Robust Metal Research Articles

Enabling Stable Li Metal Anodes for Solid-State Batteries

Solid-state batteries have the potential to transform energy storage by providing significantly higher energy densities and improved safety compared to conventional Li-ion batteries. However, robust high-capacity Li metal anodes are required to realize this technology. Current Li metal anode designs suffer from significant degradation over time due to non-uniform Li plating/stripping and loss of contact with the solid electrolyte during cycling. Carbon scaffold hosts have been shown to mitigate this problem in liquid electrolyte systems by creating a uniform electric field and providing abundant Li nucleation sites, but they have not been well explored in solid-state systems, which require the fabrication of more complicated mixed ion/electron conducting scaffolds to provide transport of both Li ions and electrons throughout the anode. We investigated the effect of scaffold architecture and chemistry on Li morphology and electrochemical performance using a combined experiment/theory approach. Scaffolds were characterized by SEM, Raman, and XPS before cycling in cells to evaluate their performance as hosts for Li plating/stripping. Atomistic and mesoscale modeling were used to help predict Li nucleation and current density hotspots and assist in guiding scaffold design. This work provides further insight into the relationship between anode design and Li metal cycling stability and will facilitate the development of safer, high-energy-density solid-state batteries.Lawrence Livermore National Laboratory is operated by Lawrence Livermore National Security, LLC, for the U.S. Department of Energy, National Nuclear Security Administration under Contract DE-AC52-07NA27344.

Wide and Thin Li Metal Powder Electrodes and Their Electrochemical Performances

Li metal powders are very useful in fabricating wide and thin Li metal electrodes due to its ease applicability to slurry-coating process. Furthermore, not only microstructure but also functional components can be controlled or added in Li metal power electrode. These beneficial characteristics can lead to more stable and robust Li metal electrode comparing to the conventional extrusion/roll-pressed, electroplated, or vacuum evaporated Li metal electrodes. In this work, we introduce how thin and wide the Li metal electrode can be fabricated using the conventional slurry-coating method. And then, it is also included how binder-induced scaffold-like electrode structure can improve the electrochemical performances of Li metal electrode. Furthermore, the role of some inorganic additives like CNTs, LiNO3 or AgNO3 will be also discussed with significant electrochemical performance enhancements. Finally, these Li metal powders are being investigated to lithiate diffusion-dependent electrodes especially for all-solid-state batteries. [References] 1. D. Kang†, D. Jin†, H. Lee*, S.-Y. Ryou*, Y. M. Lee* et al., Chemical Engineering Journal, 452 (2023) 1394092. C. B. Dzakpasu, H. Lee*, S.-Y. Ryou*, Y. M. Lee* et al., Electrochimica Acta, 430 (2022) 1410933. J. Kim†, S. Jung†, Y. M. Lee* et al., Advanced Energy Materials, 12 (2022) 21031084. D. Jin, M.-H. Ryou*, H. Lee*, Y. M. Lee* et al., Advanced Energy Materials, 11(18) (2021) 20037695. D. Jin, M.-H. Ryou*, Y. M. Lee* et al., Chemical Engineering Journal, 406 (2021) 1268346. D. Jin, Y. M. Lee*, M.-H. Ryou* et al., Electrochimica Acta, 364 (2020) 136878

Construction of urchin-like bimetallic phosphides induced by carbon dots for efficient wide pH hydrogen production

The development of an efficient noble-metal-free and pH-universal electrocatalyst for the hydrogen evolution reaction (HER) would be highly significant for hydrogen (H2) production via electrocatalytic water splitting. However, developing such a catalyst remains a formidable task. Herein, a strategy is proposed for the in situ fabrication of a novel urchin-like NiCoP microsphere catalyst (0.5CDs-NiCoP/NF) on nickel foam (NF) using carbon dots (CDs) as a directing agent. The strong bonding between the CDs and metals provides additional active sites, giving 0.5CDs-NiCoP/NF excellent electrocatalytic hydrogen evolution performance in environments ranging from acidic to basic. Moreover, the unique structure of 0.5CDs-NiCoP/NF endows this catalyst with low Tafel slopes of 73, 146 and 74 mV dec−1 for HER in acidic, neutral and alkaline conditions, respectively. This performance exceeds that of numerous other reported non-precious HER catalysts. In summary, this work offers a novel and efficient strategy for the design and synthesis of low-cost, efficient, and robust transition metal phosphides (TMPs) electrocatalysts.

The effect of polished surface microstructure of ceramic electrolyte on solid-state sodium metal batteries

Highly stable Na anode/solid-state electrolyte (SSE) interface is vital for engineering robust solid-state sodium metal battery (SSMB). To ensure the flatness and remove the surface impurities of SSE, ceramic SSE pellets commonly require to be polished. However, there are lack of standardized instructions about the polish procedure even though researchers have realized that the properties of Na/SSE interface could be influenced dramatically by the surface microstructure of SSE pellet. In this work, the Na3.3Zr1.7Pr0.3Si2PO12 SSE pellets were polished transversely and longitudinally by sandpaper with various mesh sizes on purpose for engineering Na/SSE interfaces. It is discovered that the compatibility and wettability of Na on SSE pellets could be tuned by polish procedure due to the resultant variation of roughness, contact area and ravines. By optimizing surface microstructure of SSE pellets through polishing, the assembled symmetrical battery delivers the highest critical current density of 0.55 mA cm−2 and the lowest interface impedance (11.8 Ω cm2) at room temperature, enabling the stably cycling for 5000 h at 0.1 mA cm−2. This work sheds light on the strong correlations between polish-induced surface-microstructural changes of SSE and interface stability of Na/SSE, providing a rational reference for SSE polishing when assembling SSMB.

Topological Design of Unprecedented Metal-Organic Frameworks Featuring Multiple Anion Functionalities and Hierarchical Porosity for Benchmark Acetylene Separation.

Separation of acetylene (C2 H2 ) from carbon dioxide (CO2 ) or ethylene (C2 H4 ) is industrially important but still challenging so far. Herein, we developed two novel robust metal organic frameworks AlFSIX-Cu-TPBDA (ZNU-8) with znv topology and SIFSIX-Cu-TPBDA (ZNU-9) with wly topology for efficient capture of C2 H2 from CO2 and C2 H4 . Both ZNU-8 and ZNU-9 feature multiple anion functionalities and hierarchical porosity. Notably, ZNU-9 with more anionic binding sites and three distinct cages displays both an extremely large C2 H2 capacity (7.94 mmol/g) and a high C2 H2 /CO2 (10.3) or C2 H2 /C2 H4 (11.6) selectivity. The calculated capacity of C2 H2 per anion (4.94 mol/mol at 1 bar) is the highest among all the anion pillared metal organic frameworks. Theoretical calculation indicated that the strong cooperative hydrogen bonds exist between acetylene and the pillared SiF6 2- anions in the confined cavity, which is further confirmed by in situ IR spectra. The practical separation performance was explicitly demonstrated by dynamic breakthrough experiments with equimolar C2 H2 /CO2 mixtures and 1/99 C2 H2 /C2 H4 mixtures under various conditions with excellent recyclability and benchmark productivity of pure C2 H2 (5.13 mmol/g) or C2 H4 (48.57 mmol/g).

Topological Design of Unprecedented Metal‐Organic Frameworks Featuring Multiple Anion Functionalities and Hierarchical Porosity for Benchmark Acetylene Separation

AbstractSeparation of acetylene (C2H2) from carbon dioxide (CO2) or ethylene (C2H4) is industrially important but still challenging so far. Herein, we developed two novel robust metal organic frameworks AlFSIX‐Cu‐TPBDA (ZNU‐8) with znv topology and SIFSIX‐Cu‐TPBDA (ZNU‐9) with wly topology for efficient capture of C2H2 from CO2 and C2H4. Both ZNU‐8 and ZNU‐9 feature multiple anion functionalities and hierarchical porosity. Notably, ZNU‐9 with more anionic binding sites and three distinct cages displays both an extremely large C2H2 capacity (7.94 mmol/g) and a high C2H2/CO2 (10.3) or C2H2/C2H4 (11.6) selectivity. The calculated capacity of C2H2 per anion (4.94 mol/mol at 1 bar) is the highest among all the anion pillared metal organic frameworks. Theoretical calculation indicated that the strong cooperative hydrogen bonds exist between acetylene and the pillared SiF62− anions in the confined cavity, which is further confirmed by in situ IR spectra. The practical separation performance was explicitly demonstrated by dynamic breakthrough experiments with equimolar C2H2/CO2 mixtures and 1/99 C2H2/C2H4 mixtures under various conditions with excellent recyclability and benchmark productivity of pure C2H2 (5.13 mmol/g) or C2H4 (48.57 mmol/g).

A new green system of biogenic Ni/DFNS@Pd nanoparticles for the production of 2-oxo-2-phenylethylbenzoate and cyclic carbonates by using the oxidative carboxylation of alkenes

In this paper, we report highly atom-selective and efficacious oxidation of styrenes with carbon dioxide to cyclic carbonates in the appearance of Ni/[email protected] as a magnetic nanocatalyst (MNPs). For convenient detachment of the catalyst by an exterior magnetic domain, the dendritic fibrous nanosilica (DFNS) outer layer was covered with nickel to magnetize the DFNS. Then, the palladium nanoparticles on the outer layer of Ni/DFNS were diminished. In spite of the possibility of using these biological processes in the sustainable recapturing of vital metals (e.g. Pd), the catalytic function of biosynthesised MNPs has not yet been scrutinized. Here, instead of a chemical approach, microorganisms were utilized as catalysts for the generation of Pd nanoparticles in a biological procedure. These biogenic magnetic nanoparticles have been utilized for the first time as a reusable catalyst with an exterior magnet. The catalyst’s attributes were distinguished by a variety of methods, including scanning electron microscopy (SEM), energy dispersive X-ray (EDX), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), X-ray diffraction analysis (XRD), and vibrating sample magnetometer (VSM) analyses. Biogenized Ni/[email protected] was generated as a heterogeneous catalyst to compete with a homogeneous structure. This robust metal catalyst with great accessibility level and reusability was generated by anaerobic bacteria. Examining different concentrations of the catalyst showed that the selectivity and efficiency of the reaction are significantly affected by the concentration of the catalyst. Heterogeneous reaction compounds did not cause any negative effects. The products were eliminated from the catalyst without any problems and the catalyst was employed many times without a conspicuous loss in selectivity and activity.

Robust In-Zr Metal–Organic Framework Nanosheets as Ultrathin Interlayer Toward High-Rate and Long-Cycle Lithium–Sulfur Batteries

Robust In-Zr Metal–Organic Framework Nanosheets as Ultrathin Interlayer Toward High-Rate and Long-Cycle Lithium–Sulfur Batteries

Bioinspired microenvironment modulation of metal–organic framework-based catalysts for selective methane oxidation

Inspiration from natural enzymes enabling creationary catalyst design is appealing yet remains extremely challenging for selective methane (CH4) oxidation. This study presents the construction of a biomimetic catalyst platform for CH4 oxidation, which is constructed by incorporating Fe-porphyrin into a robust metal–organic framework, UiO-66, furnished with saturated monocarboxylic fatty acid bearing different long alkyl chains. The catalysts demonstrate the high efficiency in the CH4 to methanol (CH3OH) conversion at 50 °C. Moreover, the selectivity to CH3OH can be effectively regulated and promoted through a fine-tuned microenvironment by hydrophobic modification around the Fe-porphyrin. The long-chain fatty acids anchored on the Zr-oxo cluster of UiO-66 can not only tune the electronic state of the Fe sites to improve CH4 adsorption, but also restrict the amount of H2O2 around the Fe sites to reduce the overoxidation. This behavior resembles the microenvironment regulation in methane monooxygenase, resulting in high CH3OH selectivity.

A novel robust phosphate-functionalized metal–organic framework for deep desulfurization at wide temperature

The need to decrease environmental pollution, reduce energy consumption and produce high-purity chemicals has become an increasingly important driving force for sulfur dioxide (SO2) capture. The efficient capture of low concentrations of SO2, a highly corrosive acid gas that is not typically present in high concentrations in industrial settings, is a major challenge. Herein, a novel phosphate-functionalized metal–organic framework, ZU-801, is designed with precisely controlled pore sizes and chemical environment to achieve excellent adsorption capacity for SO2 (1.44 mmol g−1 at 0.002 bar, 2.00 mmol g−1 at 0.01 bar) and high IAST selectivities for SO2/CO2 (145), which provides great potential for selective capture of SO2. ZU-801 shows excellent stability to air, water, SO2, strong acid and strong base solutions, and it is thermally stable up to 733 K. Additionally, ZU-801 exhibits outstanding separation ability in removing SO2 from SO2/CO2 mixtures at temperature as high as 383 K or in humid environments. This work demonstrates the potential of designing ion-functionalized ultramicroporous materials with tailored pore sizes and porous chemical environments for efficient capture and separation of SO2 and sheds light on designing stable high-performance materials that operate at high temperatures.

Catalytic Dehydrative Transformations Mediated by Moisture-Tolerant Zirconocene Triflate

AbstractZirconocene triflate is a powerful moisture-tolerant catalyst for activation of C–O bonds in carboxylic acids and alcohols in the absence of water scavenging techniques. Herein, an overview of the use of this robust metal complex for direct amidation, esterification, and etherification is presented, along with a discussion on mechanistic aspects of the transformations and the catalyst class.

Electronic Structures and Photoredox Chemistry of Tungsten(0) Arylisocyanides.

ConspectusThe high energy barriers associated with the reaction chemistry of inert substrates can be overcome by employing redox-active photocatalysts. Research in this area has grown exponentially over the past decade, as transition metal photosensitizers have been shown to mediate challenging organic transformations. Critical for the advancement of photoredox catalysis is the discovery, development, and study of complexes based on earth-abundant metals that can replace and/or complement established noble-metal-based photosensitizers.Recent work has focused on redox-active complexes of 3d metals, as photosensitizers containing these metals most likely would be scalable. Although low lying spin doublet ("spin flip") excited states of chromium(III) and metal-to-ligand charge transfer (MLCT) excited states of copper(I) have relatively long lifetimes, the electronic excited states of many other 3d metal complexes fall on dissociative potential energy surfaces, owing to the population of highly energetic σ-antibonding orbitals. Indeed, we and other investigators have shown that low lying spin singlet and triplet excited states of robust closed-shell metal complexes are too short-lived at room temperature to engage in bimolecular reactions in solutions. In principle, this problem could be overcome by designing and constructing 3d metal complexes containing strong field π-acceptor ligands, where thermally equilibrated MLCT or intraligand charge transfer excited states might fall well below the upper surfaces of dissociative 3d-3d states. Notably, such design elements have been exploited by investigators in very recent work on redox-active iron(II) systems. Another approach, one we have actively pursued, is to design and construct closed-shell complexes of earth-abundant 5d metals containing very strong π-acceptor ligands, where vertical excitation of 5d-5d excited states at the ground state geometry would require energies far above minima in the potential surfaces of MLCT excited states. As this requirement is met by tungsten(0) arylisocyanides, these complexes have been the focus of our work aimed at the development of robust redox-active photosensitizers.In the following Account, we review recent work on homoleptic tungsten(0) arylisocyanides. Originally reported by our group 45 years ago, W(CNAr)6 complexes have exceptionally large one- and two-photon absorption cross-sections. One- or two-photon excitation produces relatively long-lived (hundreds of nanoseconds to microsecond) MLCT excited states in high yields. These MLCT excited states, which are very strong reductants with E°(W+/*W0) = -2.2 to -3.0 V vs Fc[+/0], mediate photocatalysis of organic reactions with both visible and near-infrared (NIR) light. Here, we highlight design principles that led to the development of three generations of W(CNAr)6 photosensitizers; and we discuss likely steps in the mechanism of a prototypal W(CNAr)6-catalyzed base-promoted homolytic aromatic substitution reaction. Among the many potential applications of these very bright luminophores, two-photon imaging and two-photon-initiated polymerization are ones we plan to pursue.

Efficient CO2 Reduction to Formate on CsPbI3 Nanocrystals Wrapped with Reduced Graphene Oxide

HighlightsA rational design of metal halide perovskites for achieving efficient CO2 reduction reaction was demonstrated.The stability of CsPbI3 perovskite nanocrystal (NCs) in aqueous electrolyte was improved by compositing with reduced graphene oxide (rGO).The CsPbI3/rGO catalyst exhibited > 92% Faradaic efficiency toward formate production with high current density which was associated with the synergistic effects between the CsPbI3 NCs and rGO.Transformation of greenhouse gas (CO2) into valuable chemicals and fuels is a promising route to address the global issues of climate change and the energy crisis. Metal halide perovskite catalysts have shown their potential in promoting CO2 reduction reaction (CO2RR), however, their low phase stability has limited their application perspective. Herein, we present a reduced graphene oxide (rGO) wrapped CsPbI3 perovskite nanocrystal (NC) CO2RR catalyst (CsPbI3/rGO), demonstrating enhanced stability in the aqueous electrolyte. The CsPbI3/rGO catalyst exhibited > 92% Faradaic efficiency toward formate production at a CO2RR current density of ~ 12.7 mA cm−2. Comprehensive characterizations revealed the superior performance of the CsPbI3/rGO catalyst originated from the synergistic effects between the CsPbI3 NCs and rGO, i.e., rGO stabilized the α-CsPbI3 phase and tuned the charge distribution, thus lowered the energy barrier for the protonation process and the formation of *HCOO intermediate, which resulted in high CO2RR selectivity toward formate. This work shows a promising strategy to rationally design robust metal halide perovskites for achieving efficient CO2RR toward valuable fuels.

Toward robust solid-state lithium metal batteries by stabilizing a polyethylene oxide-based solid electrolyte interface with a biomass polymer filler

Achieving all-solid-state lithium-based batteries with high energy densities requires lightweight and ultrathin solid-state electrolytes (SSEs) with high Li+ conductivity, but this still poses significant challenges. Herein, we designed a robust and mechanically flexible SSE (denoted BC-PEO/LiTFSI) by using an environmentally friendly and low-cost approach that involves bacterial cellulose (BC) as a three-dimensional (3D) rigid backbone. In this design, BC-PEO/LiTFSI is tightly integrated and polymerized through intermolecular hydrogen bonding, and the rich oxygen-containing functional groups from the BC filler also provide the active site for Li+ hopping transport. Therefore, the all-solid-state Li-Li symmetric cell with BC-PEO/LiTFSI (containing 3% BC) showed excellent electrochemical cycling properties over 1000 h at a current density of 0.5 mA cm−2. Furthermore, the Li-LiFePO4 full cell showed steady cycling performance under 3 mg cm−2 areal loading at a current of 0.1 C, and the resultant Li–S full cell maintained over 610 mAh g−1 for upward of 300 cycles at 0.2 C and 60 °C.

Alloyed Pt Single‐Atom Catalysts for Durable PEM Water Electrolyzer

AbstractThe high cost of noble metals is one of the key factors hindering the large‐scale application of proton exchange membrane (PEM) water electrolyzer for hydrogen production. Recently, single‐atom catalysts (SACs) with a potential of maximum atom utilization efficiency enable lowering the metal amount as much as possible; unfortunately, their durability remains a challenge under PEM water electrolyzer working conditions. Herein, a highly‐stable alloyed Pt SAC is demonstrated through a plasma‐assisted alloying strategy and applies to a PEM water electrolyzer. In this catalyst, single Pt atoms are firmly anchored onto a Ru support via a robust metal–metal bonding strength, as evidenced by these complementary characterizations. This SAC is used in a PEM water electrolyzer system to achieve a cell voltage as low as 1.8 V at 1000 mA cm−2. Impressively, it can operate over 1000 h without obvious decay, and the catalyst is present in the form of individual Pt atoms. To the knowledge, this will be the first SAC attempt at a cell level toward long‐term PEM. This work paves the way for designing durable SACs employed in the actual working condition in the PEM water electrolyzer.

Binary NiCo nanoalloys and single-atoms implanted nitrogen-doped carbon nanotubes as highly efficient, robust electrocatalyst for overall water splitting

Finding robust, high-efficiency, noble-metal-free electrocatalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) particularly at a low overpotential is a crucial endeavor for water electrolyzer-based green H2 harvesting, but challenges remain. Fortunately, atomically dispersed metal catalysts hold great potential for OER and HER owing to the exclusive electronic structure and maximized atom utilization, however, the insufficient population of reactive sites and unfortunate electrical conductivity seriously limit their performance. Herein, we rationally designed and synthesized a single-atom catalyst consisting of atomic Co and Ni with NiCo alloys encapsulated nitrogen-doped carbon nanotubes (N-CNTs). The NiCo-N-CNTs catalyst annealed at 900 °C (NiCo-N-CNTs-900) displays ultralow overpotential of 210 mV and 54 mV at 10 mA/cm2 for OER and HER, respectively, which are attributed to the robust synergistic effects of Ni/Co single atoms and NiCo nanoalloys. Furthermore, NiCo-N-CNTs-900 electrode exhibits higher mass activity of 2188 A/gNiCo and 468.75 A/gNiCo and turnover frequency of 0.679 O2 s−1 and 0.285 H2 s−1 for OER and HER, respectively, which is much better than those of commercial RuO2 and Pt/C catalysts. We further employed the NiCo-N-CNTs-900 as both anode and cathode catalyst for constructing a two-electrode electrolyzer, generating a current density of 10 mA/cm2 at a low cell voltage of 1.483 V, surpassing the benchmark Pt/C//RuO2 pair. This work not only provides a robust and effective non-precious metal catalyst but also a facile, efficient method to fabricate atomically dispersed metal atoms integrated with alloys for clean hydrogen production and beyond.

Molecular Exclusion Separation of 1‐Butene Isomers by a Robust Metal–Organic Framework under Humid Conditions

AbstractSeparating n‐butene and i‐butene by adsorption is an energy‐efficient alternative, but designing porous adsorbents that distinguish the subtle differences between the isomers is extremely challenging. Currently, adsorbents that can sieve 1‐butene isomers and are stable enough to withstand humid gas mixtures are largely unmet. Herein, we propose a robust ultramicroporous metal–organic framework (MET‐Fe) that can separate 1‐butene isomers through molecular exclusion. The pore aperture size (4.6 Å) precisely matches the kinetic diameters of the isomers, as verified by static and kinetic adsorption experiments and theoretical calculations. Furthermore, dynamic breakthrough experiments confirmed the excellent separation performance, easy regeneration, and remarkable reusability of MET‐Fe in both dry and humid conditions. With its high selectivity, large breakthrough capacity, and outstanding stability, MET‐Fe provides an ideal platform for industrial butene isomers separation.

Structural functionalization in robust metal–organic frameworks for p-xylene separation with superior adsorption capacity

The subtle differences between the xylene isomers make the separation of p-xylene/m-xylene/o-xylene mixtures one of the most challenging tasks in the petrochemical industry. In this study, CAU-1 was used as a platform compound to construct functionalized pore environment with high stability for selective PX adsorption and separation. Single-component adsorption tests and liquid-phase multicomponent adsorption experiments showed that a series of functionalized scaffolds exhibited PX selective adsorption compared to the other two isomers, among them functional groups optimized CAU-1-OH ([Al8(OH)4(OCH3)8(BDC-OH)6])(BDC = 1,4-benzenedicarboxylate) showed ultra-high PX adsorption capacity (460 mg/g), superior to most reported MOFs. And the PX/MX selectivity of functionalized CAU-1-OH was improved by 18% compared to the original CAU-1. Furthermore, vapor breakthrough experiments on CAU-1-OH showed that it can effectively extract PX from ternary PX/MX/OX mixtures. The fundamental PX selective adsorption mechanism was also visually illustrated using grand canonical Monte Carlo simulation. In addition, the stability of the adsorbent was investigated under different conditions (RH = 40% and 80%, pH = 1–11, different solvents, and high temperatures), and the unchanged PXRD and BET curves indicate that the adsorbent has excellent structural stability. As thus, the large PX adsorption capacity, ultra-high structural stability, and excellent isomer separation performance make these materials good candidates for industrial PX purification from xylene isomers mixture.

Robust and Wide Temperature-Range Zinc Metal Batteries with Unique Electrolyte and Substrate Designing.

Rechargeable zinc metal batteries are promising for large-scale energy storage. However, their practical application is limited by harsh issues such as uncontrollable dendrite growth, low Coulombic efficiency, and poor temperature tolerance. Herein, a unique design strategy using γ-valerolactone electrolyte and nanocarbon-coated aluminum substrate was reported to solve the above problems. The γ-valerolactone electrolyte with extremely low freezing point and high thermal stability enables the symmetric cells with long cycle life over a wide temperature range (-50 °C to 80 °C) due to its ability to regulate zinc nucleation and preferential epitaxial growth. Besides, the nanocarbon-coated aluminum substrate can also promote a higher Coulombic efficiency over a wide temperature range in contrast to the low Coulombic efficiency of copper substrates with significant irreversible alloying reactions because this unique substrate with excellent chemical stabilization can homogenize the interfacial electron/ion distribution. The optimized zinc metal batteries can operate stably under various temperature conditions (2000 cycles at 30 °C with 66% depth of discharge and 1200 cycles at 80 °C with 50% depth of discharge). This unique electrolyte and substrate design strategy achieves a robust zinc metal battery over a wide temperature range.

Robust and Wide Temperature‐Range Zinc Metal Batteries with Unique Electrolyte and Substrate Design

AbstractRechargeable zinc metal batteries are promising for large‐scale energy storage. However, their practical application is limited by harsh issues such as uncontrollable dendrite growth, low Coulombic efficiency, and poor temperature tolerance. Herein, a unique design strategy using γ‐valerolactone‐based electrolyte and nanocarbon‐coated aluminum substrate was reported to solve the above problems. The electrolyte with extremely low freezing point and high thermal stability enables the symmetric cells with long cycle life over a wide temperature range (−50 °C to 80 °C) due to its ability to regulate zinc nucleation and preferential epitaxial growth. Besides, the nanocarbon‐coated aluminum substrate can also promote a higher Coulombic efficiency over a wide temperature range in contrast to the low Coulombic efficiency of copper substrates with significant irreversible alloying reactions because this unique substrate with excellent chemical stabilization can homogenize the interfacial electron/ion distribution. The optimized zinc metal capacitors can operate stably under various temperature conditions (2000 cycles at 30 °C with 66 % depth of discharge and 1200 cycles at 80 °C with 50 % depth of discharge). This unique electrolyte and substrate design strategy achieves a robust zinc metal battery over a wide temperature range.