High-performance Zn-ion Batteries Research Articles

Zinc-Ion Anchor Induced Highly Reversible Zn Anodes for High Performance Zn-Ion Batteries.

Unstable Zn interface with serious detrimental parasitic side-reactions and uncontrollable Zn dendrites severely plagues the practical application of aqueous zinc-ion batteries. The interface stability was closely related to the electrolyte configuration and Zn2+ depositional behavior. In this work, a unique Zn-ion anchoring strategy is originally proposed to manipulate the coordination structure of solvated Zn-ions and guide the Zn-ion depositional behavior. Specifically, the amphoteric charged ion additives (denoted as DM), which act as zinc-ion anchors, can tightly absorb on the Zn surface to guide the uniform zinc-ion distribution by using its positively charged -NR4 + groups. While the negatively charged -SO3 - groups of DM on the other hand, reduces the active water molecules within solvation sheaths of Zn-ions. Benefiting from the special synergistic effect, Zn metal exhibits highly ordered and compact (002) Zn deposition and negligible side-reactions. As a result, the advanced Zn||Zn symmetric cell delivers extraordinarily 7000 hours long lifespan (0.25 mA cm-2, 0.25 mAh cm-2). Additionally, based on this strategy, the NH4V4O10||Zn pouch-cell with low negative/positive capacity ratio (N/P ratio=2.98) maintains 80.4 % capacity retention for 180 cycles. A more practical 4 cm*4 cm sized pouch-cell could be steadily cycled in a high output capacity of 37.0 mAh over 50 cycles.

Pre-doped cations in V 2O 5 for high-performance Zn-ion batteries

Pre-doped cations in V ₂O ₅ for high-performance Zn-ion batteries

Spent shell as a calcium source for constructing calcium vanadate for high-performance Zn-ion batteries.

In this article, waste shell is directly used as a raw material to synthesize CaV3O7 as a cathode for aqueous zinc ion batteries. The obtained cathode material exhibits better performance than that of CaV3O7 prepared from pure calcium carbonate as a raw material. At 0.1 A g-1, the CaV3O7 prepared by spent shell as a calcium source displays a highly reversible discharge capacity of 373 mA h g-1. A high initial discharge capacity of 177.7 mA h g-1 can be gained at 5.0 A g-1, and the specific capacity remains at 133.3 mA h g-1 with a capacity retention of 75% after 3000 cycles. This work may spark inspiration for energy storage and generate more effective routes for recycling solid waste.

Gallium regulated MnO2 toward high performance Zn ion batteries

α-MnO2 with open tunnel structure has received ever-increasing attention because of its superior specific capacity, yet generally undergoes unstable phase transition from the tunnel architecture to layered structure upon Zn2+ insertion as well as the disadvantages of low electrical conductivity and slow Zn2+ diffusion kinetics, thereafter triggering inactive reaction dynamics. In this regard, a gallium (Ga) doped α-MnO2 nanowires (denoted as MnO2-Ga) is firstly built in this work to address the abovementioned issue and the MnO2-Ga2 displays enhanced performance with reversible capacity of 205.1 ± 5 mAh g−1 undergoing 200 cycles at 0.2 A g−1. After repeated 2000 cycles at 1 A g−1, a capacity of 123.7 ± 5 mAh g−1 can be still obtained. Validated by the theoretical calculation, it is noted that the Ga could effectively regulate the electronic distribution of α-MnO2 and narrows the bandgap, prompting the electronic cloud polarization of O and therafter accelerating ion diffusion efficiency. Fundamentally, the Ga intercalation results in the formation of Ga–O bonds. This special building not only guarantees the reversible phase transition and alleviates the Mn dissolution of Ga-MnO2, but also weakens the Zn2+-O2- interactions, leading to elevated cyclic durability and capacity.

Facile Synthesis of Oxygen-Vacancy-Rich Li–K Coinsertion Vanadate Nanoflakes for High-Performance Zn-Ion Batteries

Facile Synthesis of Oxygen-Vacancy-Rich Li–K Coinsertion Vanadate Nanoflakes for High-Performance Zn-Ion Batteries

Unlocking the Interfacial Adsorption-Intercalation Pseudocapacitive Storage Limit to Enabling All-Climate, High Energy/Power Density and Durable Zn-Ion Batteries.

Sluggish storage kinetics and insufficient performance are the major challenges that restrict the transition metal dichalcogenides (TMDs) applied for zinc ion storage, especially at the extreme temperature conditions. Herein, a multiscale interface structure-integrated modulation concept was presented, to unlock the omnidirectional storage kinetics-enhanced porous VSe2-x ⋅n H2 O host. Theory research indicated that the co-modulation of H2 O intercalation and selenium vacancy enables enhancing the interfacial zinc ion capture ability and decreasing the zinc ion diffusion barrier. Moreover, an interfacial adsorption-intercalation pseudocapacitive storage mechanism was uncovered. Such cathode displayed remarkable storage performance at the wide temperature range (-40-60 °C) in aqueous and solid electrolytes. In particular, it can retain a high specific capacity of 173 mAh g-1 after 5000 cycles at 10 A g-1 , as well as a high energy density of 290 Wh kg-1 and a power density of 15.8 kW kg-1 at room temperature. Unexpectedly, a remarkably energy density of 465 Wh kg-1 and power density of 21.26 kW kg-1 at 60 °C also can be achieved, as well as 258 Wh kg-1 and 10.8 kW kg-1 at -20 °C. This work realizes a conceptual breakthrough for extending the interfacial storage limit of layered TMDs to construct all-climate high-performance Zn-ion batteries.

Stabilizing Zn anodes by constructing PEGMA protecting layers for high-performance Zn-ion batteries

As a promising candidate for grid-scale energy storage, rechargeable aqueous Zn-ion batteries (ZIBs) have many advantages including low cost, high safety, and environmental benignity. However, the Zn metal anode still suffers from severe dendrite and corrosion issues, hindering the practical application of ZIBs. Herein, we report a dense and uniform poly (ethylene glycol methyl ether methacrylate) (PEGMA) artificial protecting layer to alleviate these issues, by preventing the direct electrolyte/Zn anode contact while guiding the uniform migration of Zn2+ ions. Thanks to these merits, the cycling stability of Zn//Zn symmetrical cells is remarkably improved from 248 h up to 1096 h (at 1 mA cm−2 and 1 mAh cm−2), and the Coulombic efficiencies (CEs) of the Zn striping/plating reaction is increased from 85.9% to 99.1%. Furthermore, the potential application of this strategy is further demonstrated in Zn//iodine (I2) full batteries. Compared with the Bare-Zn//I2 batteries, the PEGMA-Zn//I2 full batteries deliver better CEs (99.5% vs. 99.3% in average at 0.2 A g−1), cycling stability (capacity retention: 89.0% vs. 74.7% after 4000 cycles at 1 A g−1) and shelf life (capacity retention: 78% vs. 71% after 50 h open-circuit storage), underscoring the application potential of this strategy in high-performance ZIBs.

A Janus separator towards dendrite-free and stable zinc anodes for long-duration aqueous zinc ion batteries

Critical issues of Zn anodes including undesirable dendrites formation and parasitic reactions severely limit the reversibility and cyclability of Zn anodes. To address these issues, a functional Janus separator with the structure of a mechanically strong sulfonated poly(arylene ether sulfone) (SPAES) dense layer composited on a porous glass fiber (GF) substrate is designed. The SPAES dense layer that faces the Zn anode containing abundant sulfonic acid groups effectively promotes the desolvation process of hydrated Zn ions, guides uniform Zn ion transfer, and blocks anions and water, contributing to dendrite-free and highly reversible Zn plating/stripping cycles, while the porous GF substrate retains high electrolyte uptake. As a result, the Zn symmetric cell with the Janus separator demonstrates an ultralong cycling lifespan of over 2000 h at the areal capacity of 1 mA h cm−2, which is 23-fold superior to that with a pristine glass fiber separator (<90 h). More impressively, the as-prepared Janus separator enables outstanding rate performance and excellent cycling stability of full Zn ion batteries with diverse cathode materials. For instance, when paired with the V2O5 cathode, the full battery with a Janus separator attains an ultrahigh initial specific capacity of 416.3 mA h g−1 and capacity retention of 60% over 450 cycles at 1 A g−1, exceeding that with a glass fiber separator. Hence, this work provides a facile yet effective approach to mitigating the dendrites formation and ameliorating the parasitic reactions of Zn metal anodes for high-performance Zn ion batteries.

Surface Engineering for Ultrathin Metal Anodes Enabling High-Performance Zn-Ion Batteries.

Zn-ion batteries with low cost and high safety have been regarded as a promising energy storage technology for grid storage. It is well-known that the metal anode surface orientation is vital to its reversibility. Herein, we demonstrate a facile route to control the Zn metal anode surface orientation through electrodeposition with electrolyte additives. An ultrathin (101)-inclined Zn metal anode (down to 2 μm) is obtained by adding a small amount of dimethyl sulfoxide (DMSO) in the ZnSO4 aqueous electrolyte. Scanning electron microscopy indicates the formation of flat terrace-like surfaces, while in situ optical observations demonstrate the reversible plating and stripping. DFT calculations reveal that the large reconstruction of the Zn-(101) surface with DMSO and H2O adsorption to lower the interface energy is the main driving force for surface preference. Raman, XPS, and ToF-SIMS characterizations are performed to unveil the surface SEI components. Exceptional electrochemical performance is demonstrated for the (101)-inclined Zn metal anode in a half cell, which could cycle for 200 h with a low overpotential (<50 mV). The Zn||V2O full cells are assembled, showing much better cycle performance for the 5 μm (101)-inclined Zn metal anode as compared to the commercialized 10 μm Zn metal foil, with a maximum specific capacity of 359 mAh/g and >170 mAh/g after over 300 cycles. We hope this study will spur further interest in the control of surface crystallographic orientation for a stable ultrathin Zn metal anode.

A Double-Functional Additive Containing Nucleophilic Groups for High-Performance Zn-Ion Batteries.

Aqueous zinc-ion batteries (AZIBs) have attracted attention for their low cost and environmental friendliness. Unfortunately, commercialization has been hampered by several problems with dendrite growth and side reactions. Herein, we select sodium tartrate (TA-Na) as a dual-functional electrolyte additive to enhance the reversibility of AZIBs. The tartrate anions are preferentially adsorbed on the Zn surface, and then the highly nucleophilic carboxylate will coordinate with Zn2+ to promote the desolvation of [Zn(H2O)6]2+, leading to uniform Zn deposition on the beneficial (002) plane and inhibiting side reactions and dendrite growth. Consequently, the Zn|Zn cells show a long-term cycling stability of over 1500 cycles at 0.5 mA cm-2. Moreover, the Ta-Na additive improves the performance of Zn||MnO2 full cells, evidenced by a cycling life of 1000 cycles at 1 A g-1 under practical conditions with a limited Zn anode (negative/positive capacity ratio of 10/1) and controlled electrolyte (electrolyte/capacity ratio of 20 μL mAh-1).

High-performance Zn-ion batteries constructed byin situconversion of surface-oxidized vanadium nitride into Zn3(OH)2V2O7·2H2O with oxygen defects

Surface-oxidized vanadium nitride transforms into Zn3V2O7(OH)2-based materials with oxygen defects by electrochemical conversion, which act as cathodes for high performance aqueous zinc ion batteries.

Conductive Framework-Stabilized Zn-Metal Anodes for High-Performance Zn-Ion Batteries and Capacitors

Aqueous zinc (Zn)-based energy storage devices possess promising applications for large-scale energy storage systems due to the advantage of high safety, low price, and environment-friendliness. However, their development is restricted by dendrite growth and hydrogen evolution issues from the Zn-metal anode. Herein, a facile stress-pressing method is reported for constructing a grid zinc anode (GZn) with a conductive framework. The highly conductive copper (Cu)-mesh framework reduces electrode hydrogen evolution and increases electrode conductivity. Meanwhile, the in situ-formed Cu-Zn nano-alloy stabilizes the Zn deposition interface. As a result, the GZn symmetrical cell presents a low overpotential of 49 mV after cycling for 1,200 h (0.2 mA∙cm −2 ). In addition, GZn displays its potential application as a universal anode for Zn-ion capacitors and batteries. An activated carbon||GZn Zn-ion capacitor delivers a stable cycling performance after 10,000 cycles at 5 A∙g −1 and MnO 2 ||GZn Zn-ion batteries exhibit satisfactory cycle stability and excellent rate performance. This demonstrates that GZn appears to be a promising universal anode for Zn-ion capacitors and batteries.

Porous surface-induced growth of HCl-doped PANi flexible electrode for high performance Zn-ion batteries with convertible storage sites

Polyaniline (PANi) has brought new enthusiasm in the field of aqueous Zn-ion batteries due to the unique nature of high conductivity, excellent structural flexibility, and fast ions de-/intercalation ability. However, the naked and densified PANi usually suffers from capacity fade and limited rate performance owing to the deprotonation of the polymer and imbalanced electron-ion transmission. Herein, a HCl-doped porous PANi electrode was prepared by electrodepositing the aniline monomer onto a porous carbon cloth (PCC), which plays an important role in elevating the loading mass and inducing porous structure of the PANi, thus enhancing the mass energy density and ions diffusion coefficient of the electrode; On the other hand, the HCl-doping could facilitate the charge delocalization and increase the conductivity of the PANi. Besides, a convertible behavior of the energy storage sites during charging-discharging processes was firstly observed for PANi, which should be responsible for the high-rate and cycling performance of the Zn-ion batteries, there is very small capacity decay from 170 mAh g−1 at 1 A g−1 to 161 mAh g−1 at 10 A g−1, and 87 % of the initial the capacity can maintain after 2000 cycles at 5 A g−1. Furthermore, the quasi-solid-state Zn-ion battery can also display superior performance, showing potential application of the PCC@PANi for wearable devices

Porous Electrode Materials for Zn-Ion Batteries: From Fabrication and Electrochemical Application

Porous materials as electrode materials have demonstrated numerous benefits for high-performance Zn-ion batteries in recent years. In brief, porous materials as positive electrodes provide distinctive features such as faster electron transport, shorter ion diffusion distance, and richer electroactive reaction sites, which improve the kinetics of positive electrode reactions and achieve higher rate capacity. On the other hand, the porous structures as negative electrodes also exhibit electrochemical properties possessing higher surface area and reducing local current density, which favors the uniform Zn deposition and restrains the dendrite formation. In view of their advantages, porous electrode materials for ZIB are expected to be extensively applied in electric and hybrid electric vehicles and portable electronic devices. In this review, we highlight the methods of synthesizing porous electrode materials and discuss the mechanism of action of porous structures as electrodes on their electrochemical properties. At the end of this review, the perspectives on the future development of porous materials in the field of electrochemical energy storage are also discussed.

Adjusting the V5+ content of vanadium oxide cathodes for high-performance Zn-ion batteries by aging

Vanadium oxides are promising cathode materials with great potential. Here, we present a simple, safe, and environmentally friendly aging treatment to change the content of V5+ in vanadium oxides. The influence of different V5+ contents in vanadium oxides cathodes on the properties of Zn-ion batteries (ZIBs) is studied. V6O13 and V3O7/V6O13 nanosheets are synthesized by aging VO2 precursors for different periods of time. V6O13 is found to exhibit higher specific capacity and excellent cycling performance compared to VO2 and V3O7/V6O13. It is also characterized by an extremely high capacity of 300 mA h g−1 at a high current density of 5 A g−1. At 0.3 A g−1, it maintains a capacity of 421 mA h g−1 during 100 cycles with a high capacity retention rate of 95%. Changes in the vanadium valence state, structure, and morphology of electrodes during charging and discharging are also investigated for a better understanding of the underlying electrochemical processes.

Rationally designed In@Zn@In trilayer structure on 3D porous Cu towards high-performance Zn-Ion batteries

Metallic Zn has been regarded as a promising anode for rechargeable aqueous zinc-ion batteries (ZIBs) due to its abundant reserves, low cost, high safety, low redox potential and high theoretical capacity. However, such ZIBs usually suffer from dendrite growth and serious side reactions of Zn anode, and incur poor cycling stability and battery safety issues, thus limiting their practical applications. Herein a unique In@Zn@In trilayer structure grown on three-dimensional (3D) porous Cu framework (3D In@Zn@In) is rationally designed and developed by electroless plating coupled with electrodepositing for high-performance ZIBs. The sandwich-like In@Zn@In trilayer structure not only efficiently inhibits the dendrite growth and side reactions of Zn anode, but also exhibits remarkably enhanced Zn plating/stripping kinetics. Meanwhile, 3D porous architectures possess some favorable merits for ZIBs including rapid electrolyte penetration, sufficient electron/ion transport channels, restricting Zn dendrite growth, and robust structure integrity. In this work, 3D In@Zn@In efficiently combines the advantages of In@Zn@In trilayer structure and 3D porous framework, and shows highly stable Zn storage for over 400 h in symmetry cell and 2000 cycles in full cell coupled with Mn2O3 cathode. This work provides a facile, efficient and controllable strategy to inhibit Zn dendrite and side reactions for realizing highly stable Zn anode, showing a great potential for other metal anode applications.

Polyacrylonitrile/bio-based polyurethane electrospun fiber mats as advanced separators for high-performance Zn-ion batteries

Polyacrylonitrile/bio-based polyurethane electrospun fiber mats as advanced separators for high-performance Zn-ion batteries

Achieving both high reversible and stable Zn anode by a practical glucose electrolyte additive toward high-performance Zn-ion batteries

Achieving both high reversible and stable Zn anode by a practical glucose electrolyte additive toward high-performance Zn-ion batteries

K-preintercalated MnO2 nanosheets as cathode for high-performance Zn-ion batteries

Manganese oxides are regarded as promising cathode materials for aqueous zinc ion batteries (ZIBs) due to their low cost and high theoretical capacity. However, their practical application is seriously hindered because of the inferior electronic conductivity, sluggish diffusion kinetics and structural instability. Herein, we develop a new K-preintercalated MnO 2 (K 0.19 MnO 2 ·0.56H 2 O, KMO) nanosheet by a facile hydrothermal method. Preintercalation of K + ions into the MnO 2 crystal layers with structural reconstruction can activate more active sites, strengthen the crystal structural stability and facilitate the insertion/extraction of Zn 2+ ions. The charge shielding effect of crystal water promotes the diffusion kinetics of Zn 2+ ions. The obtained KMO electrode delivers high specific capacity (107 mAh g −1 ) and good cycling stability (~87.5% capacity retention after 2000 cycles), revealing its potential application for aqueous ZIBs.

Ultra-Fast and Scalable Saline Immersion Strategy Enabling Uniform Zn Nucleation and Deposition for High-Performance Zn-Ion Batteries.

Although aqueous Zn-ion batteries (ZIBs) with low cost and high safety show great potential in large-scale energy storage system, metallic Zn anode still suffers from unsatisfactory cycle stability due to unregulated growth of Zn dendrites, corrosion, and formation of various side products during electrochemical reaction. Here, an ultrafast and simple method to achieve a stable Zn anode is developed. By simply immersing a Zn plate into an aqueous solution of CuSO4 for only 10-60 s, a uniform and robust protective layer (Zn4 SO4 (OH)6 ·5H2 O/Cu2 O) is formed on commercial Zn plate (Zn/ZCO), which enables uniform electric field distribution and controllable dendrite growth, leading to a long-term cycle life of over 1400 h and high average Coulombic efficiency (CE) of 99.2% at 2.0mA cm-2 and 2.0 mAh cm-2 . These excellent characteristics of the prepared Zn anode show great potential in practical applications for high-performance aqueous Zn-ion batteries.