Ion Sieve Interface Assisted Zinc Anode with High Zinc Utilization and Ultralong Cycle Life for 61 Wh/kg Mild Aqueous Pouch Battery.

The cycling stability of a thin zinc anode under high zinc utilization has a critical impact on the overall energy density and practical lifetime of zinc ion batteries. In this study, an ion sieve protection layer (ZnSnF@Zn) was constructed in situ on the surface of a zinc anode by chemical replacement. The ion sieve facilitated the transport and desolvation of zinc ions at the anode/electrolyte interface, reduced the zinc deposition overpotential, and inhibited side reactions. Under a 50% zinc utilization, the symmetrical battery with this protection layer maintained stable cycling for 250 h at 30 mA cm-2. Matched with high-load self-supported vanadium-based cathodes (18-20 mg cm-2), the coin battery with 50% zinc utilization possessed an energy density retention of 94.3% after 1000 cycles at 20 mA cm-2. Furthermore, the assembled pouch battery delivered a whole energy density of 61.3 Wh kg-1, surpassing the highest mass energy density among reported mild zinc batteries, and retained 76.7% of the energy density and 85.3% (0.53 Ah) of the capacity after 300 cycles.

Preferred Orientation Deposition via Multifunctional Gel Electrolyte with Molecular Anchor Enabling Highly Reversible Zn Anode.

The high activity of water molecules results in a series of awful parasitic reaction, which seriously impede the development of aqueous zinc batteries. Herein, a new gel electrolyte with multiple molecular anchors is designed by employing natural biomaterials from chitosan and chlorophyll derivative. The gel electrolyte firmly anchors water molecules by ternary hydrogen bonding to reduce the activity of water molecules and inhibit hydrogen evolution reaction. Meanwhile, the multipolar charged functional groups realize the gradient induction and redistribution of Zn2+ , which drives oriented Zn (002) plane deposition of Zn2+ and then achieves uniform Zn deposition and dendrite-free anode. As a result, it endows the Zn||Zn cell with over 1700 h stripping/plating processes and a high efficiency of 99.4% for the Zn||Cu cell. In addition, the Zn||V2 O5 full cells also exhibit capacity retention of 81.7% after 600 cycles at 0.5 A g-1 and excellent long-term stability over 1600 cycles at 2 A g-1 , and the flexible pouch cells can provide stable power for light-emitting diodes even after repeated bending. The gel electrolyte strategy provides a reference for reversible zinc anode and flexible wearable devices.

Energy Band Engineering Guided Design of Bidirectional Catalyst for Reversible Li-CO2 Batteries.

Li-CO2 batteries arouse great interest in the context of carbon neutralization, but their practicability is severely hindered by the sluggish CO2 redox reaction kinetics at the cathode, which brings about formidable challenges such as high overpotential and low Coulombic efficiency. For the complex multi-electron transfer process, the design of catalysts at the molecular or atomic level and the understanding of the relationship between electron state and performance are essential for the CO2 redox. However, little attention is paid to it. In this work, using Co3 S4 as a model system, density functional theory (DFT) calculations reveal that the adjusted d-band and p-band centers of Co3 S4 with the introduction of Cu and sulfur vacancies are hybridized between CO2 and Li species, respectively, which is conducive to the adsorption of reactants and the decomposition of Li2 CO3 , and the experimental results further verify the effectiveness of energy band engineering. As a result, a highly efficient bidirectional catalyst is produced and shows an ultra-small voltage gap of 0.73 V and marvelous Coulombic efficiency of 92.6%, surpassing those of previous catalysts under similar conditions. This work presents an effective catalyst design and affords new insight into the high-performance cathode catalyst materials for Li-CO2 batteries.

Recycled Tandem Catalysts Promising Ultralow Overpotential Li-CO2 Batteries.

Lithium-carbon dioxide (Li-CO2 ) batteries are regarded as a prospective technology to relieve the pressure of greenhouse emissions but are confronted with sluggish CO2 redox kinetics and low energy efficiency. Developing highly efficient and low-cost catalysts to boost bidirectional activities is craved but remains a huge challenge. Herein, derived from the spent lithium-ion batteries, a tandem catalyst is subtly synthesized and significantly accelerates the CO2 reduction and evolution reactions (CO2 RR and CO2 ER) kinetics with an in-built electric field (BEF). Combining with the theoretical calculations and advanced characterization techniques, this work reveals that the designed interface-induced BEF regulates the adsorption/decomposition of the intermediates during CO2 RR and CO2 ER, endowing the recycled tandem catalyst with excellent bidirectional activities. As a result, the spent electronics-derived tandem catalyst exhibits remarkable bidirectional catalytic performance, such as an ultralow voltage gap of 0.26 V and an ultrahigh energy efficiency of 92.4%. Profoundly, this work affords new opportunities to fabricate low-cost electrocatalysts from recycled spent electronics and inspires fresh perceptions of interfacial regulation including but not limited to BEF to engineer better Li-CO2 batteries.

Remodeling Zinc Deposition via Multisite Zincophilic Chlorophyll for Powerful Aprotic Zinc Batteries.

The organic electrolyte can resolve the hurdle of hydrogen evolution in aqueous electrolytes but suffers from sluggish electrochemical reaction kinetics due to a compromised mass transfer process. Herein, we introduce a chlorophyll, zinc methyl 3-devinyl-3-hydroxymethyl-pyropheophorbide-a (Chl), as a multifunctional electrolyte additive for aprotic zinc batteries to address the related dynamic problems in organic electrolyte systems. The Chl exhibits multisite zincophilicity, which significantly reduces the nucleation potential, increases the nucleation sites, and induces uniform nucleation of Zn metal with a nucleation overpotential close to zero. Furthermore, the lower LUMO of Chl contributes to a Zn-N-bond-containing SEI layer and inhibits the decomposition of the electrolyte. Therefore, the electrolyte enables repeated zinc stripping/plating up to 2000 h (2 Ah cm-2 cumulative capacity) with an overpotential of only 32 mV and a high Coulomb efficiency of 99.4%. This work is expected to enlighten the practical application of organic electrolyte systems.

In Situ Buildup of Zinc Anode Protection Films with Natural Protein Additives for High-Performance Zinc Battery Cycling.

The uncontrolled growth of dendrites and serious side reactions, such as hydrogen evolution and corrosion, significantly hinder the industrial application and development of aqueous zinc-ion batteries (ZIBs). This article presents ovalbumin (OVA) as a multifunctional electrolyte additive for aqueous ZIBs. Experimental characterizations and theoretical calculations reveal that the OVA additive can replace the solvated sheath of recombinant hydrated Zn2+ through the coordination water, preferentially adsorb on the surface of the Zn anode, and construct a high-quality self-healing protective film. Notably, the OVA-based protective film with strong Zn2+ affinity will promote uniform Zn deposition and inhibit side reactions. As a result, Zn||Zn symmetrical batteries in ZnSO4 electrolytes containing OVA achieve a cycle life exceeding 2200 h. Zn||Cu batteries and Zn||MnO2 (2 A g-1) full batteries show excellent cycling stability for 2500 cycles, demonstrating promising application prospects. This study provides insights into utilizing natural protein molecules to modulate the kinetics of Zn2+ diffusion and enhance the stability of the anode interface.

Bimetal Substitution Enabled Energetic Polyanion Cathode for Sodium-Ion Batteries.

The practical application of Na-superionic conductor structured materials is hindered by limited energy density and structure damage upon activating the third Na+. We propose a bimetal substitution strategy with cheaper Fe and Ni elements for costive vanadium in the polyanion to improve both ionic and electronic conductivities, and a single two-phase reaction during Na+ intercalation/deintercalation and much reduced Na+ diffusion barrier are uncovered by ex-situ X-ray diffraction and density functional theory calculations. Thus, the obtained cathode, Na3Fe0.8VNi0.2(PO4)3, shows excellent electrochemical performances including high specific capacity (102.2 mAh g-1 at 0.1C), excellent rate capability (79.3 mAh g-1 at 20C), cycling stability (84.6% of capacity retention over 1400 cycles at 20C), low-temperature performance (89.7 mAh g-1 at 2C and -10 °C), and structure stability in an extended voltage window for the third Na+ utilization. A competitive energy density of ≈287 Wh kg-1 for full batteries based on cathode and anode materials is also confirmed.

Electrolytes for Multivalent Metal-Ion Batteries: Current Status and Future Prospect.

Electrochemical energy storage has experienced unprecedented advancements in recent years and extensive discussions and reviews on the progress of multivalent metal-ion batteries have been made mainly from the aspect of electrode materials, but relatively little work comprehensively discusses and provides an outlook on the development of electrolytes in these systems. Under this circumstance, this Review will initially introduce different types of electrolytes in current multivalent metal-ion batteries and explain the basic ion conduction mechanisms, preparation methods, and pros and cons. On this basis, we will discuss in detail the research and development of electrolytes for multivalent metal-ion batteries in recent years, and finally, critical challenges and prospects for the application of electrolytes in multivalent metal-ion batteries will be put forward.

A dual conducting network corbelled hydrated vanadium pentoxide cathode for high-rate aqueous zinc-ion batteries.

Aqueous zinc-ion batteries (ZIBs) are widely recognized for their excellent safety and high theoretical capacity but are hindered by the scarcity of cathode materials with high-rate performance and stability. Herein, a dual conducting network corbelled hydrated vanadium pentoxide that involves structural water as a pillar to enlarge the layer spacing of vanadium pentoxide and ensure cycling stability was reported. Along with the proton co-insertion, the hydrated vanadium pentoxide delivers nearly theoretical specific capacities of 524.6 mA h g-1 at 0.3 A g-1 and 258.7 mA h g-1 at 10 A g-1, which was largely due to non-faradaic contribution, and retains 196.8 mA h g-1 at 4.8 A g-1 after 1100 cycles. Notably, a high energy density of 409.3 W h kg-1 at 0.3 A g-1 and a power density of 6666.4 W kg-1 at 10 A g-1 have also been achieved. The design strategy offers a potential path to develop high-rate ZIBs.

Revealing the Superiority of Fast Ion Conductor in Composite Electrolyte for Dendrite-Free Lithium-Metal Batteries.

Composite electrolytes composed of a nanoceramic and polymer have been widely studied because of their high ionic conductivity, good Li-ion transference number, and excellent machinability, whereas the intrinsic reason for the improvement of performance is ambiguous. Herein, we have designed a functional polymer skeleton with different types of nanofiller to reveal the superiority of fast ion conductors in composite electrolyte. Three types of ceramics with different dielectric constants and Li-ion transfer ability were selected to prepare composite electrolytes, the composition, structure, and electrochemical performances of which were systematically investigated. It was found that the addition of fast ion conductive ceramics could provide a high Li-ion transference ability and decreased diffusion barrier because the additional pathways existed in the ceramic, which are revealed by experiment and density functional theory calculations. Benefiting from the superiority of fast ion conductor, Li-metal batteries with this advanced composite electrolyte exhibit an impressive cycling stability and enable a dendrite-free Li surface after cycling. Our work enriches the understanding of the function of fast ion conductors in composite electrolyte and guides the design for other high-performance composite electrolytes in rechargeable solid batteries.

A Covalent Organic Framework with Extended π-Conjugated Building Units as a Highly Efficient Recipient for Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries have recently become a research hotspot because of their tempting theoretical capacity and energy density. Nevertheless, the notorious shuttle of polysulfides hinders the advancement of Li-S batteries. Herein, a two-dimensional covalent organic framework (COF) with extended π-conjugated units has been designed, synthesized, and used as sulfur recipients with 88.4 wt % in loading. The COF offers an elaborate platform for sufficient Li-S redox reactions with almost theoretical capacity release (1617 mA h g-1 at 0.1 C), satisfactory rate capability, and intensively traps polysulfides for a decent Coulombic efficiency (ca. 98.0%) and extremely low capacity decay (0.077% per cycle after 528 cycles at 0.5 C). The structural factors of the COF on the high-performance batteries are revealed by density functional theory calculations to be the high degrees of conjugation and proper interlayer space. This work not only demonstrates the great potential of COFs as highly efficient sulfur recipients but also provides a viable guidance for further design of COF materials to tackle shuttling issues toward active materials in electrochemical energy storage.

Enabling a Durable Electrochemical Interface via an Artificial Amorphous Cathode Electrolyte Interphase for Hybrid Solid/Liquid Lithium-Metal Batteries.

A hybrid solid/liquid electrolyte with superior security facilitates the implementation of high-energy-density storage devices, but it suffers from inferior chemical compatibility with cathodes. Herein, an optimal lithium difluoro(oxalato)borate salt was introduced to build in situ an amorphous cathode electrolyte interphase (CEI) between Ni-rich cathodes and hybrid electrolyte. The CEI preserves the surface structure with high compatibility, leading to enhanced interfacial stability. Meanwhile, the space-charge layer can be prominently mitigated at the solid/solid interface via harmonized chemical potentials, acquiring promoted interfacial dynamics as revealed by COMSOL simulation. Consequently, the amorphous CEI integrates the bifunctionality to provide an excellent cycling stability, high Coulombic efficiency, and favorable rate capability in high-voltage Li-metal batteries, innovating the design philosophy of functional CEI strategy for future high-energy-density batteries.

Preparation of a porous graphite felt electrode for advance vanadium redox flow batteries.

Rapid mass transfer and great electrochemical activity have become the critical points for designing electrodes in vanadium redox flow batteries (VRFBs). In this research, we show a porous graphite felt (GF@P) electrode to improve the electrochemical properties of VRFBs. The generation of pores on graphite felt electrodes is based on etching effects of iron to carbon. The voltage and energy efficiencies of VRFB based on the GF@P electrode can reach 72.6% and 70.7% at a current density of 200 mA cm-2, respectively, which are 8.3% and 7.9% better than that of untreated GF@U (graphite felt). Further, the VRFBs based on GF@P electrodes possess supreme stability after over 500 charge-discharge cycles at 200 mA cm-2. The high-efficiency approach reported in this study offers a new strategy for designing high-performance electrode materials applied in VRFBs.

Engineering Janus Interfaces of Ceramic Electrolyte via Distinct Functional Polymers for Stable High-Voltage Li-Metal Batteries.

The fast-ionic-conducting ceramic electrolyte is promising for next-generation high-energy-density Li-metal batteries, yet its application suffers from the high interfacial resistance and poor interfacial stability. In this study, the compatible solid-state electrolyte was designed by coating Li1.4Al0.4Ti1.6(PO4)3 (LATP) with polyacrylonitrile (PAN) and polyethylene oxide (PEO) oppositely to satisfy deliberately the disparate interface demands. Wherein, the upper PAN constructs soft-contact with LiNi0.6Mn0.2Co0.2O2, and the lower PEO protects LATP from being reduced, guaranteeing high-voltage tolerance and improved stability toward Li-metal anode performed in one ceramic. Moreover, the core function of LATP is amplified to guide homogeneous ions distribution and hence suppresses the formation of a space-charge layer across interfaces, uncovered by the COMSOL Multiphysics concentration field simulation. Thus, such a bifunctional modified ceramic electrolyte integrates the respective superiority to render Li-metal batteries with excellent cycling stability (89% after 120 cycles), high Coulombic efficiency (exceeding 99.5% per cycle), and a dendrite-free Li anode at 60 °C, which represents an overall design of ceramic interface engineering for future practical solid battery systems.

Unveiling the Role of Heteroatom Gradient-Distributed Carbon Fibers for Vanadium Redox Flow Batteries with Long Service Life.

The fundamental understanding of electrocatalytic reaction process is anticipated to guide electrode upgradation and acquirement of high-performance vanadium redox flow batteries (VRFBs). Herein, a carbon fiber prototype system with a heteroatom gradient distribution has been developed with enlarged interlayer spacing and a high graphitization that improve the electronic conductivity and accelerate the electrocatalytic reaction, and the mechanism by which gradient-distributed heteroatoms enhance vanadium redox reactions was elucidated with the assistance of density functional theory calculations. All these contributions endow the obtained electrode prominent redox reversibility and durability with only 1.7% decay in energy efficiency over 1000 cycles at 150 mA cm-2 in the VRFBs. Our work sheds light on the significance of elaborated electrode design and impels the in-depth investigation of VRFBs with long service life.

Hierarchical Carbon Micro/Nanonetwork with Superior Electrocatalysis for High-Rate and Endurable Vanadium Redox Flow Batteries.

Vanadium redox flow batteries (VRFBs) are receiving increasing interest in energy storage fields because of their safety and versatility. However, the electrocatalytic activity of the electrode is a pivotal factor that still restricts the power and cycling capabilities of VRFBs. Here, a hierarchical carbon micro/nanonetwork (HCN) electrode codoped with nitrogen and phosphorus is prepared for application in VRFBs by cross-linking polymerization of aniline and physic acid, and subsequent pyrolysis on graphite felt. Due to the hierarchical electron pathways and abundant heteroatom active sites, the HCN exhibits superior electrocatalysis toward the vanadium redox couples and imparts the VRFBs with an outstanding energy efficiency and extraordinary stability after 2000 cycles at 250 mA cm-2 and a discharge capacity of 10.5 mA h mL-1 at an extra-large current density of 400 mA cm-2. Such a micro/nanostructure design will force the advancement of durable and high-power VRFBs and other electrochemical energy storage devices.

Robust Electrodes with Maximized Spatial Catalysis for Vanadium Redox Flow Batteries.

Catalytic efficiency is a crucial index for electrodes in flow batteries, and tremendous efforts have been devoted to exploring catalysts with as many reaction zones as possible. Nevertheless, the space between the reaction sites, especially for interstitial space utilization, is usually ignored and challengeable to exploit owing to the balance between the catalytic efficiency and structural stability. Herein, a three-dimensional conducting network was constructed via a nitrogen-rich carbon film-bridged graphite felt framework (GF@N-C) to maximize its electrocatalytic effectiveness toward redox species. As the electrode, GF@N-C exhibits a superior rate constant and catalytic efficiency at 370 mA cm-2 and enables the vanadium redox flow battery to operate steadily at 200 mA cm-2 with an energy efficiency of 74.3% and a discharge specific capacity of 23 A h L-1. It is anticipated that the conducting network with optimized space utilization and catalysis will provide guidance for the design of high-efficiency electrodes and advance their development in flow batteries.

Constructing a Stable Lithium Metal-Gel Electrolyte Interface for Quasi-Solid-State Lithium Batteries.

Interfacial problems, including interfacial stability and contact issues, severely plague the practical application of Li metal anodes. Here we report an interfacial regulation strategy that stabilizes the Li metal-gel electrolyte interface through in situ constructing a stable solid electrolyte interphase (SEI) layer. By stabilizing the interface of Li metal anodes, the gel electrolyte enables dendrite-free morphology and high plating/stripping efficiency. A systematic analysis further confirms that the formed SEI layer is responsible for homogeneous deposition and stable cycling performance. Benefiting from the interfacial stability between electrodes and electrolytes, the lifespan of Li metal batteries is extended.

Designing High-Performance Composite Electrodes for Vanadium Redox Flow Batteries: Experimental and Computational Investigation.

Highly catalytic electrodes play a vital role in exploiting the capability of vanadium redox flow batteries (VRFBs), but they suffer from a tedious synthesis process and ambiguous interaction mechanisms for catalytic sites. Herein, a facile urea pyrolysis process was applied to prepare graphitic carbon nitride-modified graphite felt (GF@CN), and by the virtue of a density functional theory-assisted calculation, the electron-rich pyridinic nitrogen atom of CN granules is demonstrated as the adsorption center for redox species and plays the key role in improving the performance of VRFBs, with 800 cycles and an energy efficiency of 75% at 150 mA cm-2. Such experimental and computational collaborative investigations guide a realizable and cost-effective solution for other high-power flow batteries.

Gradiently Polymerized Solid Electrolyte Meets with Micro-/Nanostructured Cathode Array.

The poor contact between the solid-state electrolyte and cathode materials leads to a high interfacial resistance, severely limiting the rate capability of solid Li metal batteries. Herein, an integrative battery design is introduced with a gradiently polymerized solid electrolyte (GPSE), a microchannel current collector array, and nanosized cathode particles. An in situ formed GPSE encapsulates cathode nanoparticles in the microchannel with ductile inclusions to lower the interfacial impedance, and the stiff surface layer of GPSE toward anode suppresses the Li dendrite growth. The Li metal batteries based on GPSE and the Li-free hydrogenated V2O5 (V2O5-H) cathode exhibit an outstanding high rate response of up to 5 C (the capacity ratio of 5 C/1 C is 90.3%) and an ultralow capacity fade rate of 0.07% per cycle over 300 cycles. The other Li-containing cathodes such as LiFePO4 and LiNi0.5Mn0.3Co0.2O2 can also operate effectively at the rates of 5 and 2 C, respectively. Such an ingenious design may provide new insights into other solid metal batteries through an interfacial engineering manipulation at the micro- and nanolevel.