Interfacial binary doping strategy to achieve high capacity and cyclic stability in polyaniline cathodes for aqueous zinc ion batteries

Industrial VN@reduced graphene oxide cathode for aqueous zinc ion batteries with high rate capability and long cycle stability

With the fast development of diverse electronics, the demand for safe energy storage systems with high energy density and high stability has increased rapidly. So far, lithium-ion batteries (LIBs) have dominated the market, from small smart electronics to electric vehicles. Nevertheless, LIBs have several limitations, such as high cost, limited raw material resources, high flammability, and harsh environmental impact. Therefore, novel rechargeable batteries which can mitigate these shortcomings must be explored. Aqueous zinc-ion batteries (ZIBs) have shown a promising future. Zinc with high theoretical volumetric capacity (5855 mAh cm-3) and high stability in aqueous electrolytes should enable high-performing, safe, and low-cost batteries. Additionally, the simple assembly of ZIBs in the ambient environment results in low capital costs. Despite these attractive merits, developing cathode materials with high capacity, rate performance, and stability in order to build commercial high-performing ZIBs, remains a great challenge.Cathode materials directly influence the electrochemical performance of ZIBs. Manganese oxide (MnO2) has been investigated as a promising cathode in ZIBs research due to its good specific capacity, low cost and high safety. However, the low ionic conductivity, slow diffusion kinetics, and low stability of MnO2 severely deteriorate the electrochemical performance and cycling stability of zinc-ion batteries. Recently, a series of studies have revealed the high effectiveness of coating on improving MnO2 cathode stability, including polymer coatings, carbon-based material coatings, artificial cathode-electrolyte interfaces, and metal oxide coatings.[1] Nevertheless, the improvement of other parameters, such as the rate performance, could be further improved for practical usage. In this research, we develop a novel modification method combining coating and doping strategies to induce MnO2 cathode with high capacity, high rate performance and low capacity decay after long-term operation. First, we utilize a facile one-step hydrothermal synthesis for Ag-doped α-MnO2. Different amounts of AgNO3 are added into reactors with KMnO4 and MnSO4 (n(Ag):n(Mn)=1:100-4:100) to investigate the influence of doping on capacity and rate performance. Subsequently, the doped tunnel-type MnO2 cathodes are mixed with precursor solutions of Al2O3 and then thoroughly stirred. Finally, an annealing process is conducted to achieve a nanoscale Al2O3 coating on the tunnel type MnO2. The coating configurations influence the electrochemical performance of cathodes;[2] thus, we test precursor solutions with different concentrations (1-3 wt% Al2O3) and annealing temperatures (500-700 °C) to investigate the influence of coating thickness and annealing treatment.With the assistance of scanning and transmission electron microscopes, the nanoscale Al2O3 layer coating on the doped active material is verified. The stable Al2O3 coating protects active materials from dissolution and structural collapse, improving cycling stability and resulting in high capacity retention after long-term operation. Moreover, a significant improvement in rate performance compared to unmodified MnO2 is verified through electrochemical tests. The X-ray photoelectron spectroscopy (XPS) and EPR spectra showed that the doped Ag+ ions lead to oxygen vacancies due to the formation of Ag-O-Mn.[3] The abundant vacancies act as active sites, significantly improving conductivity and ion insertion rates. The ex-situ X-ray diffractometer (XRD) and electrochemical tests are used to investigate the ion insertion mechanism during charging/discharging operations. The Ag-MnO2 @ Al2O3 cathode is synthesized through a facile methodology with environment-friendly materials. The modified cathode exhibits promising performance, especially regarding cycling stability and rate performance, which will be a crucial step for developing high-performing cathodes in aqueous zinc-ion batteries.Reference:[1] Shi, W., Lee, W. S. V., & Xue, J. (2021). Recent development of Mn‐based oxides as zinc‐ion battery cathode. ChemSusChem, 14(7), 1634-1658.[2] Zhou, A., Xu, J., Dai, X., Yang, B., Lu, Y., Wang, L., ... & Li, J. (2016). Improved high-voltage and high-temperature electrochemical performances of LiCoO2 cathode by electrode sputter-coating with Li3PO4. Journal of Power Sources, 322, 10-16.[3] Pu, X., Li, X., Wang, L., Maleki Kheimeh Sari, H., Li, J., Xi, Y., ... & Wu, Y. (2022). Enriching Oxygen Vacancy Defects via Ag–O–Mn Bonds for Enhanced Diffusion Kinetics of δ-MnO2 in Zinc-Ion Batteries. ACS Applied Materials & Interfaces, 14(18), 21159-21172. Figure 1

Aqueous zinc ion batteries (ZIBs) are becoming increasingly popular in the field of energy storage due to their high safety and environmental friendliness. This study comparatively investigated the electrochemical performance of β-MnO2 as a cathode for ZIBs after doping with different ratios of three-dimensional graphene (3D-GPE)/carbon nanotube (CNT) cross-linked composite materials with ball milling. The results show that 3D-GPE/CNT cross-linked composite has an effect on β-MnO2 microstructure and particle morphology. The cathode made of β-MnO2/(3D-GPE/CNT) with a mass ratio of 9:1 has a very high reversible capacity of 1078.93 mAh/g at a current density of 10 mA g−1, which is about 2.24 and 1.87 times the other two ratio materials (18:1 and 12:1), respectively. After 100 cycles, the median voltage difference of the β-MnO2/(3D-GPE/CNT) mass ratio 9:1 specimen battery increased. The higher the median voltage, the higher the energy of the battery. The improvement of cathode performance is directly related to the micro-state, such as the three-dimensional frameworks and carbon nanotube structures of 3D-GPE/CNT, and the macro-state, such as particle refinement, homogenization, and layered structure.

Ultrastable organic cathode derived by pigment/rGO for aqueous zinc-ion batteries

Owing to high safety and low cost, aqueous rechargeable zinc-ion batteries (ZIBs) is currently a major research topic. In this study, we propose the microwave-assisted hydrothermal synthesis of polypyrrole (PPy)-coated Na1.1V3O7.9 (P-NVO) nanorods for the first time as a highenergy and high-power cathode material for ZIBs. The highly conductive PPy surface-coating layer is significant to enhance the electronic conductivity and Zn2+ diffusion kinetics, leading to utilize the V3+/V4+/V5+ multiple redox reactions of the NVO cathode in ZIBs. Compared to the NVO cathode, therefore, the P-NVO cathode offers higher discharge capacity, power capability and cycling stability; in particular, PPy coating triggers the full theoretical capacity of the NVO cathode (527 mAh g- 1 with ~ 3 mol Zn insertion per formula unit) and directly reflects a superior energy density of 408 Wh kg-1. Even at a high current density of 6000 mA g- 1, the P-NVO cathode sustains 1000 cycles with almost 100% capacity retention. Galvanostatic intermittent titration technique, cyclic voltammetry, in situ X-ray diffraction, and ex situ X-ray absorption near edge structure analyses are combined to verify the superior Zn2+ storage mechanism of the P-NVO cathode.

Unravelling the proton hysteresis mechanism in vacancy modified vanadium oxides for High-Performance aqueous zinc ion battery

Polyaniline intercalation induced great enhancement of electrochemical properties in ammonium vanadate nanosheets as an advanced cathode for high-performance aqueous zinc-ion batteries

Vanadium nitride (VN), as a cathode material for aqueous zinc ion batteries (ZIBs), has the advantage of high stability and theoretical specific capacity. Here, we aim at the disadvantages of the poor conductivity of VN and NH3 as a nitrogen source, and prepare vanadium nitride@nitrogen-doped graphene (VN@NGr) in N2 atmosphere, using dicyandiamide (DCDA) as the nitrogen source and glucose as the carbon source. The VN@NGr electrode shows excellent reversible rate performance, and, after that, the electrode maintained ∼100% capacity retention to 1000 cycles at 1 A g–1 current density. In addition, at the current densities of 0.1 and 20 A g–1, the electrode maintained 96% and 70% capacity retention after 75 and 26 000 cycles. VN@NGr material has the advantages of simple preparation, low cost, and good electrochemical stability, so we believe it will be competitive in future large-scale energy storage fields.

Manganese-based oxide is arguably one of the most well-studied cathode materials for zinc-ion battery (ZIB) due to its wide oxidation states, cost-effectiveness, and matured synthesis process. As a result, there are numerous reports that show significant strides in the progress of Mn-based oxides as ZIB cathode. However, ironically, due to the sheer number of Mn-based oxides that have been published in recent years, there remain certain contemplations with regards to the electrochemical performance of each type of Mn-based oxides and their performance comparison among various Mn polymorphs and oxidation states. Thus, to provide a clearer indication of the development of Mn-based oxides, the recent progress in Mn-based oxides as ZIB cathode was summarized systematically in this Review. More specifically, (1) the classification of Mn-based oxides based on the oxidation states (i. e., MnO2 , Mn3 O4 , Mn2 O3 , and MnO), (2) their respective polymorphs (i. e., α-MnO2 and δ-MnO2 ) as ZIB cathode, (3) the modification strategies commonly employed to enhance the performance, and (4) the effects of these modification strategies on the performance enhancement were reviewed. Lastly, perspectives and outlook of Mn-based oxides as ZIB cathode were discussed at the end of this Review.

A high-rate performance can be achieved using the VS4@rGO nanocomposite as the cathode for zinc ion batteries.

Tunnel-type vanadium oxides are promising cathodes for aqueous zinc ion batteries. However, unlike layer-type cathodes with adjustable layer distances, enhancing ion-transport kinetics in tunnels characterized by fixed sizes poses a considerable challenge. This study highlights that the macroscopic arrangement of the electrode crucially determines tunnel orientation, thereby influencing ion transport. By changing the material morphology, the tunnel orientation can be optimized to facilitate rapid ion diffusion. In a proof-of-concept demonstration, it is revealed that (00l) facets-dominated VO2 (B) nanobelts with dispersive morphology (VO2-D) tend to adopt a stacking pattern with directional ion transport along the c-axis on the electrode and guarantee fast ion diffusion. Compared with the aggregated sample (VO2-A) that tends to random arrangement on the electrode with isotropic and slow ion transfer behavior, the electrode featuring dispersive (00l) facets-dominated VO2 (B) nanobelts displays directional and fast ion diffusion behavior, thus exhibits an ultrahigh-rate performance (420.8 and 344.8 mAh g-1 at 0.1 and 10 A g-1, respectively) and long cycling stability (84.3% capacity retention under 5000 cycles at 10 A g-1). The results suggest that simultaneous manipulation of exposed crystal facet and morphology-related electrode arrangement should be promising for boosting the ion-transport kinetics in tunnel-type vanadium oxide cathodes.

Nano-sized split V2O5 with H2O-intercalated interfaces as a stable cathode for zinc ion batteries without an aging process

Aqueous zinc-ion batteries (AZIBs) have been investigated intensively as effective energy storage devices that are environmentally friendly, safe, and have a lower cost than current Li-ion batteries.[1-5] Being outstandingly safe due to usage of non-organic electrolyte, AZIBs could also be used as power supply for wearable electronics. This also put high standard requirements in terms of flexibility, stability and electrochemical performance to AZIBs. On the other hand, the general challenges, such as the formation of the dendrites on the Zn anodes, hydrogen evolution and side reactions, have been obstructing the practical application of AZIBs. In this presentation, a simple method to assemble quasi-solid-state Zn ion pouch cell with excellent mechanical performance, flexibility and electrochemical performance was developed, combining in-situ electrodeposition of MnO2 cathode and aramid nano fiber-based hydrogel with Zn plate as anode. In-situ and cycling measurements of the electrodeposition of MnO2 on carbon nanotube mat shows excellent capacitance and superior cycling stability. In addition, Kevlar derivatized aramid nanofiber-based hydrogel shows extremely strong strength when combined with polyvinyl alcohol, which prolonged the lifetime of the cell by preventing Zn dendrite growth largely.[5,6] Moreover, the method to assemble the AZIBs pouch cell enables us to optimize the process, decrease the steps, and save time effectively by taking advantage of hydrogel formation stage and avoiding conventional verbose slurry-casting-drying steps. This work paves an efficient path to assemble flexible and stable AZIBs pouch cells with high capacity and cycling stability.[1] Tang, Boya, et al. "Issues and opportunities facing aqueous zinc-ion batteries." Energy & Environmental Science 12.11 (2019): 3288-3304.[2] Li, Chang, et al. "Toward practical aqueous zinc-ion batteries for electrochemical energy storage." Joule 6.8 (2022): 1733-1738.[3] Yu, Feng, et al. "An aqueous rechargeable zinc-ion battery on basis of an organic pigment." Rare Metals 41.7 (2022): 2230-2236.[4] Lin, Yuexing, et al. "Dendrite-free Zn anode enabled by anionic surfactant-induced horizontal growth for highly-stable aqueous Zn-ion pouch cells." Energy & Environmental Science 16.2 (2023): 687-697.[5] Wang, Peng, and Petru Andrei. "High Performance Separator and Hydrogel Based on Aramid Fibers for Zn Ion Batteries." Electrochemical Society Meeting s 242. No. 4. The Electrochemical Society, Inc., 2022.[6] Xu, Lizhi, et al. "Water‐rich biomimetic composites with abiotic self‐organizing nanofiber network." Advanced Materials 30.1 (2018): 1703343.

From 0D to 3D: Controllable synthesis of ammonium vanadate materials for Zn2+ storage with superior rate performance and cycling stability

In-situ electrochemical conversion of Na5V12O32@graphene for enhanced cycle stability in aqueous zinc ion batteries