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Abstract The application of high-voltage positive electrode materials in sulfide all-solid-state lithium batteries is hindered by the limited oxidation potential of sulfide-based solid-state electrolytes (SSEs). Consequently, surface coating on positive electrode materials is widely applied to alleviate detrimental interfacial reactions. However, most coating layers also react with sulfide-based SSEs, generating electronic conductors and causing gradual interface degradation and capacity fading. To address this, we propose a Li2ZrF6 coating layer on LiCoO2, which exhibits minimal reaction with SSEs, and its decomposition products are electron-conductive-free. Furthermore, this coating layer also efficiently mitigates the layered-to-spinel/rock-salt surface structural transformation in LiCoO2. As a result, the In-Li|Li6PS5Cl | Li2ZrF6-LiCoO2 all-solid-state cell demonstrates an initial areal capacity of 5.2 mAh cm−2 and a capacity retention of 80.5% after 1500 cycles at 70 mA/g with high LiCoO2 areal mass loading (30.19 mg cm−2) and a cut-off voltage of 3.9 V (corresponding to potential of 4.5 V versus Li+/Li), at 25 °C.

Abstract In this study, a novel concept of multipoint anionic bridge (MAB) is proposed and proved, which utilizes anions with different sites to connect with the asymmetric solvation structure (ASS). Compared to usual solvation structures, this study utilizes the multifunctional groups of difluoro(oxalate)borate anion (ODFB−), which can connect with Li+. By tailoring the concentration, the anion serves as a bridge between different solvated structures. The electrolyte is investigated through in situ techniques and simulations to draw correlations between different solvation structures and reaction pathways. The proposed design demonstrates remarkable high‐temperature performance on both the anode and cathode sides, enabling stable cycling of LCO||graphite (0.5 Ah, 1.0 C) pouch cell for over 200 cycles at 80 °C and facilitating Li||MCMB and Li||LFP cells to deliver stable performance for 200 cycles at 100 °C. This work paves the way for the development of high‐performance electrolyte systems by designing and using new multipoint anions to construct ASSs.

Abstract Commonly-used ether and carbonate electrolytes show distinct advantages in active lithium-metal anode and high-voltage cathode, respectively. While these complementary characteristics hold promise for energy-dense lithium metal batteries, such synergy cannot be realized solely through physical blending. Herein, a linear functionalized solvent, bis(2-methoxyethyl) carbonate (BMC), is conceived by intramolecularly hybridizing ethers and carbonates. The integration of the electron-donating ether group with the electron-withdrawing carbonate group can rationalizes the charge distribution, imparting BMC with notable oxidative/reductive stability and relatively weak solvation ability. Furthermore, BMC also offers advantages including the ability to slightly dissolve LiNO3, excellent thermostability and nonflammability. Consequently, the optimized BMC-based electrolyte, even with typical concentrations in the single solvent, demonstrates high-voltage tolerance (4.4 V) and impressive Li plating/stripping Coulombic efficiency (99.4%). Moreover, it fulfills practical lithium metal batteries with satisfactory cycling performance and exceptional tolerance towards thermal/mechanical abuse, showcasing its suitability for safe high-energy lithium metal batteries.

Abstract Understanding the physical picture of Li ion transport in the current ionic conductors is quite essential to further develop lithium superionic conductors for solid-state batteries. The traditional practice of directly extrapolating room temperature ion diffusion properties from the high-temperature (>600 K) ab initio molecular dynamics simulations (AIMD) simulations by the Arrhenius assumption unavoidably cause some deviations. Fortunately, the ultralong-time molecular dynamics simulation based on the machine-learning interatomic potentials (MLMD) is a more suitable tool to probe into ion diffusion events at low temperatures and simultaneously keeps the accuracy at the density functional theory level. Herein, by the low-temperature MLMD simulations, the non-linear Arrhenius behavior of Li ion was found for Li3ErCl6, which is the main reason for the traditional AIMD simulation overestimating its ionic conductivity. The 1μs MLMD simulations capture polyanion rotation events in Li7P3S11 at room temperature, in which four [PS4]3− tetrahedra belonging to a part of the longer-chain [P2S7]4− group are noticed with remarkable rotational motions, while the isolated group [PS4]3− does not rotate. However, no polyanion rotation is observed in Li10GeP2S12, β-Li3PS4, Li3ErCl6, and Li3YBr6 at 300 K during 1μs simulation time. Additionally, the ultralong-time MLMD simulations demonstrate that not only there is no paddle-wheel effect in the crystalline Li7P3S11 at room temperature, but also the rotational [PS4]3− polyanion groups have weakly negative impacts on the overall Li ion diffusion. The ultralong-time MLMD simulations deepen our understanding of the relationship between the polyanion rotation and cation diffusion in ionic conductors at room environments.

It is challenging to prepare electrolyte that could achieve wide electrochemical window, broad working temperature, non-inflammability, and fast ion transport simultaneously. Here the authors report a rocking-chair proton battery utilizing a solvent-free protic liquid electrolyte, which could operate in a broad temperature range from 0 to 250 celsius degree.

Ammonium-ion batteries are promising solutions for large-scale energy storage systems owing to their cost-effectiveness, safety, and sustainability. Herein, we propose an aqueous ammonium-ion battery based on an organic poly(1,5-naphthalenediamine) anode and an inorganic Prussian blue cathode in 19 ​M ​(M: mol kg−1) CH3COONH4 electrolyte. Its operation involves a reversible coordination reaction (C=N/C–N– conversion) in the anode and the NH4+ insertion/extraction reaction in the cathode, along with NH4+ acting as the charge carrier in a rocking-chair battery. Benefiting from the fast kinetics and stability of both electrodes, this aqueous ammonium-ion battery shows an excellent rate capability and long cycle stability for 500 cycles. Moreover, an energy density as high as 31.8 ​Wh kg−1 can be achieved, based on the total mass of the cathode and anode. Surprisingly, this aqueous ammonium-ion battery works well over a wide temperature range from −40 to 80 ​°C. This work will provide new opportunities to build wide-temperature aqueous batteries and broaden the horizons for large-scale energy storage systems.

Highlights An artificial solid–electrolyte interface composed of a perovskite type material, BaTiO3, is introduced to Zn anode surface in aqueous zinc ion batteries. The BaTiO3 layer endowing inherent character of the switched polarization can regulate the interfacial electric field at anode/electrolyte interface. Zn dendrite can be restrained, and Zn metal batteries based on BaTiO3 layer show stable cycling. Abstract Aqueous zinc ion batteries show prospects for next-generation renewable energy storage devices. However, the practical applications have been limited by the issues derived from Zn anode. As one of serious problems, Zn dendrite growth caused from the uncontrollable Zn deposition is unfavorable. Herein, with the aim to regulate Zn deposition, an artificial solid–electrolyte interface is subtly engineered with a perovskite type material, BaTiO3, which can be polarized, and its polarization could be switched under the external electric field. Resulting from the aligned dipole in BaTiO3 layer, zinc ions could move in order during cycling process. Regulated Zn migration at the anode/electrolyte interface contributes to the even Zn stripping/plating and confined Zn dendrite growth. As a result, the reversible Zn plating/stripping processes for over 2000 h have been achieved at 1 mA cm−2 with capacity of 1 mAh cm−2. Furthermore, this anode endowing the electric dipoles shows enhanced cycling stability for aqueous Zn-MnO2 batteries. The battery can deliver nearly 100% Coulombic efficiency at 2 A g−1 after 300 cycles.

Increasing energy demand calls for high‐performance lithium‐ion batteries with good low‐temperature resilience. Conventional intercalation cathodes pose problems such as sluggish interfacial Li‐ion transportation and slow diffusion in bulk electrode at low temperature, hindering their application in cold environment. Prussian blue analogues (PBA) with open framework structure provide viable fast kinetics for low‐temperature operation. Herein, a Mn‐based PBA (MnHCF@CNT composite) is synthesized and forms a unique necklace‐like conductive network by nucleating MnHCF nanoparticles on carbon nanotubes (CNT). Such features endow it with surface‐controlled intercalation pseudocapacitive behavior and high diffusion coefficient of Li+, which shows a high capacity of 103 mAh g−1 at the rate of 20C. Moreover, interfacial pseudocapacitance and fast bulk Li+ diffusion help realize excellent low‐temperature performance, which obtains high capacity of 117 mAh g−1 (corresponding to a capacity retention of 73%) under −40 °C and keeps 52% of its capacity at −70 °C. Full cell based on MnHCF@CNT cathode and Nb2O5 anode can exhibit 57% of its capacity at −40 °C. This research takes a further step toward developing cathode material at low temperature and provides feasible design for battery under subzero environment.

The authors show a hydronium-ion battery with an organic pyrene-4,5,9,10-tetraone anode and a MnO2@graphite cathode and H3O+ as the charge carrier. In addition to exhibiting promising energy density and power density, this battery works well even under low temperatures ranging from −40 °C to −70 °C.

Abstract Conventional intercalation compounds for lithium‐ion batteries (LIBs) suffer from rapid capacity fading and are even unable to charge–discharge with temperature decline, owing to the sluggish kinetics and solvation/desolvation process. In this work, a high‐performance rechargeable battery at ultralow temperature is developed by employing a nanosized Ni‐based Prussian blue (NiHCF) cathode. The battery delivers a high capacity retention of 89% (low temperature of −50 °C) and 82% (ultralow temperature of −70 °C) compared with that at +25 °C. Various characterizations and electrochemical investigations, including operando Fourier transform infrared spectra, in situ X‐ray diffraction, cyclic voltammetry response, and galvanostatic intermittent titration technique are carried out to detect the structural stability and electrochemical behavior at different temperatures. It turns out that the pseudocapacitive behavior drives the desolvation process at the interface, while fast diffusion in the bulk electrode accelerates the movement of Li+ from the interface to the bulk materials. The unique synergistic features of intercalation pseudocapacitance at the electrolyte/electrode interface and high diffusion coefficient in the bulk electrode enables the NiHCF cathode with excellent low temperature performance. These findings offer a new direction for the design of LIBs operated at low temperature.

Summary: Garnet-based bulk-type all-ceramic lithium battery (ACLB) is considered to be highly safe, but its electrochemical performance is severely hindered by the huge cathode/electrolyte interfacial resistance. Here, we demonstrate an in situ coated Li2.985B0.005OCl as sintering solder, which is uniformly coated on both LiCoO2 and Li7La3Zr2O12. With the low melting point (267°C) and high ionic conductivity (6.8 × 10−5 S cm−1), the Li2.985B0.005OCl solder not only restricts La/Co interdiffusion, but also provides fast Li+ transportation in the cathode. A low cathode/electrolyte interfacial resistance (386 Ω cm2) is realized owing to the densification of the ACLB by hot-press sintering. The strain/stress of the LiCoO2 is also released by the small elasticity modulus of Li2.985B0.005OCl, leading to a superior cycling stability. The study sheds light on the design of advanced garnet-based bulk-type ACLB by exploring proper solders with higher ionic conductivity, lower melting point, and smaller elasticity modulus.

Zn-MnO2 batteries offer high energy density, but phase changes that lead to poor cathode stability hinder development of rechargeable versions. Here the authors report structurally reinforced polyaniline-intercalated MnO2 nanolayers that boost performance by eliminating phase transformation.

The chlor-alkali process is an important industrial process to make commodity chemicals; however, it usually requires the use of dangerous chemicals as membrane material. Here, the authors demonstrate clean, membrane-free chlor-alkali electrolysis, where chlorine evolution and hydrogen/sodium hydroxide production are completely decoupled.

Alkaline water electrolyzers are promising devices for hydrogen generation, although hydrogen/oxygen mixing can be problematic. Here, the authors use nickel hydroxide as a redox mediator to decouple the hydrogen and oxygen production, overcoming the gas-mixing issue.

The lithium- (Li-) metal anode is crucial for developing high-energy-density batteries, while its dendritic growth and the low charge/discharge Coulombic efficiency in organic electrolytes hinder its practical application. Herein, we employed an in situ optical microscope to investigate the effect of the electrolyte concentration and the working temperature on the Li-plating/-stripping process. It is found that a higher concentration electrolyte can suppress its side reaction to improve the charge/discharge Coulombic efficiency, and a higher temperature can help lithium plate/strip uniformly with less lithium dendritic growth. An average Coulombic efficiency was obtained as high as 99.2% for over 150 cycles with a fixed plating capacity of 2 mAh cm-2 on copper foil in a 3 mol/kg ether-based electrolyte under 60°C, which provides an efficient and facile strategy for developing high-performance Li-metal batteries.

Direct use of metals as battery anodes could significantly boost the energy density, but suffers from limited cycling. To make the batteries more sustainable, one strategy is mitigating the propensity for metals to form random morphology during plating through orientation regulation, e.g., hexagonal Zn platelets locked horizontally by epitaxial electrodeposition or vertically aligned through Zn/electrolyte interface modulation. Current strategies center around obtaining (002) faceted deposition due to its minimum surface energy. Here, benefiting from the capability of preparing a library of faceted monocrystalline Zn anodes and controlling the orientation of Zn platelet deposits, we challenge this conventional belief. We show that while monocrystalline (002) faceted Zn electrode with horizontal epitaxy indeed promises the highest critical current density, the (100) faceted electrode with vertically aligned deposits is the most important one in suppressing Zn metal corrosion and promising the best reversibility. Such uniqueness results from the lowest electrochemical surface area of (100) faceted electrode, which intrinsically builds upon the surface atom diffusion barrier and the orientation of the pallets. These new findings based on monocrystalline anodes advance the fundamental understanding of electrodeposition process for sustainable metal batteries and provide a paradigm to explore the processing-structure-property relationships of metal electrodes. [ABSTRACT FROM AUTHOR]