Highly reversible Zn metal anode enabled by sustainable hydroxyl chemistry.

Rechargeable Zn metal batteries (RZMBs) may provide a more sustainable and lower-cost alternative to established battery technologies in meeting energy storage applications of the future. However, the most promising electrolytes for RZMBs are generally aqueous and require high concentrations of salt(s) to bring efficiencies toward commercially viable levels and mitigate water-originated parasitic reactions including hydrogen evolution and corrosion. Electrolytes based on nonaqueous solvents are promising for avoiding these issues, but full cell performance demonstrations with solvents other than water have been very limited. To address these challenges, we investigated MeOH as an alternative electrolyte solvent. These MeOH-based electrolytes exhibited exceptional Zn reversibility over a wide temperature range, with a Coulombic efficiency > 99.5% at 50% Zn utilization without cell short-circuit behavior for > 1,800 h. More important, this remarkable performance translates well to Zn || metal-free organic cathode full cells, supporting < 6% capacity decay after > 800 cycles at -40 °C.

Modular Design of Functional Glucose Monomer and Block Co-Polymer toward Stable Zn Anodes.

Aqueous Zn batteries employing mildly acidic electrolytes have emerged as promising contenders for safe and cost-effective energy storage solutions. Nevertheless, the intrinsic reversibility of the Zn anode becomes a focal concern due to the involvement of acidic electrolyte, which triggers Zn corrosion and facilitates the deposition of insulating byproducts. Moreover, the unregulated growth of Zn over cycling amplifies the risk of internal short-circuiting, primarily induced by the formation of Zn dendrites. In this study, a class of glucose-derived monomers and a block copolymer are synthesized through a building-block assembly strategy, ultimately leading to uncover the optimal polymer structure that suppresses the Zn corrosion while allowing efficient ion conduction with a substantial contribution from cation transport. Leveraging these advancements, remarkable enhancements are achieved in the realm of Zn reversibility, exemplified by a spectrum of performance metrics, including robust cycling stability without voltage overshoot and short-circuiting during 3000 h of cycling, stable operation at a high depth of charge/discharge of 75% and a high current density, >95% Coulombic efficiency over 2000 cycles, successful translation of the anode improvement to full cell performance. These polymer designs offer a transformative path based on the modular synthesis of polymeric coatings toward highly reversible Zn anode.

Se-p Orbitals Induced "Strong d-d Orbitals Interaction" Enable High Reversibility of Se-Rich ZnSe/MnSe@C Electrode as Excellent Host for Sodium-Ion Storage.

The heterostructure of transition-metal chalcogenides is a promising approach to boost alkali ion storage due to fast charge kinetics and reduction of activation energy. However, cycling performance is a paramount challenge that is suffering from poor reversibility. Herein, it is reported that Se-rich particles can chemically interact with local hexagonal ZnSe/MnSe@C heterostructure environment, leading to effective ions insertion/extraction, enabling high reversibility. Enlightened by theoretical understanding, Se-rich particles endow high intrinsic conductivities in term of low energy barriers (1.32 eV) compared with those without Se-rich particles (1.50 eV) toward the sodiation process. Moreover, p orbitals of Se-rich particles may actively participate and further increase the electronegativity that pushes the Mn d orbitals (dxy and dx2-y2) and donate their electrons to dxz and dyz orbitals, manifesting strong d-d orbitals interaction between ZnSe and MnSe. Such fundamental interaction will adopt a well-stable conducive electronic bridge, eventually, charges are easily transferred from ZnSe to MnSe in the heterostructure during sodiation/desodiation. Therefore, the optimized Se-rich ZnSe/MnSe@C electrode delivered high capacity of 576 mAh g-1 at 0.1 A g-1 after 100 cycles and 384 mAh g-1 at 1 A g-1 after 2500 cycles, respectively. In situ and ex situ measurements further indicate the integrity and reversibility of the electrode materials upon charging/discharging.

A Passivation-Free Solid Electrolyte Interface Regulated by Magnesium Bromide Additive for Highly Reversible Magnesium Batteries.

Highly reversible Mg battery chemistry demands a suitable electrolyte formulation highly compatible with currently available electrodes. In general, conventional electrolytes form a passivation layer on the Mg anode, requiring the use of MgCl2 additives that lead to severe corrosion of cell components and low anodic stability. Herein, for the first time, we conducted a comparative study of a series of Mg halides as potential electrolyte additives in conventional magnesium bis(hexamethyldisilazide)-based electrolytes. A novel electrolyte formulation that includes MgBr2 showed unprecedented performance in magnesium plating/stripping, with an average Coulombic efficiency of 99.26% over 1000 cycles at 0.5 mA/cm2 and 0.5 mAh/cm2. Further analysis revealed the in situ formation of a robust Mg anode-electrolyte interface, which leads to dendrite-free Mg deposition and stable cycling performance in a Mg-Mo6S8 battery over 100 cycles. This study demonstrates the rational formulation of a novel MgBr2-based electrolyte with high anodic stability of 3.1 V for promising future applications.

High Utilization of Composite Magnesium Metal Anodes Enabled by a Magnesiophilic Coating.

Metallic magnesium is a promising high-capacity anode material for energy storage technologies beyond lithium-ion batteries. However, most reported Mg metal anodes are only cyclable under shallow cycling (≤1 mAh cm-2) and thus poor Mg utilization (<3%) conditions, significantly compromising their energy-dense characteristic. Herein, composite Mg metal anodes with high capacity utilization of 75% are achieved by coating magnesiophilic gold nanoparticles on copper foils for the first time. Benefiting from homogeneous ionic flux and uniform deposition morphology, the Mg-plated Au-Cu electrode exhibits high average Coulombic efficiency of 99.16% over 170 h cycling at 75% Mg utilization. Moreover, the full cell based on Mg-plated Au-Cu anode and Mo6S8 cathode achieves superior capacity retention of 80% after 300 cycles at a low negative/positive ratio of 1.33. This work provides a simple yet effective general strategy to enhance Mg utilization and reversibility, which can be extended to other metal anodes as well.

Anode-Free Lithium Metal Batteries Based on an Ultrathin and Respirable Interphase Layer.

Anode-free lithium (Li) metal batteries are desirable candidates in pursuit of high-energy-density batteries. However, their poor cycling performances originated from the unsatisfactory reversibility of Li plating/stripping remains a grand challenge. Here we show a facile and scalable approach to produce high-performing anode-free Li metal batteries using a bioinspired and ultrathin (250 nm) interphase layer comprised of triethylamine germanate. The derived tertiary amine and Lix Ge alloy showed enhanced adsorption energy that significantly promoted Li-ion adsorption, nucleation and deposition, contributing to a reversible expansion/shrinkage process upon Li plating/stripping. Impressive Li plating/stripping Coulombic efficiencies (CEs) of ≈99.3 % were achieved for 250 cycles in Li/Cu cells. In addition, the anode-free LiFePO4 full batteries demonstrated maximal energy and power densities of 527 Wh kg-1 and 1554 W kg-1 , respectively, and remarkable cycling stability (over 250 cycles with an average CE of 99.4 %) at a practical areal capacity of ≈3 mAh cm-2 , the highest among state-of-the-art anode-free LiFePO4 batteries. Our ultrathin and respirable interphase layer presents a promising way to fully unlock large-scale production of anode-free batteries.

Latticed-Confined Conversion Chemistry of Battery Electrode.

The electrochemical conversion reaction, usually featured by multiple redox processes and high specific capacity, holds great promise in developing high-energy rechargeable battery technologies. However, the complete structural change accompanied by spontaneous atomic migration and volume variation during the charge/discharge cycle leads to electrode disintegration and performance degradation, therefore severely restricting the application of conventional conversion-type electrodes. Herein, latticed-confined conversion chemistry is proposed, where the "intercalation-like" redox behavior is realized on the electrode with a "conversion-like" high capacity. By delicately formulating the high-entropy compounds, the pristine crystal structure can be preserved by the inert lattice framework, thus enabling an ultra-high initial Coulombic efficiency of 92.5% and a long cycling lifespan over a thousand cycles after the quasistatic charge-discharge cycle. This lattice-confined conversion chemistry unfolds a ubiquitous insight into the localized redox reaction and sheds light on developing high-performance electrodes toward next-generation high-energy rechargeable batteries.

Ion/Electron Redistributed 3D Flexible Host for Achieving Highly Reversible Li Metal Batteries.

3D carbon frameworks are promising hosts to achieve highly reversible lithium (Li) metal anodes, whereas insufficient effects are attributed to their single electron conductivity causing local aggregating of electron/Li+ and uncontrollable Li dendrites. Herein, an ion/electron redistributed 3D flexible host is designed by lithiophilic carbon fiber cloth (CFC) modified with metal-organic framework (MOF)-derived porous carbon sheath with embedded CoP nanoparticles (CoP-C@CFC). Theory calculations demonstrate the strong binding energy and plenty of charge transfer from the reaction between CoP and Li atom are presented, which is beneficial to in situ construct a Li3 P@Co ion/electron conductive interface on every single CoP-C@CFC. Thanks to the high ionic conductive Li3 P and electron-conductive Co nanoparticles, the rapid dispersion of Li+ and obviously reduced local current density can be achieved simultaneously. Furthermore, in situ optical microscopy observations display obvious depression for volume expansion and Li dendrites. As expected, a miraculous average Coulombic efficiency (CE) of 99.96% over 1100 cycles at 3 mA cm-2 and a low overpotential of 11.5 mV with prolonged cycling of over 3200 h at 20% depth of discharge are successfully obtained. Consequently, the CoP-C@CFC-Li||LiFePO4 full cells maintain a capacity retention of 95.8% with high CE of 99.96% over 500 cycles at 2 C and excellent rate capability.

A Lattice-Matching Strategy for Highly Reversible Copper-Metal Anodes in Aqueous Batteries.

Copper metal is an attractive anode material for aqueous rechargeable batteries due to its high theoretical specific capacity (844 mAh g-1 ), good environmental compatibility and high earth abundance. However, the Cu anodes often suffer from poor deposition/stripping reversibility and nonuniform deposition during the charge/discharge process, degrading the lifetime of aqueous Cu-metal batteries. Herein, a lattice-matching strategy was developed to design high-performance Cu-metal anodes. In such a strategy, Ni substrates that exhibit high lattice matching with Cu were selected to support the Cu anodes. The high lattice matching endows Cu anodes with high deposition/stripping reversibility, low nucleation overpotential as well as a uniform and dense electrodeposition on Ni substrates. Based on the Ni substrate-supported Cu anodes, the full cells paired with lead dioxide cathodes show a stable cycling behavior. This work provides a route for the design of high-performance Cu electrodes in aqueous rechargeable batteries.

Self-Templated Formation of P2-type K0.6CoO2 Microspheres for High Reversible Potassium-Ion Batteries.

Layered metal oxides have been widely used as the best cathode materials for commercial lithium-ion batteries and are being intensively explored for sodium-ion batteries. However, their application to potassium-ion batteries (PIBs) is hampered because of the poor cycling stability and low rate capability due to the larger ionic size of K+ than of Li+ or Na+. Herein, a facile self-templated strategy was used to synthesize unique P2-type K0.6CoO2 microspheres that consist of aggregated primary nanoplates as PIB cathodes. The unique K0.6CoO2 microspheres with aggregated structure significantly enhanced the kinetics of the K+ intercalation/deintercation and also minimized the parasitic reactions between the electrolyte and K0.6CoO2. The P2-K0.6CoO2 microspheres demonstrated a high reversible capacity of 82 mAh g-1 at 10 mA g-1, high rate capability of 65 mAh g-1 at 100 mA g-1, and long cycle life (87% capacity retention over 300 cycles). The high reversibility of the P2-K0.6CoO2 full cell paired with a hard carbon anode further demonstrated the feasibility of PIBs. This work not only successfully demonstrates exceptional performance of P2-type K0.6CoO2 cathodes and microspheres K0.6CoO2∥hard carbon full cells, but also provides new insights into the exploration of other layered metal oxides for PIBs.

A Photolithographable Electrolyte for Deeply Rechargeable Zn Microbatteries in On-Chip Devices.

Zn batteries show promise for microscale applications due to their compatibility with air fabrication but face challenges like dendrite growth and chemical corrosion, especially at the microscale. Despite previous attempts in electrolyte engineering, achieving successful patterning of electrolyte microscale devices has remained challenging. Here, successful patterning using photolithography is enabled by incorporating caffeine into a UV-crosslinked polyacrylamide hydrogel electrolyte. Caffeine passivates the Zn anode, preventing chemical corrosion, while its coordination with Zn2+ ions forms a Zn2+-conducting complex that transforms into ZnCO3 and 2ZnCO3·3Zn(OH)2 over cycling. The resulting Zn-rich interphase product significantly enhances Zn reversibility. In on-chip microbatteries, the resulting solid-electrolyte interphase allows the Zn||MnO2 full cell to cycle for over 700 cycles with an 80% depth of discharge. Integrating the photolithographable electrolyte into multilayer microfabrication creates a microbattery with a 3D Swiss-roll structure that occupies a footprint of 0.136 mm2. This tiny microbattery retains 75% of its capacity (350 µAh cm-2) for 200 cycles at a remarkable 90% depth of discharge. The findings offer a promising solution for enhancing the performance of Zn microbatteries, particularly for on-chip microscale devices, and have significant implications for the advancement of autonomous microscale devices.

Programmable DNA Interphase Layers for High-Performance Anode-Free Lithium Metal Batteries.

Anode-free lithium (Li) metal batteries are promising candidates for advanced energy storage, attributed to their appealing characteristics such as high energy density, low cost, and convenient production. However, their major challenges lie in the poor cycling and rate performance owing to the inferior reversibility and kinetics of Li plating and stripping, which significantly hinder their real-world applications. Here, it is demonstrated that deoxyribonucleic acid (DNA), the most important genetic material in nature, can serve as a highly programmable interphase layer for innovation of anode-free Li metal batteries. It is found that the abundant base pairs in DNA can contribute transient Li-N bonds that facilitate homogeneous Li+ flux, thus resulting in excellent Li plating/stripping kinetics and reversibility even at a harsh areal current of 15 mA cm-2. The anode-free LiFePO4 full batteries based on an ultrathin (0.12 µm) and ultralight (≈0.01 mg cm-2) DNA interphase layer show high CEs (≈99.1%) over 400 cycles, corresponding to an increase of ≈186% compared with bare copper (Cu) foil. These results shed light on the excellent programmability of DNA as a new family of interphase materials for anode-free batteries, and provide a new paradigm for future battery innovation toward high programmability, high sustainability, and remarkable electrochemical performance.

Unravelling Twin Topotactic/Nontopotactic Reactive TiSe2 Cathodes for Aqueous Batteries.

Titanium selenide (TiSe2 ), a model transition metal chalcogenide material, typically relies on topotactic ion intercalation/deintercalation to achieve stable ion storage with minimal disruption of the transport pathways but has restricted capacity (<130 mAh g-1 ). Developing novel energy storage mechanisms beyond conventional intercalation to break capacity limits in TiSe2 cathodes is essential yet challenging. Herein, the ion storage properties of TiSe2 are revisited and an unusual thermodynamically stable twin topotactic/nontopotactic Cu2+ accommodation mechanism for aqueous batteries is unraveled. In situ synchrotron X-ray diffraction and ex situ microscopy jointly demonstrated that topotactic intercalation sustained the ion transport framework, nontopotactic conversion involved localized multielectron reactions, and these two parallel reactions are miraculously intertwined in nanoscale space. Comprehensive experimental and theoretical results suggested that the twin-reaction mechanism significantly improved the electron transfer ability, and the reserved intercalated TiSe2 structure anchored the reduced titanium monomers with high affinity and promoted efficient charge transfer to synergistically enhance the capacity and reversibility. Consequently, TiSe2 nanoflake cathodes delivered a never-before-achieved capacity of 275.9 mAh g-1 at 0.1 A g-1 , 93.5% capacity retention over 1000 cycles, and endow hybrid batteries (TiSe2 -Cu||Zn) with a stable energy supply of 181.34 Wh kg-1 at 2339.81 W kg-1 , offering a promising model for aqueous ion storage.

Designing New Sustainable Polyurethane Adhesives: Influence of the Nature and Content of Diels-Alder Adducts on Their Thermoreversible Behavior.

With a view to the development of new sustainable and functional adhesives, two Diels-Alder (DA) adducts are incorporated as a third component into the curing process of solvent-based and solvent-free polyurethanes in this study. The influence of the nature and content of the DA molecules on the retro-DA (rDA) reaction and its reversibility and cyclability is investigated. It is demonstrated that the bonding/debonding properties of the adhesives are mainly controlled by the concentration of the DA adducts, with a minimum thermoreversible bond (TB) content required that depends on the system and the total ratio between all the diols in the formulation. For the solvent-based system, rDA/DA reversibility can be repeated up to ~20 times without deterioration, in contrast to the solvent-free system where a gradual loss in the DA network reconstruction efficiency is observed. Despite this limitation, the solvent-free system presents clear advantages from an environmental point of view. The changes observed in the physical properties of these new thermoreversible adhesives are of great relevance for recycling strategies and, in particular, their potential for separating multilayered film packaging materials in order to recycle the individual polymer films involved.

Architecting a Hydrated Ca0.24V2O5 Cathode with a Facile Desolvation Interface for Superior-Performance Aqueous Zinc Ion Batteries.

Vanadium-based materials are promising cathode candidates for low-cost and high-safety aqueous zinc-ion batteries (AZIBs). However, they suffer from inferior rate capability and undesirable capacity fading due to their intrinsic poor conductivity and structural instability. Herein, we synthesize hydrated Ca0.24V2O5·0.75H2O (CaVOH) nanoribbons with in situ incorporations of the carbon nanotubes via a one-step hydrothermal method, achieving an integrated architecture hybrid cathode (C/CaVOH) design. Benefitting from the robust structure and low desolvation interface, the prefabricated C/CaVOH cathodes deliver a high capacity of 384.2 mA h g-1 at 0.5 A g-1 with only 5.6% capacity decay over 300 cycles, enable an ultralong cycling life of 10,000 cycles at 20.0 A g-1 with 80.2% capacity retention, and exhibit an impressive rate capability (165 mA h g-1 at 40.0 A g-1) with a high mass loading of ∼4 mg cm-2. Moreover, through the theoretical calculations and a series of ex situ characterizations, we demonstrate the Zn2+/H+ co-intercalation storage mechanism, the key role of the gallery water, and the function of the induced C-O groups in promoting kinetics of the C/CaVOH electrode. This work highlights the strategy of in situ implanted high conductivity materials to engineer vanadium-based or other cathodes for high-performance AZIBs.

Highly Reversible and Rapid Sodium Storage in GeP3 with Synergistic Effect from Outside-In Optimization.

The composite GeP3/C@rGO as a sodium ion battery anode material was fabricated by introducing a carbon matrix into GeP3 through high-energy ball milling, followed by encapsulating the resultant composite with graphene via a solution-based ultrasonic method. To delineate the individual role of carbon matrix and graphene, material characterization and electrochemical analyses were performed for GeP3/C@rGO and three other samples: bare GeP3, GeP3 with graphene coating (GeP3@rGO), and GeP3 with carbon matrix (GeP3/C). GeP3/C@rGO exhibits the highest electric conductivity (5.89 × 10-1 S cm-1) and the largest surface area (167.85 m2 g-1) among the four samples. The as-prepared GeP3/C@rGO delivered a reversible high capacity of 1084 mA h g-1 at 50 mA g-1, excellent rate capacity (435.4 mA h g-1 at a high rate of 5 A g-1), and long-term cycling stability (400 cycles with a reversible capacity of 823.3 mA h g-1 at 0.2 A g-1), all of which outperform the other three samples. The kinetics investigation reveals a "pseudocapacitive behavior" in GeP3/C and GeP3/C@rGO, where solely faradic reactions took place in bare GeP3 and GeP3@rGO with a typical "battery behavior". Based on ex-situ X-ray photoelectron spectroscopy and ex-situ electrochemical impedance spectroscopy, the carbon matrix serves to activate and stabilize the interior of the composite, while the graphene protects and restrains the exterior surface. Benefiting from the synergistic combination of these two components, GeP3/C@rGO achieved extremely stable cycling stability as well as outstanding rate performance.

Amorphous Tin Oxide Nanohelix Structure Based Electrode for Highly Reversible Na-Ion Batteries.

An array of amorphous tin oxide (a-SnOx) nanohelixes (NHs) was fabricated on copper foil as an electrode for Na-ion batteries via the oblique angle deposition method, a solution- and surfactant-free process. The combination of the amorphous phase SnOx with a low oxidation number and its vertically aligned NH geometry with a large surface area and high porosity, which facilitate Na-ion dynamics and accommodate the volume changes, enabled a reversible capacity of up to 915 mA h g-1 after 50 cycles, fast rate capability with 48.1% retention at 2 A g-1, and high stability, which are superior to those of crystalline nanoparticle-based electrodes.