Manipulating OH−-Mediated Anode-Cathode Cross-Communication Toward Long-Life Aqueous Zinc-Vanadium Batteries

The anode-cathode interplay is an important but rarely considered factor that initiates the degradation of aqueous zinc ion batteries (AZIBs). Herein, to address the limited cyclability issue of V-based AZIBs, Al₂(SO₄)₃ is proposed as decent electrolyte additive to manipulate OH⁻-mediated cross-communication between Zn anode and NaV₃O₈ ⋅ 1.5H₂O (NVO) cathode. The hydrolysis of Al³⁺ creates a pH≈0.9 strong acidic environment, which unexpectedly prolongs the anode lifespan from 200 to 1000 h. Such impressive improvement is assigned to the alleviation of interfacial OH⁻ accumulation by Al³⁺ adsorption and solid electrolyte interphase formation. Accordingly, the strongly acidified electrolyte, associated with the sedated crossover of anodic OH⁻ toward NVO, remarkably mitigate its undesired dissolution and phase transition. The interrupted OH⁻-mediated communication between the two electrodes endows Zn||NVO batteries with superb cycling stability, at both low and high scan rates.     

Boosting Zn Anode Utilization by Trace Iodine Ions in Organic-Water Hybrid Electrolytes through Formation of Anion-rich Adsorbing Layers

Aqueous Zn batteries are attracting extensive attentions, but their application is still hindered by H₂O-induced Zn-corrosion and hydrogen evolution reactions. Addition of organic solvents into aqueous electrolytes to limit the H₂O activity is a promising solution, but at the cost of greatly reduced Zn anode kinetics. Here we propose a simple strategy for this challenge by adding 50 mM iodine ions into an organic-water (1,2-dimethoxyethane (DME)+water) hybrid electrolyte, which enables the electrolyte simultaneously owns the advantages of low H₂O activity and accelerated Zn kinetics. We demonstrate that the DME breaks the H₂O hydrogen-bond network and exclude H₂O from Zn²⁺ solvation shell. And the I⁻ is firmly adsorbed on the Zn anode, reducing the Zn²⁺ de-solvation barrier from 74.33 kJ mol⁻¹ to 32.26 kJ mol⁻¹ and inducing homogeneous nucleation behavior. With such electrolyte, the Zn//Zn symmetric cell exhibits a record high cycling lifetime (14.5 months) and achieves high Zn anode utilization (75.5 %). In particular, the Zn//VS₂@SS full cell with the optimized electrolyte stably cycles for 170 cycles at a low N : P ratio (3.64). Even with the cathode mass-loading of 16.7 mg cm⁻², the full cell maintains the areal capacity of 0.96 mAh cm⁻² after 1600 cycles.     

Hybrid Superlattice-Triggered Selective Proton Grotthuss Intercalation in δ-MnO2 for High-Performance Zinc-Ion Battery

A great deal of attention has been paid on layered manganese dioxide (δ−MnO₂) as promising cathode candidate for aqueous zinc-ion battery (ZIB) due to the excellent theoretical capacity, high working voltage and Zn²⁺/H⁺ co-intercalation mechanism. However, caused by the insertion of Zn²⁺, the strong coulomb interaction and sluggish diffusion kinetics have resulted in significant structure deformation, insufficient cycle stability and limited rate capability. And it is still far from satisfactory to accurately modulate H⁺ intercalation for superior electrochemical kinetics. Herein, the terrace-shape δ−MnO₂ hybrid superlattice by polyvinylpyrrolidone (PVP) pre-intercalation (PVP−MnO₂) was proposed with the state-of-the-art ZIBs performance. Local atomic structure characterization and theoretical calculations have been pioneering in confirming the hybrid superlattice-triggered synergy of electron entropy stimulation and selective H⁺ Grotthuss intercalation. Accordingly, PVP−MnO₂ hybrid superlattice exhibits prominent specific capacity (317.2 mAh g⁻¹ at 0.125 A g⁻¹), significant rate performance (106.1 mAh g⁻¹ at 12.5 A g⁻¹), and remarkable cycle stability at high rate (≈100 % capacity retention after 20,000 cycles at 10 A g⁻¹). Therefore, rational design of interlayer configuration paves the pathways to the development of MnO₂ superlattice for advanced Zn−MnO₂ batteries.     

Steric-hindrance Effect Tuned Ion Solvation Enabling High Performance Aqueous Zinc Ion Batteries

Despite many additives have been reported for aqueous zinc ion batteries, steric-hindrance effect of additives and its correlation with Zn²⁺ solvation structure have been rarely reported. Herein, large-sized sucrose biomolecule is selected as a paradigm additive, and steric-hindrance electrolytes (STEs) are developed to investigate the steric-hindrance effect for solvation structure regulation. Sucrose molecules do not participate in Zn²⁺ solvation shell, but significantly homogenize the distribution of solvated Zn²⁺ and enlarge Zn²⁺ solvation shell with weakened Zn²⁺−H₂O interaction due to the steric-hindrance effect. More importantly, STEs afford the water-shielding electric double layer and in situ construct the organic and inorganic hybrid solid electrolyte interface, which effectively boost Zn anode reversibility. Remarkably, Zn//NVO battery presents high capacity of 3.9 mAh ⋅ cm⁻² with long cycling stability for over 650 cycles at lean electrolyte of 4.5 μL ⋅ mg⁻¹ and low N/P ratio of 1.5, and the stable operation at wide temperature (−20 °C~+40 °C).     

Constructing a Super-Saturated Electrolyte Front Surface for Stable Rechargeable Aqueous Zinc Batteries

Rechargeable aqueous zinc batteries (RAZB) have been re-evaluated because of the superiority in addressing safety and cost concerns. Nonetheless, the limited lifespan arising from dendritic electrodeposition of metallic Zn hinders their further development. Herein, a metal–organic framework (MOF) was constructed as front surface layer to maintain a super-saturated electrolyte layer on the Zn anode. Raman spectroscopy indicated that the highly coordinated ion complexes migrating through the MOF channels were different from the solvation structure in bulk electrolyte. Benefiting from the unique super-saturated front surface, symmetric Zn cells survived up to 3000 hours at 0.5 mA cm⁻², near 55-times that of bare Zn anodes. Moreover, aqueous MnO₂–Zn batteries delivered a reversible capacity of 180.3 mAh g⁻¹ and maintained a high capacity retention of 88.9 % after 600 cycles with MnO₂ mass loading up to 4.2 mg cm⁻².     

Proton-Reservoir Hydrogel Electrolyte for Long-Term Cycling Zn/PANI Batteries in Wide Temperature Range

Advanced aqueous batteries are promising for next generation flexible devices owing to the high safety, yet still requiring better cycling stability and high capacities in wide temperature range. Herein, a polymeric acid hydrogel electrolyte (PAGE) with 3 M Zn(ClO₄)₂ was fabricated for high performance Zn/polyaniline (PANI) batteries. With PAGE, even at −35 °C the Zn/Zn symmetrical battery can keep stable for more than 1 500 h under 2 mA cm⁻², and the Zn/PANI battery can provide ultra-high stable specific capacity of 79.6 mAh g⁻¹ for more than 70 000 cycles at 15 A g⁻¹. This can be mainly ascribed to the −SO₃⁻H⁺ function group in PAGE. It can generate constant protons and guide the (002) plane formation to accelerate the PANI redox reaction kinetics, increase the specific capacity, and suppress the side reaction and dendrites. This proton-supplying strategy by polymeric acid hydrogel may further propel the development of high performance aqueous batteries.     

Organic pH Buffer for Dendrite-Free and Shuttle-Free Zn-I2 Batteries

Aqueous Zn-Iodine (I₂) batteries are attractive for large-scale energy storage. However, drawbacks include, Zn dendrites, hydrogen evolution reaction (HER), corrosion and, cathode “shuttle” of polyiodines. Here we report a class of N-containing heterocyclic compounds as organic pH buffers to obviate these. We evidence that addition of pyridine /imidazole regulates electrolyte pH, and inhibits HER and anode corrosion. In addition, pyridine and imidazole preferentially absorb on Zn metal, regulating non-dendritic Zn plating /stripping, and achieving a high Coulombic efficiency of 99.6 % and long-term cycling stability of 3200 h at 2 mA cm⁻², 2 mAh cm⁻². It is also confirmed that pyridine inhibits polyiodines shuttling and boosts conversion kinetics for I⁻/I₂. As a result, the Zn-I₂ full battery exhibits long cycle stability of >25 000 cycles and high specific capacity of 105.5 mAh g⁻¹ at 10 A g⁻¹. We conclude organic pH buffer engineering is practical for dendrite-free and shuttle-free Zn-I₂ batteries.     

Bio-Inspired Trace Hydroxyl-Rich Electrolyte Additives for High-Rate and Stable Zn-Ion Batteries at Low Temperatures

High-rate and stable Zn-ion batteries working at low temperatures are highly desirable for practical applications, but are challenged by sluggish kinetics and severe corrosion. Herein, inspired by frost-resistant plants, we report trace hydroxyl-rich electrolyte additives that implement a dual remodeling effect for high-performance low-temperature Zn-ion batteries. The additive with high Zn absorbability not only remodels Zn²⁺ primary solvent shell by alternating H₂O molecules, but also forms a shielding layer thus remodeling the Zn surface, which effectively enhances fast Zn²⁺ de-solvation reaction kinetics and prohibits Zn anode corrosion. Taking trace α-D-glucose (αDG) as a demonstration, the electrolyte obtains a low freezing point of −55.3 °C, and the Zn//Zn cell can stably cycle for 2000 h at 5 mA cm⁻² under −25 °C, with a high cumulative capacity of 5000 mAh cm⁻². A full battery that stably operates for 10000 cycles at −50 °C is also demonstrated.     

Proton Intercalation/De-intercalation Chemistry in Phenazine-based Anode for Hydronium-ion Batteries

Hydronium-ion batteries have received significant attention owing to the merits of extraordinary sustainability and excellent rate abilities. However, achieving high-performance hydronium-ion batteries remains a challenge due to the inferior properties of anode materials in strong acid electrolyte. Herein, a hydronium-ion battery is constructed which is based on a diquinoxalino [2,3-a:2’,3’-c] phenazine (HATN) anode and a MnO₂@graphite felt cathode in a hybrid acidic electrolyte. The fast kinetics of hydronium-ion insertion/extraction into HATN electrode endows the HATN//MnO₂@GF battery with enhanced electrochemical performance. This battery exhibits an excellent rate performance (266 mAh g⁻¹ at 0.5 A g⁻¹, 97 mAh g⁻¹ at 50 A g⁻¹), attractive energy density (182.1 Wh kg⁻¹) and power density (31.2 kW kg⁻¹), along with long-term cycle stability. These results shed light on the development of advanced hydronium-ion batteries.     

Hydrophobic Organic-Electrolyte-Protected Zinc Anodes for Aqueous Zinc Batteries

Aqueous Zn batteries are promising energy-storage devices. However, their lifespan is limited by irreversible Zn anodes owing to water decomposition and Zn dendrite growth. Here, we separate aqueous electrolyte from Zn anode by coating a thin MOF layer on anode and filling the pores of MOF with hydrophobic Zn(TFSI)₂-tris(2,2,2-trifluoroethyl)phosphate (TFEP) organic electrolyte that is immiscible with aqueous Zn(TFSI)₂–H₂O bulk electrolyte. The MOF encapsulated Zn(TFSI)₂-TFEP forms a ZnF₂-Zn₃(PO₄)₂ solid electrolyte interphase (SEI) preventing Zn dendrite and water decomposition. The Zn(TFSI)₂-TFEP@MOF electrolyte protected Zn anode enables a Zn||Ti cell to achieve a high average Coulombic efficiency of 99.1 % for 350 cycles. The highly reversible Zn anode brings a high energy density of 210 Wh kg⁻¹ (of cathode and anode mass) and a low capacity decay rate of 0.0047 % per cycle over 600 cycles in a Zn||MnO₂ full cell with a low capacity ratio of Zn:MnO₂ at 2:1.     

Inhibiting VOPO4⋅x H2O Decomposition and Dissolution in Rechargeable Aqueous Zinc Batteries to Promote Voltage and Capacity Stabilities

VOPO₄?x H₂O has been proposed as a cathode for rechargeable aqueous zinc batteries. However, it undergoes significant voltage decay in conventional Zn(OTf)₂ electrolyte. Investigations show the decomposition of VOPO₄?x H₂O into VO_x in the electrolyte and voltage drops after losing the inductive effect from polyanions.PO₄^3? was thus added to shift the decomposition equilibrium. A high concentration of cheap, highly soluble ZnCl₂ salt in the electrolyte further prevents VOPO₄?x H₂O dissolution. The cathode shows stable capacity and voltage retentions in 13 m ZnCl₂/0.8 m H₃PO₄ aqueous electrolyte, in direct contrast to that in Zn(OTf)₂ where the decomposition product VO_x provides most electrochemical activity over cycling. Sequential H⁺ and Zn²⁺ intercalations into the structure are revealed, delivering a high capacity (170 mAh g^?1). This work shows the potential issue with polyanion cathodes in zinc batteries and proposes an effective solution using fundamental chemical principles.     

A Covalent Organic Framework as a Long-life and High-Rate Anode Suitable for Both Aqueous Acidic and Alkaline Batteries

Aqueous rechargeable batteries are prospective candidates for large-scale grid energy storage. However, traditional anode materials applied lack acid-alkali co-tolerance. Herein, we report a covalent organic framework containing pyrazine (C=N) and phenylimino (−NH−) groups (HPP-COF) as a long-cycle and high-rate anode for both acidic and alkaline batteries. The HPP-COF′s robust covalent linkage and the hydrogen bond network between −NH− and water molecules collectively improve the acid-alkaline co-tolerance. More importantly, the hydrogen bond network promotes the rapid transport of H⁺/OH⁻ by the Grotthuss mechanism. As a result, the HPP-COF delivers a superior capacity and cycle stability (66.6 mAh g⁻¹@ 30 A g⁻¹, over 40000 cycles in 1 M H₂SO₄ electrolyte; 91.7 mAh g⁻¹@ 100 A g⁻¹, over 30000 cycles @ 30 A g⁻¹ in 1 M NaOH electrolyte). The work opens a new direction for the structural design and application of COF materials in acidic and alkaline batteries.     

A Janus Separator based on Cation Exchange Resin and Fe Nanoparticles-decorated Single-wall Carbon Nanotubes with Triply Synergistic Effects for High-areal Capacity Zn−I2 Batteries

Zn−I₂ batteries stand out in the family of aqueous Zn-metal batteries (AZMBs) due to their low-cost and immanent safety. However, Zn dendrite growth, polyiodide shuttle effect and sluggish I₂ redox kinetics result in dramatically capacity decay of Zn−I₂ batteries. Herein, a Janus separator composed of functional layers on anode/cathode sides is designed to resolve these issues simultaneously. The cathode layer of Fe nanoparticles-decorated single-wall carbon nanotubes can effectively anchor polyiodide and catalyze the redox kinetics of iodine species, while the anode layer of cation exchange resin rich in −SO₃⁻ groups is beneficial to attract Zn²⁺ ions and repel detrimental SO₄²⁻/polyiodide, improving the stability of cathode/anode interfaces synergistically. Consequently, the Janus separator endows outstanding cycling stability of symmetrical cells and high-areal-capacity Zn−I₂ batteries with a lifespan over 2500 h and a high-areal capacity of 3.6 mAh cm⁻².     

The Construction of Anion-Induced Solvation Structures in Low-concentration Electrolyte for Stable Zinc Anodes

Aqueous zinc-ion batteries (ZIBs) are promising large-scale energy storage devices because of their low cost and high safety. However, owing to the high activity of H₂O molecules in electrolytes, hydrogen evolution reaction and side reactions usually take place on Zn anodes. Herein, additive-free PCA−Zn electrolyte with capacity of suppressing the activity of free and solvated H₂O molecules was designed by selecting the cationophilic and solventophilic anions. In such electrolyte, contact ion-pairs and solvent-shared ion-pairs were achieved even at low concentration, where PCA⁻ anions coordinate with Zn²⁺ and bond with solvated H₂O molecules. Simultaneously, PCA⁻ anions also induce the construction of H-bonds between free H₂O molecules and them. Therefore, the activity of free and solvated H₂O molecules is effectively restrained. Furthermore, since PCA⁻ anions possess a strong affinity with metal Zn, they can also adsorb on Zn anode surface to protect Zn anode from the direct contact of H₂O molecules, inhibiting the occurrence of water-triggered side reactions. As a result, plating/stripping behavior of Zn anodes is highly reversible and the coulombic efficiency can reach to 99.43 % in PCA−Zn electrolyte. To illustrate the feasibility of PCA−Zn electrolyte, the Zn||PANI full batteries were assembled based on PCA−Zn electrolyte and exhibited enhanced cycling performance.     

Hewettite ZnV6O16 ⋅ 8H2O with Remarkably Stable Layers and Ultralarge Interlayer Spacing for High-Performance Aqueous Zn-Ion Batteries

Aqueous Zn-ion batteries (ZIBs) are promising candidates for grid-scale energy storage because of their intrinsic safety, low-cost and high energy-intensity. Vanadium-based materials are widely used as the cathode of ZIBs, especially A₂V₆O₁₆ ⋅ nH₂O (AVO, A=NH₄⁺, Na, K). However, AVO suffers from serious dissolution, phase transformation and narrow gallery spacing (∼3 Å), leading to poor cycling stability and rate capability. Herein, we unveiled the root cause of the performance degradation in the AVO cathode and therefore developed a new high-performance cathode of ZnV₆O₁₆ ⋅ 8H₂O (ZVO) for ZIB. Through a method of ion exchange induced phase transformation, AVO was converted to hewettite ZVO with larger gallery spacing (∼6 Å) and more stable V₆O₁₆ layers. ZVO cathode thus constructed delivers a high capacity of 365 and 170 mAh g⁻¹ at 0.5 and 15 A g⁻¹, while 86 % and 70 % of its capacity are retained at 0.5 A g⁻¹ after 300 cycles and at 15 A g⁻¹ after 10000 cycles, substantially better than conventional AVO.     

Amphoteric Cellulose-Based Double-Network Hydrogel Electrolyte Toward Ultra-Stable Zn Anode

Zinc (Zn) metal anode suffers from uncontrollable Zn dendrites and parasitic side reactions at the interface, which restrict the practical application of aqueous rechargeable zinc batteries (ARZBs). Herein, an amphoteric cellulose-based double-network is introduced as hydrogel electrolyte to overcome these obstacles. On one hand, the amphoteric groups build anion/cation transport channels to regulate electro-deposition behavior on Zn (002) crystal plane enabled by homogenizing Zn²⁺ ions flux. On the other hand, the strong bonding between negatively charged carboxyl groups and Zn²⁺ ions promote the desolvation process of [Zn(H₂O)₆]²⁺ to eliminate side reactions. Based on the above two functions, the hydrogel electrolyte enables an ultra-stable cycling with a cumulative capacity of 7 Ah cm⁻² at 20 mA cm⁻²/20 mAh cm⁻² for Zn||Zn cell. This work provides significant concepts for developing hydrogel electrolytes to realize stable anode for high-performance ARZBs.     

High-Capacity and Stable Li-O2 Batteries Enabled by a Trifunctional Soluble Redox Mediator

Li-O₂ batteries with ultrahigh theoretical energy densities usually suffer from low practical discharge capacities and inferior cycling stability owing to the cathode passivation caused by insulating discharge products and by-products. Here, a trifunctional ether-based redox mediator, 2,5-di-tert-butyl-1,4-dimethoxybenzene (DBDMB), is introduced into the electrolyte to capture reactive O₂⁻ and alleviate the rigorous oxidative environment of Li-O₂ batteries. Thanks to the strong solvation effect of DBDMB towards Li⁺ and O₂⁻, it not only reduces the formation of by-products (a high Li₂O₂ yield of 96.6 %), but also promotes the solution growth of large-sized Li₂O₂ particles, avoiding the passivation of cathode as well as enabling a large discharge capacity. Moreover, DBDMB makes the oxidization of Li₂O₂ and the decomposition of main by-products (Li₂CO₃ and LiOH) proceed in a highly effective manner, prolonging the stability of Li-O₂ batteries (243 cycles at 1000 mAh g⁻¹ and 1000 mA g⁻¹).     

A Practical High-Energy Cathode for Sodium-Ion Batteries Based on Uniform P2-Na0.7CoO2 Microspheres

Layered metal oxides have attracted increasing attention as cathode materials for sodium-ion batteries (SIBs). However, the application of such cathode materials is still hindered by their poor rate capability and cycling stability. Here, a facile self-templated strategy is developed to synthesize uniform P2-Na_0.7CoO₂ microspheres. Due to the unique microsphere structure, the contact area of the active material with electrolyte is minimized. As expected, the P2-Na_0.7CoO₂ microspheres exhibit enhanced electrochemical performance for sodium storage in terms of high reversible capacity (125 mAh g⁻¹ at 5 mA g⁻¹), superior rate capability and long cycle life (86 % capacity retention over 300 cycles). Importantly, the synthesis method can be easily extended to synthesize other layered metal oxide (P2-Na_0.7MnO₂ and O3-NaFeO₂) microspheres.     

Proton/Mg2+ Co-Insertion Chemistry in Aqueous Mg-Ion Batteries: From the Interface to the Inner

Co-insertion of protons happens widely and enables divalent-ion aqueous batteries to achieve high performances. However, detailed investigations and comprehensive understandings of proton co-insertion are scarce. Herein, we demonstrate that proton co-insertion into tunnel materials is determined jointly by interface derivation and inner diffusion: at the interface, hdrated Mg²⁺ has poor insertion kinetics, and therefore accumulates and hydrolyzes to produce protons; in the tunnels, co-inserted/lattice H₂O molecules block the Mg²⁺ diffusion while facilitate the proton diffusion. When monoclinic vanadium dioxide (VO₂(B)) anode is tested in Mg(CH₃COO)₂ aqueous solution, the formation of Mg-rich solid electrolyte interphase on the VO₂(B) electrode and co-insertion of derived protons are probed; in the tunnels, the diffusion energy barrier of Mg²⁺+H₂O is 2.7 eV, while that of the protons is 0.37 eV. Thus, protons dominate the subsequent insertion and inner diffusion. As a consequence, the VO₂(B) achieves a high capacity of 257.0 mAh g⁻¹ at 1 A g⁻¹, a high rate retention of 59.1 % from 1 to 8 A g⁻¹, and stable cyclability of 3000 times with a capacity retention of 81.5 %. This work provides an in-depth understanding of the proton co-insertion and may promote the development of rechargeable aqueous batteries.     

Boosting the “Solid–Liquid–Solid” Conversion Reaction via Bifunctional Carbonate-Based Electrolyte for Ultra-long-life Potassium–Sulfur Batteries

Potassium–sulfur (K−S) batteries have attracted wide attention owing to their high theoretical energy density and low cost. However, the intractable shuttle effect of K polysulfides results in poor cyclability of K−S batteries, which severely limits their practical application. Herein, a bifunctional concentrated electrolyte (3 mol L⁻¹ potassium bis(trifluoromethanesulfonyl)imide in ethylene carbonate (EC)) with high ionic conductivity and low viscosity is developed to regulate the dissolution behavior of polysulfides and induce uniform K deposition. The organic groups in the cathode electrolyte interphase layer derived from EC can effectively block the polysulfide shuttle and realize a “solid–liquid–solid” reaction mechanism. The KF-riched solid-electrolyte interphase inhibits K dendrite growth during cycling. As a result, the achieved K−S batteries display a high reversible capacity of 654 mAh g⁻¹ at 0.5 A g⁻¹ after 800 cycles and a long lifespan over 2000 cycles at 1 A g⁻¹.