In all-solid-state batteries, a solid electrolyte with high ionic conductivity is required for fast charging, uniform lithium deposition, and increased cathode capacity. Lithium argyrodite with BH4 - substitution has promising potential due to its higher ionic conductivity compared to argyrodites substituted with halides. In this study, Li5.25PS4.25(BH4)1.75, characterized by a high ionic conductivity of 13.8 mS cm-1 at 25 °C, is synthesized via wet ball-milling employing o-xylene. The investigation focused on optimizing wet ball-milling parameters such as ball size, xylene content, drying temperature, as well as the amount of BH4 - substitution in argyrodite. An all-solid-state battery prepared using Li5.25PS4.25(BH4)1.75 as the electrolyte and LiNbO3 coated NCM811 as the cathode exhibits an initial coulombic efficiency of 90.2% and maintains 93.9% of its initial capacity after 100 cycles at fast charging rate (5C). It is anticipated that the application of this wet mechanochemical synthesis will contribute further to the commercialization of all-solid-state batteries using BH4-substituted argyrodites.

Lithium metal batteries operated with high voltage cathodes are predestined for the realization of high energy storage systems, where solid polymer electrolytes offer a possibility to improve battery safety. Al2O3_PCL is introduced as promising hybrid electrolyte made from polycaprolactone (PCL) and Al2O3 nanoparticles that can be prepared in a one-pot synthesis as a random mixture of linear PCL and PCL-grafted Al2O3. Upon grafting, synergistic effects of mechanical stability and ionic conductivity are achieved. Due to the mechanical stability, manufacture of PCL-based membranes with a thickness of 50 µm is feasible, yielding an ionic conductivity of 5·10-5 S cm-1 at 60 °C. The membrane exhibits an impressive performance of Li deposition in symmetric Li||Li cells, operating for 1200 h at a constant and low overvoltage of 54 mV and a current density of 0.2 mA cm-2. NMC622 | Al2O3_PCL | Li cells are cycled at rates of up to 1 C, achieving 140 cycles at >80% state of health. The straightforward synthesis and opportunity of upscaling as well as solvent-free polymerization render the Al2O3_PCL hybrid material as rather safe, potentially sustainable and affordable alternative to conventional polymer-based electrolytes.

Lignin as a natural biopolymer is becoming increasingly in demand due to its eco-friendly properties, while lignin-based electrolyte with high conductivity and reliable durability for applications in supercapacitors is still challenging. Herein, a facile method to prepare lignin nanoparticles (LNPs)-based solid electrolyte thin film (LF) was proposed through chemical cross-linking reaction. The fabricated LF exhibited a distinctive spongy porous structure with the ionic conductivity of 3.26 mS cm-1, demonstrating the exceptional flexibility and favorable mechanical properties. Moreover, the assembly of all-LNPs-based symmetric supercapacitor (SSC) devices was achieved using LF electrolyte and LCA electrodes for the first time, confirming the LF3 electrolyte superior to commercial cellulose separator in capacitive behaviour. This SSC device exhibited a specific capacitance of 122.7 F g-1 at 0.5 A g-1 and the maximum energy density of 17.04 W h kg-1. Furthermore, the incorporation of sodium alginate (SA) significantly enhanced the ionic conductivity of SA/LF3 electrolyte, and the resulting SSC device delivered a higher specific capacitance of 174.5 F g-1 at 0.5 A g-1 and the maximum energy and power densities of 24.24 W h kg-1 and 5023 W kg-1, respectively. This study proposes a promising approach for sustainable utilization of lignin in energy storage applications.

Cation-doped cubic Li7La3Zr2O12 is regarded as a promising solid electrolyte for safe and energy-dense solid-state lithium batteries. However, it suffers from the formation of Li2CO3 and high electronic conductivity, which give rise to an unconformable Li/Li7La3Zr2O12 interface and lithium dendrites. Herein, composite AlF3-Li6.4La3Zr1.4Ta0.6O12 solid electrolytes were created based on thermal AlF3 decomposition and F/O displacement reactions under a high-temperature sintering process. When the AlF3 is thermally decomposed, it leaves Al2O3/AlF3 meliorating the grain boundaries and F- ions partially displacing O2- ions in the grains. Due to the higher electronegativity of F- in the grains and the grain-boundary modification, these AlF3-Li6.4La3Zr1.4Ta0.6O12 deliver optimized electronic conduction and chemical stability against the formation of Li2CO3. The Li/AlF3-Li6.4La3Zr1.4Ta0.6O12/Li cell exhibits a low interfacial resistance of ∼16 Ω cm2 and an ultrastable long-term cycling behavior for 800 h under a current density of 200 μA/cm2, leading to Li//LiCoO2 solid-state batteries with good rate performance and cycling stability.

Graphene oxide (GO)-based all-solid-state supercapacitors (SCs) provide an important complement to liquid- and gel-electrolyte-based SCs in a variety of applications, including flexible electronics. Still, their mediocre capacitance and complex fabrication methods hold back the realization of their full potential. Here, a simple fabrication of all-solid-state SCs with layered GO as a solid electrolyte and MXene as electrodes is demonstrated. The resultant SCs show excellent energy storage capacitance comparable to other MXene-based SCs using liquid electrolytes. The outperformance is attributed to extra interlayer spacing expansion and improved ion transport kinetics thanks to a synergistic water-absorbing effect due to the hydrophilicity of both MXene and GO in combination, which interestingly satisfies the intrinsic surface-dominated pseudocapacitive behavior of MXene. The application of this SC in humidity sensing has also been demonstrated to be fast responsive. The findings describe in this work provide a means of improving the capacitance performance using GO as a solid electrolyte with MXene as the electrodes and exploit the potential application as electronic elements for smart devices.

Reference electrode is the foundation of electrochemical study; thus, most electrode materials are tested in a three-electrode mode to acquire potential-dependent kinetics. However, it is difficult to directly use conventional reference electrodes to detect potential information in solid electrolyte devices due to their compact assembly structure. Therefore, the kinetic study of an electrochemical device faces challenges in precise identification of specific problems originating from the anode or cathode. Here, focusing on proton exchange membrane water electrolysis, we design a solid electrolyte reversible hydrogen electrode (SE-RHE), which can be used for electrode diagnosis under various operating conditions. Compared to the reference electrodes reported in the literature, which are mainly based on liquid electrolyte, the SE-RHE is highly sensitive and compatible, as well as easy to assemble. The potential deviation is less than ±0.5 mV, and the cell voltage derived from the electrode potential well reproduces the value that was directly measured with a deviation less than 0.2%. The reference electrode developed in this work enables the kinetic study of a specific electrode rather than the entire cell. For instance, an interesting observation is that the cathode shows distinct stability under stable and fluctuating operations. Differing from the high stability under stable operation, the cathode degrades significantly under fluctuating operations.

We use low-dose cryogenic transmission electron microscopy (cryo-TEM) to investigate the atomic-scale structure of antiperovskite Na2NH2BH4 crystals by preserving the room-temperature cubic phase and carefully monitoring the electron dose. Via quantitative analysis of electron beam damage using selected area electron diffraction, we find cryogenic imaging provides 6-fold improvement in beam stability for this solid electrolyte. Cryo-TEM images obtained from flat crystals revealed the presence of a new, long-range-ordered supercell with a cubic phase. The supercell exhibits doubled unit cell dimensions of 9.4 Å × 9.4 Å as compared to the cubic lattice structure revealed by X-ray crystallography of 4.7 Å × 4.7 Å. The comparison between the experimental image and simulated potential map indicates the origin of the supercell is a vacancy ordering of sodium atoms. This work demonstrates the potential of using cryo-TEM imaging to study the atomic-scale structure of air- and electron-beam-sensitive antiperovskite-type solid electrolytes.

Lithium metal batteries (LMBs), with high energy densities, are strong contenders for the next generation of energy storage systems. Nevertheless, the unregulated growth of lithium dendrites and the unstable solid electrolyte interphase (SEI) significantly hamper their cycling efficiency and raise serious safety concerns, rendering LMBs unfeasible for real-world implementation. Covalent organic frameworks (COFs) and their derivatives have emerged as multifunctional materials with significant potential for addressing the inherent problems of the anode electrode of the lithium metal. This potential stems from their abundant metal-affine functional groups, internal channels, and widely tunable architecture. The original COFs, their derivatives, and COF-based composites can effectively guide the uniform deposition of lithium ions by enhancing conductivity, transport efficiency, and mechanical strength, thereby mitigating the issue of lithium dendrite growth. This review provides a comprehensive analysis of COF-based and derived materials employed for mitigating the challenges posed by lithium dendrites in LMB. Additionally, we present prospects and recommendations for the design and engineering of materials and architectures that can render LMBs feasible for practical applications.

Here, all-solid scanning electrochemical cell microscopy (SECCM) is first established by filling polyacrylamide (PAM) into nanocapillaries as a solid electrolyte. A solid PAM nanoball at the tip of a nanocapillary contacts graphene and behaves as an electrochemical cell for simultaneously measuring the morphology and electrochemical activity. Compared with liquid droplet-based SECCM, this solid nanoball is stable and does not leave any electrolyte at the contact regions, which permits accurate and continuous scanning of the surface without any intervals. Accordingly, the resolutions in the lateral (x-y) and vertical (z) directions are improved to ∼10 nm. The complete scanning of the wrinkles on graphene records low currents at the two sidewalls of the wrinkles and a relatively high current at the center of the wrinkles. The heterogeneity in the electrochemical activity of the wrinkle illustrates different electron transfer features on surfaces with varied curvatures, which is hardly observed by the current electrochemical or optical methods. The successful establishment of this high spatial electrochemical microscopy overcomes the current challenges in investigating the electrochemical activity of materials at the nanoscale, which is significant for a better understanding of electron transfer in materials.

Electrochemical carbon dioxide (CO2) reduction reaction (CO2RR) to valuable liquid fuels, such as formic acid/formate (HCOOH/HCOO-) is a promising strategy for carbon neutrality. Enhancing CO2RR activity while retaining high selectivity is critical for commercialization. To address this, we developed metal-doped bismuth (Bi) nanosheets via a facile hydrolysis method. These doped nanosheets efficiently generated high-purity HCOOH using a porous solid electrolyte (PSE) layer. Among the evaluated metal-doped Bi catalysts, Co-doped Bi demonstrated improved CO2RR performance compared to pristine Bi, achieving ~90 % HCOO- selectivity and boosted activity with a low overpotential of ~1.0 V at a current density of 200 mA cm-2. In a solid electrolyte reactor, Co-doped Bi maintained HCOOH Faradaic efficiency of ~72 % after a 100-hour operation under a current density of 100 mA cm-2, generating 0.1 M HCOOH at 3.2 V. Density functional theory (DFT) results revealed that Co-doped Bi required a lower applied potential for HCOOH generation from CO2, due to stronger binding energy to the key intermediates OCHO* compared to pure Bi. This study shows that metal doping in Bi nanosheets modifies the chemical composition, element distribution, and morphology, improving CO2RR catalytic activity performance by tuning surface adsorption affinity and reactivity.