Bulk Electrode Research Articles

Does Anisotropic ‘Lattice’ Collapse Always Lead to Cracking in Ni-Rich Layered Oxide Cathode Particles?

Single-crystalline Ni-rich layered oxides (LiNi x Mn y Co1−x−y O2; x ≥ 0.8) are promising high-energy-density cathodes for future Li-ion batteries as they can withstand cathode particle cracking, which is a significant contributor to electrochemical capacity loss. The absence of grain/particle boundaries substantially mitigates the build-up of bulk structural strain in these materials generated from the anisotropic structural evolution (i.e., lattice collapse) during electrochemical cycling. However, compared to their polycrystalline counterparts, rigorous evaluations of their long-term electrochemical performance and their dependence on electrode structure changes, impedance, and particle cracking, are still necessary to take it towards commercialisation. Operando X-ray diffraction (XRD) and absorption spectroscopy (XAS) are ideal probes of these bulk electrode structure properties and provide a direct temporal correlation between the battery electrochemistry and the non-equilibrium structural changes in the electrodes. However, such studies often use electrochemically compromised cells modified for X-ray transmission that are neither representative of a real-world full-cell architecture nor operable long-term under industrially relevant cycling conditions, thereby compromising the results' practicality. This is especially problematic for technologically mature cathodes like single-crystalline Ni-rich layered oxides, which require greater scrutiny of their long-term degradation modes after hundreds of cycles. In this work, using in-house operando X-ray studies and large-area post-mortem electron tomography of a (TRL-5) pilot-line-built A7 pouch full cells with industry-relevant specifications, we demonstrate how single-crystalline LiNi0.8Mn0.1Co0.1O2 (NMC811) cathodes can withstand the severe anisotropic structural evolution and show no particle cracking even when cycled under harsh conditions of 2.5–4.4 V at 40 °C for 100 cycles. The bulk structural changes in both electrodes as well as the associated electrochemical performance loss are also evaluated. Furthermore, the validity of the in-house pilot line cell results is benchmarked against a commercially sourced Li-ion cell. In addition to furthering our understanding of single-crystalline Ni-rich cathodes, this work emphasises the need for real-world-relevant reproducible fundamental investigations of academic Li-ion cells and presents a methodology for doing so. Figure 1

Development of in situ high resolution NMR: Proof-of-principle for a new (spinning) cylindrical mini-pellet approach applied to a Lithium ion battery

Solid-state nuclear magnetic resonance (ssNMR) spectroscopy is a powerful technique for characterizing the local structure and dynamics of battery and other materials. It has been widely used to investigate bulk electrode compounds, electrolytes, and interfaces. Beside common ex situ investigations, in situ and operando techniques have gained considerable importance for understanding the reaction mechanisms and cell degradation of electrochemical cells.Herein, we present the recent development of in situ magic angle spinning (MAS) NMR methodologies to study batteries with high spectral resolution, setting into context possible advances on this topic. A mini cylindrical cell type insert for 4 mm MAS rotors is introduced here, being demonstrated on a Li/VO2F electrochemical system, allowing the acquisition of high-resolution 7Li MAS NMR spectra, spinning the electrochemical cell up to 15 kHz.

Surface chemistry induced robust SEI on graphite surface via soft carbon coating enables fast lithium storage

The realization of fast-charging lithium-ion batteries with long cycle life using graphite anode is typically hindered by the uncontrollable lithium plating on graphite surface. Herein we have systematically investigated the effects of soft carbon coating on SEI properties and Li+ storage capability. A variety of analytical studies combined with three-electrode impedance measurement and interface analysis demonstrate that the carbon coating effectively mitigates the formation of resistive films on the graphite surface, leading to facilitated charge transfer and low energy barrier. The depth-profiling XPS analysis clearly shows that the formation of a uniform, robust and LiF-rich SEI plays a dominant role in enhancing the interfacial kinetics, whereas the Li+ diffusion in bulk electrode is merely affected. As a result, the graphite anode with carbon coating exhibits enhanced fast-charging performance and cycle life, including a capacity retention ratio of 98.3 % after 100 cycles at 2C-CV. In general, this work reveals the critical role of coating layer chemistry in regulating the SEI properties and Li+ storage performance, which provides a valuable guidance for the rational design of practical graphite anode for fast-charging.

Investigation of electrocatalytic activity of palladium nanoparticle for ammonia borane oxidation via single‐entity electrochemistry

AbstractAmmonia borane (AB) has garnered significant attention as a high‐efficiency energy source, prompting extensive investigations into its electrochemical oxidation. One prominent avenue of research focuses on the development of electrocatalysts to enhance the oxidation of AB. Employing the novel approach of single‐entity electrochemistry (SEE), the electrocatalytic properties of gold (Au), silver (Ag), and palladium (Pd) nanoparticles (NPs) for AB oxidation were explored. In the case of Au and Ag NPs, SEE experiments yielded no discernible current signal, in contrast to the electrocatalytic currents observed with bulk electrodes. However, when Pd NPs were utilized, characteristic staircase signals in the SEE measurements were observed. The variation of the SEE current signal for Pd NPs under different applied potentials, AB concentrations, and NP concentrations was further investigated. An analysis of the SEE signal elucidated the conditions under which Pd NPs can effectively catalyze AB oxidation at the single NP level.

LiCoO2 Cathode Modified With Liquid-exfoliated Graphene for High-performance Full Batteries

Graphene has been successfully applied for modification of LiCoO2 cathode, but finding a large-scale preparation method of high-quality graphene for commercial application remains a great challenge. In this work, we have demonstrated a facile strategy to prepare few-layer defect-free graphene. The prepared graphene performs well in application for LiCoO2 cathode in the full battery system as conductive additives. The superior conductive graphene is attached to LiCoO2 particles, and fast pathways of electronic transport in the bulk electrode and protective layer on the interface between LiCoO2 and electrolyte are constructed. The cathode with 0.35% wt% graphene displays superior rate capacity (145 mAh/g at 2C) and excellent 4.5 V high-voltage cycle performance, which can be contributed to lower internal resistance and a more stabilized interface. The graphene shows great potential in commercial applications for high-performance LiCoO2-based full batteries.

Improving radio frequency heating uniformity in cauliflower by changing density in different zones

Radio frequency (RF) treatment is one of the most promising approaches for disinfesting, drying, and pasteurizing agricultural products. However, the inhomogeneous heating of RF treatment is the primary barrier for practical applications. To improve the RF heating uniformity, a 27.12 MHz, 6 kW pilot-scale RF system was applied to heat the cauliflower by changing its density in different zones of a rectangular container. The results proved that the RF heating rate and the average mass change rate of the cauliflower decreased with increasing electrode gap and bulk density of the cauliflower. The RF heating uniformity of the cauliflower was improved by increasing the electrode gap and the bulk density of the cauliflower during RF heating. With increasing of the bulk density of sample at the edges in the container, the RF heating rate and heating uniformity index of the sample firstly decreased and then increased when the sample density at the center and the corners were 405.5 and 516.8 kg/m3, respectively. The mass change rate of the sample presented an inverse relationship with the heating rate and heating uniformity index during RF treatment. The best heating uniformity and highest mass change rate were obtained when the bulk density of the cauliflowers at the center, edges, and corners in the container was 405.5, 461.1, and 516.8 kg/m3, respectively. The results of this study can offer effective method for improving the RF heating uniformity in high moisture products.

Kinetics of Hydrogen Evolution Reaction on Monometallic Bulk Electrodes in Various Electrolytic Solutions

The hydrogen evolution reaction (HER) holds pivotal significance in electrochemical energy conversion. In this study, we present essential HER kinetic parameters encompassing nine metals (Ag, Au, Co, Cr, Fe, Ni, Pt, W, and Zn) evaluated within seven distinct electrolytes (0.1 mol dm−3 HClO4, 0.1 mol dm−3 HCl, 0.5 mol dm−3 NaCl, 1 mol dm−3 KH2PO4, 0.1 mol dm−3 KOH, 0.1 mol dm−3 LiOH, and 1 mol dm−3 KOH). Through careful measures to restrain oxide formation, HER activity was measured on clean electrodes, while the assessment of HER activity on oxidatively treated metals was also performed. By correlating HER exchange current densities with calculated hydrogen binding energies, we show that the shape of HER volcano curves is largely preserved in studied electrolytes, at least around their apexes. Additionally, depending on the metal–electrolyte combination, the presence of surface oxide can have both positive and negative effects on HER kinetics. Finally, we collated HER kinetic data for bulk surfaces from diverse literature sources, offering a comprehensive overview of the kinetic parameters governing hydrogen evolution across distinct electrolytic environments. These insights have practical significance, guiding the development of new catalytic materials for different water electrolysis technologies, optimizing electrolyte formulations for boosting HER, and enhancing energy efficiency and catalytic performance through catalyst–electrolyte synergies.

Facile preparation of urchin-like morphology V2O3-VN nano-heterojunction cathodes for high-performance Aqueous zinc ion battery

Rechargeable aqueous zinc ion batteries (RAZIBs) are of interest for energy storage in smart grids. However, slow Zn2+ diffusion kinetics, insufficient active sites, and poor intrinsic conductivity are always challenging to exploit the huge potential of the batteries. Here, we prepare V2O3-VN nano-heterojunction composites with sea urchin-like morphology as the cathode for AZIBs. The electrode achieves high capacities (e.g., 0.1 A g−1, 532.6 mAh g−1), good rate and cycle performance (263.4 mAh g−1 at 5 A g−1 current density with 90.8% capacity retention). Detailed structural analyses suggest that the V2O3-VN composite is composed of different crystal planes of V2O3 and VN, which form an efficient heterogeneous interfacial network in the bulk electrode, accounting for its good electrochemical properties. Theoretical calculations reveal that compared with V2O3, VN and physically mixed V2O3/VN, the V2O3-VN heterostructure exhibits good cation adsorption and electrode conductivity, thereby accelerating the charge carrier mobility and electrochemical activity of the electrode. Moreover, ex-situ characterization techniques are utilized to investigate the zinc storage mechanism in detail, providing new ideas for the development of AZIBs cathode materials through the construction of heterojunction structures.

Nanomechanical pumping of Cooper pairs through NS junction

We consider a system consisting of a single-level quantum dot that performs mechanical periodic oscillations between spatially distant normal and superconducting electrodes, approaching them at a distance that allows the exchange of electrons through the vacuum tunnel barrier. Considering that the distance between the electrodes is much greater than the tunneling length, we show that charge pumping occurs in such a nanosystem even when the electrochemical potentials of the electrodes coincide. In this case, the direction of the electron flow is determined by the position of the quantum dot level relative to the electrochemical potential in bulk electrodes. The latter can be controlled by applying a voltage between the ground and the electrodes. It is also shown that the value of the average current is critically sensitive to the strength of the tunnel coupling between the quantum dot and the superconducting electrode, which, in turn, is controlled by the amplitude of mechanical oscillations.

Wood-structured, hydrophilic, low-tortuosity thick electrode enables high-performance supercapacitor

It is a natural ingenuity to ignite the aspiration of wood-structured biomaterials with largely-distributed porosity, mechanical integrity, and tunable functionalities in energy engineering. As a hierarchically architectured carbon scaffold with well-aligned channels and high active-mass loading, free-standing wood thick electrode expedites the electron/ion transfer kinetics to heighten storage capacitance. Herein, we have facilely designed a holey wood-structured bulk electrode (a thickness of ∼1 mm) with the depositing of MoS2 and NiS2 clusters by a tandem hydrothermal and pyrolysis strategy for the efficient supercapacitors. In the perpendicular direction, artificial small holes (∼ 0.5 mm diameter) are drilled across the 3D-wood thick electrode to perforate the growth channels, hence ameliorating ion migration as well as reducing diffused impedance. Benefitting from the vertical low-tortuosity channels, high charge conductivities, superhydrophilic interface, reversible redox behavior, and excellent mechanical stability, the superior areal capacitance (7806–8538 mF cm−2 at a current density of 10 mA cm−2) and long-term cycling lifespan (∼ 100 % retention over 10,000 cycles even at 100 mA cm−2) of wood thick electrodes (energy densities of 0.287 −0.423 mWh cm−2 in the asymmetric supercapacitors) are achieved without the structural deformation. The wood-structured, self-supporting thick electrode sketch a promising blueprint of high-performance biocompatible supercapacitors with maximum active-substance loading and monolithic low-tortuosity design that also can be popularized to rechargeable batteries.

Analysis of Structural Degradation Effects in a Solid Oxide Fuel Cell after Long-Term Operation

The sustainable production of hydrogen as well as its re-conversion into electricity will be a key aspect in a future green energy environment that is depending on regenerative resources. In order to ensure the eminent position of solid oxide cells (SOC) in this future hydrogen economy their reliability and long-term performance still needs to be improved. Having this in mind, we performed detailed investigations on samples from cells that were operated for 100,000h to get a profound understanding of structural degradation effects after long-term operation.The investigated samples originate from a two layer stack of fuel electrode supported solid oxide cells that were operated at 700°C and 0.5 A/cm2 in fuel cell mode. The cells consist of a Ni/Y-stabilized ZrO2 (YSZ) fuel electrode, a dense YSZ electrolyte layer, a Gd doped CeO2 (GDC) barrier layer and a La0.58Sr0.4Co0.2Fe0.8O3-d (LSCF) air electrode. Furthermore, an additional contact layer of La0.97Mn0.4Co0.3Cu0.3O3-d was applied on the air electrode surface and, in order to inhibit Cr-poisoning the interconnector material was coated with a manganese oxide layer by wet powder spraying. The stack represents the usual material status from 2009 when the stack operation has been starting.In the post-test analysis the microstructure and chemical composition was investigated by scanning electron microscopy (SEM) in combination with energy dispersive X-ray spectroscopy (EDS). The EDS analysis revealed localized, correlated enrichments of Sr and Cr in the bulk of the LSCF air electrode as well as at the LSCF / GDC interface. Moreover, non-correlated, localized Co enrichments could also be detected at the LSCF / GDC interface. In order to get an insight into localized structural changes and to identify impurity phases after long-term operation Raman spectroscopy measurements were performed. Hereby, it was for example possible to visualize, in accordance with the EDS analysis, the formation of a SrCrO4 impurity phase on the LSCF air electrode surface as well as inside the bulk of the LSCF by running Raman measurements on the air electrode surface as well as on embedded and polished cross-section samples. To study the structural degradation in detail with high spatial resolution, additional µ-beam Laue diffraction measurements were performed at the CRG-IF BM32 beamline at European Synchrotron Radiation Facility (ESRF).

Effective coating of Si@NiO nanoflowers with nitrogen-doped wheat protein-derived biochar for efficient lithium-ion and lithium-sulfur batteries anode materials

As the most promising anode material for ultra-high specific capacity lithium-ion batteries, Si has been hindered from widespread use by large volume effects and limited electrical conductivity during cycling. In this study, NiO nanoflowers were coated onto the exterior of Si NPs by hydrothermal method. Si@NiO was then mixed and annealed with natural biomass gel extracted from moldy wheat to produce Si@NiO@Biochar ternary composites, which were prepared. Si NPs are the source of high specific capacity of anode materials. The carbon layer minimizes the electrode bulk effect and enhances cycling stability, while the NiO flowers expand the lithium-ion transport channel and reduce Si NPs bulk effect. Furthermore, the N element from wheat protein in the carbon layer enhances the electrical conductivity of the material. After 100 cycles at 0.1 A g−1 and 1000 cycles at 1 A g−1, the capacity of the electrode rose to 952.12 mAh g−1 and 1098.05 mAh g−1, respectively. The Si@NiO@Biochar material showed remarkable electrochemical stability at various current densities and the thickness grew by just 27.97% after 500 cycles. It can also be utilized in lithium-sulfur batteries because of its microporous structure and capacity to transport sulfur. The reversible capacity was 388.21 mAh g−1 after 70 cycles at 1 C. Biomass carbon from biomass gels coated on Si@NiO reduces biomass energy waste. This research is a significant step for commercializing Si anode materials and providing an eco-friendly new method for storing energy.

How do gold-nanocrystal surface facets affect their electrocatalytic activities and the benzocaine-oxidation mechanism?

Here we unveil the effect of gold (Au) nanocrystals with different surface facets on electrocatalytic sensing activities using benzocaine as an analyte. To this end, we performed cyclic voltammetry, differential pulse voltammetry, and in-situ Raman spectroelectrochemical experiments by employing Au nanocrystals with different exposed surface facets as electrocatalytic sensors for benzocaine. The experiments were complemented by density-functional calculations, where the rhombic dodecahedra nanocrystals, enclosed by {110} facets, showed stronger interaction energy with benzocaine, followed by cubes ({100} facets) and octahedra ({111} facets). Results from in-situ Raman spectroelectrochemical measurements have also demonstrated that the benzocaine adsorption displayed a facet-dependent behavior, which supports that the analyte can be strongly adsorbed on the Au{110} facets in comparison to {100} and {111} counterparts. In this case, we propose an oxidative mechanism of the benzocaine reaction, in which benzocaine may be electrochemically adsorbed at Au nanocrystals through the –NH2 groups. After that, this –NH(Au) group is oxidized to –NO and, further to –NO2, in which different profiles were observed as a function of the Au nanocrystal facets. The effect of these facets was also observed in the oxygen reduction reaction; the rhombic dodecahedra presented a potential reduction of 200 mV, and a current increased by more than twenty times relative to the values of a commercial Au electrode (bulk). Indeed, our findings provide a deeper understanding of facet-dependent electrooxidation activity, mechanisms, and electrocatalytic detection of organic compounds.

MXene@ carbonized wood monolithic electrode with hierarchical porous framework for high-performance supercapacitors

Bulk electrodes with sufficient electrochemically active substances promote the enhanced energy density of energy storage devices. Additionally, the pore structure and wettability regulation of the electrodes are key factors in determining the electrochemical performance of the device. Herein, a monolithic electrode (CW/MXene) with a dual utilization strategy for the hierarchical porous structure of carbonized wood (CW) and the high electrical conductivity as well as wettability of MXene was proposed. The combination of MXene and CW provides a hierarchical pore structure with enhanced wettability to the electrolyte to complete the electrochemical reaction. CW/MXene showed the impressive electrochemical performance of 14.48 F cm−2 (203.94 F g−1) at a current density of 1 mA cm−2. Moreover, the obtained symmetric supercapacitor exhibits high areal/specific capacitances of 4.24 F cm−2 (80.61 F g−1) at 1.0 mA cm−2 and high energy densities of 0.589 mWh cm−2/11.2 Wh kg−1. This work provides advanced multiple utilization and excellent electrochemical performance for ultra-thick carbonized wood electrode applications in supercapacitors.

Spatially expanded built-in electric field via engineering graded junction enables fast charge transfer in bulk MnO@Mn3O4 for Na+ supercapacitors

Built-in electric field (BIEF) has recently emerged as a promising strategy for promoting charge transfer by supplying additional coulomb forces. However, the challenge lies in the intelligent control over the thickness and intensity of BIEF to augment these Coulomb forces, thereby enhancing charge transfer in bulk electrodes. Here we deliberately engineer a graded MnO@Mn3O4 junction characterized by a spatially intensified BIEF to accelerate charge transfer over an extended atom layer thickness. This graded MnO@Mn3O4 junction exhibits a phase transition gradient, characterized by a steady decline in Mn valence and work function from shell to core, giving rise to an intense BIEF across the junction. The enhanced BIEF should be ascribed to the spatially accumulated polarization, resulting in an increase in electron delocalization and a decrease in the energy barrier for ion transfer. As a result, the MnO@Mn3O4 manifests improved capacity and rate performance. This work highlights the significance of modulating the BIEF’s thickness and intensity to facilitate charge transfer, thereby pushing the boundaries of electrochemical energy storage.

Aqueous Supramolecular Binder for High-Performance Lithium-Sulfur Batteries.

Developing an advanced electrode structure is highly important for obtaining lithium sulfur (Li-S) batteries with long life, low cost, and environmental friendliness. Some bottlenecks, such as large volume deformation and environmental pollution caused by the electrode preparation process, are still hindering the practical application of Li-S batteries. In this work, a new water-soluble, green, and environmentally friendly supramolecular binder (HUG) is successfully synthesized by modifying natural biopolymer (guar gum, GG) with HDI-UPy (cyanate containing pyrimidine groups). HUG can effectively resist electrode bulk deformation through a the unique three-dimensional nanonet-structure formed via covalent bonds and multiple hydrogen bonds. In addition, abundant polar groups of HUG have good adsorption properties for polysulfide and can inhibit the shuttle movement of polysulfide ions. Therefore, Li-S cell with HUG exhibits a high reversible capacity of 640 mAh g-1 after 200 cycles at 1C with a Coulombic efficiency of 99%.

Amorphization Boost Multi‐Ions Storage for High‐Performance Aqueous Batteries

AbstractRegarding the complex properties of various cations, the design of aqueous batteries that can simultaneously store multi‐ions with high capacity and satisfactory rate performance is a great challenge. Here an amorphization strategy to boost cation‐ion storage capacities of anode materials is reported. In monovalent (H+, Li+, K+), divalent (Mg2+, Ca2+, Zn2+) and even trivalent (Al3+) aqueous electrolytes, the capacity of the resulting amorphous MoOx is more than quadruple than that of crystalline MoOx and exceeds those of other reported multiple‐ion storage materials. Both experimental and theoretical calculations reveal the generation of ample active sites and isotropic ions in the amorphous phase, which accelerates cation migration within the electrode bulk. Amorphous MoOx can be coupled with multi‐ion storage cathodes to realize electrochemical energy storage devices with different carriers, promising high energy and power densities. The power density exceeded 15000 W kg−1, demonstrating the great potential of amorphous MoOx in advanced aqueous batteries.

A first-principles investigation of the effects of strain and Pd-doping on ion transfer in LSCF bulk of solid oxide cells

Applied strain can be employed to tune ion migration properties in oxygen electrode bulk. Here migration properties of oxygen vacancy in Pd doped La1−xSrxCo1−yFeyO3−δ (LSCF) bulk (LSCFPd) were investigated with density functional theory under 3 % tensile and compressive strains. Formation energies of oxygen vacancy are reduced under tensile strain while they exhibit a nontrivial dependence as a function of compressive strain near Pd-doping sites. Migration barriers of oxygen vacancy in LSCF and LSCFPd bulks are also significantly reduced with tensile strain compared to that with non-strain. However, barriers near Pd-doping site increase greatly under compressive strain. The variation of oxygen vacancy formation and migration properties can be ascribed to the redistribution of atomic charges and local structural distortion caused by Pd-doping and applied strain. Results indicate that Pd-doping and application of tensile strain can significantly improve oxygen vacancy formation and migration properties.

Dual Optimization of Back Electrode Interface and Bulk via the Synergistic Passivation Effect of Niobium Pentoxide Enables Efficient Kesterite Solar Cells

As compared to the predecessor Cu(In,Ga)Se2 device, the current efficiency of kesterite Cu2ZnSn(S,Se)4 (CZTSSe) solar cells is still much lower mainly due to the known carriers recombination issue within interface and absorber bulk. In contrast to the majority of researches concerning recombination issues that focus on either single absorber bulk or interface passivation strategy, this study is pioneering in constructing synergistic passivation effects (SPE) to address the bulk and interface recombination issue simultaneously. By introducing a novel niobium pentoxide passivation layer into the back electrode interface (BEI), it is identified that SPE can be constructed due to Nb (& O) diffusion from Nb2O5 layer to absorber bulk and BEI during high‐temperature selenization. The chemical passivation effect is fulfilled via the intrinsic high resistance characteristic of Nb2O5 layer, and also through the NbOx passivation aiming to absorber bulk benefited from Nb (& O) diffusion. Meanwhile, the occupations of Nb (& O) on the Mo (& Se) sites induce a conduction type inversion in MoSe2 interfacial layer and create a preferable interface p+‐Mo(Se,O)2:Nb/CZTSSe, achieving an interfacial field passivation effect. Ultimately, the promoted absorber quality and improved charge carrier transportation from SPE contribute to the boost of device performance beyond 10% efficiency.

Solvation Engineering Enables High‐Voltage Lithium Ion and Metal Batteries Operating Under −50 and 80 °C

AbstractExtreme temperatures (<‐20 °C or >50 °C) would seriously impair the performance of lithium batteries through deteriorating bulk ion transport and electrode interfaces. Here, a rational design of weak solvent and anti‐solvent combination is presented for wide‐temperature electrolytes. The weak solvent provides accelerated desolvation kinetics of Li+ around the anode region, while the anti‐solvent not only functions as an antifreeze agent for smooth ion migration at low temperatures but also interacts with the weak solvent to boost the formation of ionic aggregates. The weak and anti‐solvent electrolyte (WAE) exerts excellent compatibility with both lithium metal and graphite. Under −40 °C, Li anode delivers 98.5% Coulombic efficiency and graphite outputs capacity over 230 mAh g‐1. Lithium‐ion/metal batteries by pairing graphite anode with LiCoO2 cathode with a negative to positive capacity ratio of 0.75 can realize steady operation at −50 °C with an average coulombic efficiency of 99.9%. Lithium metal batteries with 4.2 mAh cm‐2 high LiCoO2 cathode loading and 50 µm thin lithium anode deliver 73.8% capacity output at −40 °C. Besides, the cells are stable up to 80 °C with an average coulombic efficiency of 99.7%. This research demonstrates a relatively loose Li+ solvation environment in WAE systems and provides wide‐temperature electrolyte for high‐performance lithium ion and metal batteries.