02.016

Energy Storage Materials

Volume 27, May 2020, Pages 418-425

https://doi.org/10.1016/j.ensm.2020.02.016 Get rights and content

Highlights

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New atomic layer deposited V₂O₅ cathode.
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New para-PBI membrane electrolyte.
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Use of low-cost, flexible electrically conducting substrates.
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Integration of three thin-film membranes into functional flexible battery.

Abstract

Flexible energy storage devices with high energy density and long lifespan are in great demand for wearable and stretchable electronics. Herein, we report a flexible Zn-ion battery comprised of atomic layer deposited V₂O₅/C cathode, electrodeposited Zn/stainless-steel mesh anode, and para-polybenzimidazole (p-PBI)-based quasi-solid-state electrolyte membrane. The electrochemical and mechanical performances of such a thin-film Zn-ion battery are excellent, exhibiting high and stable reversible capacity with great flexibility over a wide temperature range.

Graphical abstract

An advanced flexible Zn/V₂O₅ battery consisting of self-standing thin-film electrodes and p-PBI membrane electrolyte is demonstrated with flexibility, high capacity and stability over a wide-temperature-range.

Introduction

Flexible and portable energy storage devices are in high demand in recent years due to the rapid development of wearable and stretchable electronics (WSE) [1,2]. Aqueous Zn-ion batteries (ZIBs) based on mildly-acidic-to-neutral electrolytes are environmentally benign, safe and energy intense, and thus have attracted significant interests for WSE applications [3,4]. A key to the development of flexible ZIBs is to afford the three basic battery components [5], viz. electrolyte, cathode, and anode, with proper flexibility. So far, flexible ZIBs based on chemistries of Zn/MnO₂ [6], Zn/Ag [7], and Zn/Ni [8] have been reported in the literature. Despite good progress in flexibility, most research efforts are simply focused on an individual component of either electrode or electrolyte. For example, Li et al. demonstrated a flexible cathode consisting of a branch-like Co(CO₃)_0.5(OH)_x·0.11H₂O @CoMoO₄ and a trilayer ZnO@C–Zn anode in a Zn/Co battery, but still used a traditional, unoptimized gel electrolyte [9]. Similarly, Zhi et al. focused on developing a flexible electrolyte membrane based on gelatin and polyacrylamide but used a MnO₂ cathode supported on a less flexible current-collector and Zn foil anode [10]. Nevertheless, the design and integration of all three basic cell components with mechanical flexibility, chemical compatibility, and electrochemical excellence in one single battery has been rarely reported. Another lacking area for flexible ZIBs is the effect of temperature on the performance since many practical applications could involve either higher or lower than room temperature operation.

Quasi-solid-state (QSS) electrolytes consisting of Zn salts immobilized by polymeric hosts represent a promising class of ionic conductors for flexible ZIBs [11]. The intrinsic plasticity of a polymer can provide the needed flexibility and stretchability, while the liquid-phase Zn-salt offers Zn²⁺ conductivity. The polymer scaffolds that have been investigated for flexible ZIBs include gelatin [10,12], poly(vinyl alcohol) (PVA) [13], poly (vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP) [14], and cellulose nanofibers [15], etc. However, the performances of these polymer-based electrolytes are usually limited by the competing requirements for ionic conductivity and mechanical properties. More importantly, most of these polymers cannot operate over a wide-temperature-range because of their poor thermal stability. Developing flexible cathodes and anodes are equally important for the advancement of flexible ZIBs. Layer structured V₂O₅ is considered as a benchmark ZIB cathode because of its high theoretical capacity (e.g. 589 mAh g⁻¹ for V⁵⁺/V³⁺ redox couple) and large interplanar spacing suited for Zn²⁺-intercalation. However, its performance is limited by the low electronic conductivity and large structural deformation during cycling. Depositing a nanoscaled V₂O₅ layer on lightweight, strong, flexible and conductive substrates is an effective solution to simultaneously lower resistance and improve structural stability [16]. Similarly, electrodeposited nanosized Zn anode on an elastic and conductive substrate is a good candidate for flexible ZIB anode. However, while the substrate is flexible, the bonding strength between the active materials (V₂O₅ or Zn) and the substrates must also be strong enough to withstand repeated bending forces experienced in practical applications. Therefore, new designs of flexible electrode structures and electrolyte membranes are still needed for flexible ZIBs.

Herein, we report on a flexible, yet high-performance Zn/V₂O₅ battery. The battery is comprised of an atomic layer deposited (ALD) V₂O₅ cathode, a thermally stable para-polybenzimidazole (p-PBI) membrane electrolyte, and an electrodeposited Zn anode. The substrates for ALD-V₂O₅ and Zn are a commercial porous graphite paper and stainless-steel mesh (SS-mesh), respectively. The electrolyte is a p-PBI membrane imbibed with a Zn-salt. We show that such configured ZIB exhibits not only excellent mechanical flexibility and structural stability, but also superior electrochemical performance over a wide temperature range.

Section snippets

Synthesis of ALD-V2O5 on graphite paper

A commercial graphite paper (0.13 mm thick, Alfa Aesar) was first treated in a 15 M HNO₃ for 60 min at 80 °C to functionalize the surface. This acid treatment could also help the nucleation of V₂O₅ for ALD. The treated graphite paper was then rinsed with deionized (DI) water and ethanol multiple times and dried in a vacuum oven at 70 °C for 12h. The ALD process was conducted on a flow-type reactor (Ultratech Savannah 200 series). Vanadium triisopropoxide (VTIP) (96%, Alfa Aesar) and DI

Design and fabrication of flexible multilayer Zn/V₂O₅ battery

The overall structure design of the flexible multilayer Zn/V₂O₅ battery and self-standing cathode/anode films are schematically illustrated in Fig. 1a and b, respectively. A detailed fabrication procedure describing preparation of individual self-standing films as well as overall multilayer structure is provided in the Experimental Section. Fig. 1c of X-ray diffraction (XRD) pattern indicates that the as-prepared ALD-V₂O₅/C is virtually a mixture of C (as indexed by the major peak at 26.5°) and

Conclusion

In summary, a flexible pouch-type Zn/V₂O₅ battery is demonstrated based on self-standing films of ALD-V₂O₅/C cathode, Zn/SS-mesh anode, and p-PBI membrane electrolyte. In this proof-of-concept flexible battery, the electrodes of Zn nanoflakes and ALD-V₂O₅ nanolayer are tightly bonded to the 3D porous substrates, which allows high integrity of electrodes with efficient charge transfer and fast Zn²⁺ diffusion. The p-PBI membrane electrolyte with high mechanical strength and thermal/chemical

CRediT authorship contribution statement

Yanying Lu: Investigation, Data curation, Writing - original draft. Yeting Wen: Methodology. Fei Huang: Methodology, Data curation. Tianyu Zhu: Data curation, Writing - review & editing. Shichen Sun: Conceptualization, Validation. Brian C. Benicewicz: Conceptualization, Validation, Writing - review & editing. Kevin Huang: Supervision, Writing - review & editing.

Declaration of competing interest

The authors declare no conflicts of interest.

Acknowledgements

KH and BCB acknowledge the support from the South Carolina Smart State program, United States.

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Citation Excerpt :
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Rational design and demonstration of a high-performance flexible Zn/V2O5 battery with thin-film electrodes and para-polybenzimidazole electrolyte membrane

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Synthesis of ALD-V2O5 on graphite paper

Design and fabrication of flexible multilayer Zn/V2O5 battery

Conclusion

CRediT authorship contribution statement

Declaration of competing interest

Acknowledgements

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