In-Situ Construction of Electronically Insulating and Air-Stable Ionic Conductor Layer on Electrolyte Surface and Grain Boundary to Enable High-Performance Garnet-Type Solid-State Batteries.

Lithophobic Li2CO3/LiOH contaminants and high-resistance lithium-deficient phases produced from the exposure of garnet electrolyte to air leads to a decrease in electrolyte ion transfer ability. Additionally, garnet electrolyte grain boundaries (GBs) with narrow bandgap and high electron conductivity are potential channels for current leakage, which accelerate Li dendrites generation, ultimately leading to short-circuiting of all-solid-state batteries (ASSBs). Herein, a stably lithiophilic Li2ZO3 is in situ constructed at garnet electrolyte surface and GBs by interfacial modification with ZrO2 and Li2CO3 (Z+C) co-sintering to eliminate the detrimental contaminants and lithium-deficient phases. The Li2ZO3 formed on the modified electrolyte (LLZTO-(Z+C)) surface effectively improves the interfacial compatibility and air stability of the electrolyte. Li2ZO3 formed at GBs broadens the energy bandgaps of LLZTO-(Z+C) and significantly inhibits lithium dendrite generation. More Li+ transport paths found in LLZTO-Z+C by first-principles calculations increase Li+ conductivity from 1.04×10-4 to 7.45×10-4 S cm-1. Eventually, the Li|LLZTO-(Z+C)|Li symmetric cell maintains stable cycling for over 2000 h at 0.8 mA cm-2. The capacity retention of LiFePO4|LLZTO-(Z+C)|Li battery retains 70.5% after 5800 ultralong cycles at 4 C. This work provides a potential solution to simultaneously enhance the air stability and modulate chemical characteristics of the garnet electrolyte surface and GBs for ASSBs.

Subsurface Engineering Induced Fermi Level De-pinning in Metal Oxide Semiconductors for Photoelectrochemical Water Splitting.

Photoelectrochemical (PEC) water splitting is a promising approach for renewable solar light conversion. However, surface Fermi level pinning (FLP), caused by surface trap states, severely restricts the PEC activities. Theoretical calculations indicate subsurface oxygen vacancy (sub-Ov ) could release the FLP and retain the active structure. A series of metal oxide semiconductors with sub-Ov were prepared through precisely regulated spin-coating and calcination. Etching X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), and electron energy loss spectra (EELS) demonstrated Ov located at sub ∼2-5 nm region. Mott-Schottky and open circuit photovoltage results confirmed the surface trap states elimination and Fermi level de-pinning. Thus, superior PEC performances of 5.1, 3.4, and 2.1 mA cm-2 at 1.23 V vs. RHE were achieved on BiVO4 , Bi2 O3 , TiO2 with outstanding stability for 72 h, outperforming most reported works under the identical conditions.

Dual Protection of a Li-Ag Alloy Anode for All-Solid-State Lithium Metal Batteries with the Argyrodite Li6PS5Cl Solid Electrolyte.

All-solid-state lithium metal batteries (ASSLMBs) are considered promising candidates for next-generation energy storage systems. However, the growth of Li dendrites and interface side reactions hinder the practical application of ASSLMBs. To address these issues, a preformed Li-Ag alloy anode for an ASSLMB with the Li6PS5Cl electrolyte was constructed. The preformed Li-Ag alloy anode contains two distinct alloy layers, i.e., Li3Ag and Li0.98Ag0.02, with the former as a protection layer and the latter as a Li deposition site. Besides, a beneficial stable interlayer (Ag-P-S-Cl compound) produced by the reaction between Ag and Li6PS5Cl could work as a secondary protection layer between the anode and electrolyte. The dual protection (Li3Ag and Ag-P-S-Cl compound) suppresses dendritic growth and other interfacial issues effectively and simultaneously. Consequently, a LiCoO2/Li6PS5Cl/Li-Ag all-solid-state battery exhibits a remarkable specific capacity and excellent cycle stability. The dual-protection effect from the preformed Li-Ag alloy anode and the investigation of its working mechanism may enlighten a simple strategy for promoting the development of ASSLMBs.

Vertical Cu Nanoneedle Arrays Enhance the Local Electric Field Promoting C2 Hydrocarbons in the CO2 Electroreduction.

Electrocatalytic reduction of CO2 to multicarbon products is a potential strategy to solve the energy crisis while achieving carbon neutrality. To improve the efficiency of multicarbon products in Cu-based catalysts, optimizing the *CO adsorption and reducing the energy barrier for carbon-carbon (C-C) coupling are essential features. In this work, a strong local electric field is obtained by regulating the arrangement of Cu nanoneedle arrays (CuNNAs). CO2 reduction performance tests indicate that an ordered nanoneedle array reaches a 59% Faraday efficiency for multicarbon products (FEC2) at -1.2 V (vs RHE), compared to a FEC2 of 20% for a disordered nanoneedle array (CuNNs). As such, the very high and local electric fields achieved by an ordered Cu nanoneedle array leads to the accumulation of K+ ions, which benefit both *CO adsorption and C-C coupling. Our results contribute to the design of highly efficient catalysts for multicarbon products.

Insights on the Properties of the O-Doped Argyrodite Sulfide Solid Electrolytes (Li6PS5-xClOx, x=0-1).

Argyrodite sulfide solid electrolytes, such as Li6PS5Cl (LPSC), have received much attention due to their high ionic conductivity (>1 mS cm-1) and success in all-solid-state batteries (long cycle performance, high energy density, etc.). Numerous efforts are spent on modifying the properties of the electrolyte itself. Here, we combine first-principles calculations with experiments to investigate O-doped argyrodite sulfide solid electrolytes (Li6PS5-xClOx, x = 0-1). It is found that Li6PS4.75ClO0.25 (LPSCO0.25) with x = 0.25 and cubic phase (F4̅3 m) shows the highest ion conductivity of 4.7 mS cm-1 (cold-pressed), higher than that of undoped Li6PS5Cl (4.2 mS cm-1). The bare LiCoO2/LPSCO0.25/Li-In all-solid-state battery exhibits an initial capacity of 131 mA h g-1 at 0.1 C and satisfactory cycling stability with 86% capacity retention after 250 cycles to the 4th cycle at 0.3 C under 25 °C. In addition, the NCM811/LPSCO0.25/Li-In cell is assembled using bare LiNi0.83Co0.06Mn0.11O2 cathode and shows an initial discharge capacity of 181 mA h g-1 at 0.1 C and 160 mA h g-1 at 0.3 C. The doping of oxygen-forming Li6PS5-xClOx also improves the stability to Li metal, proven by cyclic voltammetry and powder X-ray diffraction tests. The calculation results for the band structure reveals that LPSC has the lowest unoccupied molecular orbital than LPSCO0.25, further confirming the above conclusion.

Photoelectrochemical Determination of Cu2+ Using a WO3/CdS Heterojunction Photoanode.

Copper ions are not only physiologically essential for life but also hazardous materials causing a series of neurodegenerative diseases. Photoelectrochemical (PEC) detection has attracted a large amount of focus as a potential strategy to develop Cu2+ ion sensors. However, relatively low photocurrent signals with poor antidisturbance ability and the limited concentration range have prevented its practical applications. Here, we designed a WO3/CdS heterojunction photoanode for the PEC determination of Cu2+ in aqueous solution through a simple two-step chemical bath deposition method. The obtained WO3/CdS photoanode had a nanoplate morphology and showed an enhanced photoresponsivity with a photocurrent density of 1.5 mA/cm2 at 1.23 V versus RHE under illumination. Naturally, it exhibited a low detection limit (0.06 µM) and wider range (0.5 µM to 1 mM) for Cu2+ PEC detection first, suggesting that the WO3/CdS heterojunction photoanode is a promising tool to monitor copper pollution in natural environments.

Ionic micro-structure and transport properties of low-temperature aluminium electrolytes containing potassium cryolite and sodium cryolite.

Nowadays, low-temperature aluminium electrolytes are reported to have good prospects for application in the industrial process of aluminium production. In this paper, low-temperature electrolytes containing potassium cryolite and sodium cryolite with a cryolite ratio of 1.3 were investigated by using first-principles molecular dynamics simulation. This calculation reproduces the ionic structure of low-temperature 1.3(KF + NaF)-AlF3 electrolytes, indicating that [AlF4]-, [AlF5]2- and [AlF6]3- are the fundamental aluminum-fluoro clusters and [AlF5]2- is the predominant species. The calculated results for the ionic structure indicate that molten 1.3(KF + NaF)-AlF3 electrolytes have a high ionic polymerization degree, which is unfavorable for the transport properties of low-temperature 1.3(KF + NaF)-AlF3 electrolytes. Fortunately, increasing the mass fraction of NaF can effectively reduce the polymerization degree of ionic structure and thus improve the ionic conductivity of low-temperature 1.3(KF + NaF)-AlF3 electrolytes, which is an important guiding factor for the component selection of low-temperature electrolytes in future. Also, DFT calculations were adopted to further analyse the small aluminum-fluoro complexes. The calculated Raman spectrum of the aluminum-fluoro complexes is excellently consistent with literature results. Our calculated ionic conductivity falls in between the estimated value of the empirical equation of different literature studies, demonstrating that our results may be more precise than the literature results. This further proves the practicability of our modified N-E equation.

Ionic structure and transport properties of KF-NaF-AlF3 fused salt: a molecular dynamics study.

We used the first-principles molecular dynamics simulations combined with the interatomic potential molecular dynamics to study the ionic structure and transport properties of KF-NaF-AlF3 fused salt. Simulation results show that the ionic structure of KF-NaF-AlF3 fused salt is principally dominated by the distorted five-coordinated [AlF5]2- and six-coordinated [AlF6]3- groups. When melting to a liquid, a part of the six-coordinated [AlF6]3- group dissociated into the four-coordinated [AlF4]- and five-coordinated [AlF5]2- groups. Four, five and six-coordinated aluminum-fluoro complexes coexist in KF-NaF-AlF3 fused salt, while the tetrahedral [AlF4]- groups are relatively rare. The content of the bridging fluorine atom is relatively small, about 5-11%, which indicates that the polymerization degree of the ionic structure of the KF-NaF-AlF3 fused salt system is lower. The KF-NaF-AlF3 fused salt has better liquidity and ionic conductivity due to the high self-diffusion coefficients of all particles in the fused salt system. KF can effectively break the F atom bridges, which reduces the polymerization degree of the ionic structure of the fused salt system and increases its ionic conductivity.

Study on the Adhesion Force Between Ga-Doped ZnO Thin Films and Polymer Substrates.

Flexible Ga doped ZnO (GZO) transparent conductive thin films were prepared on polycarbonate (PC) substrates at room temperature by magnetron sputtering. The adhesive property between the GZO film and the PC substrate was investigated quantitatively by the scratch test, which is designed for the quantitative assessment of the mechanical integrity of coated surfaces. The effect of the sputtering pressures on the adhesion forces for the GZO films was investigated. When the sputtering pressure varied from 0.2 to 0.5 Pa, no obvious adhesion force alteration was observed. However, when the sputtering pressure was increased to 0.7 Pa, the adhesion force was decreased. The lowest square resistance of the GZO film was 18.6 Ω/sq. Regardless of the sputtering pressure, the transmittance in the visible light was about 90%. When the sputtering pressure was 0.4 Pa, the optimal figure of merit (ΦTC) was 2.5×10-2 Ω-1, indicating that the optimal pressure was 0.4 Pa.

Bioinspired fiber-like porous Cu/N/C electrocatalyst facilitating electron transportation toward oxygen reaction for metal-air batteries.

Laccase is one of the most effective biocatalysts for oxygen reduction under physiological conditions. Its unique Cu- and N-based active sites with direct electrical pathways for electrons can guarantee rapid oxygen exchange and reduction. Inspired by this specific structure, we designed and fabricated porous fiber-like Cu/N/C based on MOFs as an ORR catalyst. Precision morphology control of fibers contributed to an increase in the electron transport rate compared with that of Cu/N/C nanoparticles, which could minimize interparticle ohmic contacts and provide direct electrical pathways along with sufficient active sites to catalyze oxygen reduction. The designed Cu/N/C catalyst exhibited similar electrochemical activity to that of a commercially available 20 wt% Pt/C ORR catalyst. Moreover, after being employed as the cathode of aluminium-air batteries, the catalyst outperformed a commercial 5 wt% Pt/C catalyst.

DFT investigation of capacious, ultrafast and highly conductive hexagonal Cr2C and V2C monolayers as anode materials for high-performance lithium-ion batteries.

To assess the potential of hexagonal Cr2C and V2C monolayers as anode materials in lithium-ion batteries, first-principles calculations and AIMD simulations were carried out. AIMD simulations and phonon calculations revealed that the honeycomb structure of the hexagonal Cr2C and V2C monolayers is thermodynamically and dynamically stable. A single lithium atom is preferentially absorbed over the center of the honeycomb hollow. The full lithium storage phases of the hexagonal Cr2C and V2C monolayers correspond to Li6Cr2C and Li6V2C, with considerable theoretical specific capacities of 1386 and 1412 mA h g-1, respectively. Interestingly, lithium ion diffusion on the hexagonal Cr2C and V2C monolayers is extremely fast, with low energy barriers of 32 and 28 meV, respectively; these values are much lower than those of other widely investigated anode materials. Moreover, the lithiated hexagonal Cr2C and V2C monolayers show enhanced metallic characteristics and excellent electronic conductivity during the entire lithiation process; these values are superior to those of other anode materials with semiconducting characteristics. The findings in our study suggest that hexagonal Cr2C and V2C monolayers are promising anode materials with high capacities and high rate capabilities for next generation high-performance lithium-ion batteries.

Efficient Planar Perovskite Solar Cells with Reduced Hysteresis and Enhanced Open Circuit Voltage by Using PW12-TiO2 as Electron Transport Layer.

An electron transport layer is essential for effective operation of planar perovskite solar cells. In this Article, PW12-TiO2 composite was used as the electron transport layer for the planar perovskite solar cell in the device structure of fluorine-doped tin oxide (FTO)-glass/PW12-TiO2/perovskite/spiro-OMeTAD/Au. A proper downward shift of the conduction band minimum (CBM) enhanced electron extraction from the perovskite layer to the PW12-TiO2 composite layer. Consequently, the common hysteresis effect in TiO2-based planar perovskite solar cells was significantly reduced and the open circuit voltage was greatly increased to about 1.1 V. Perovskite solar cells using the PW12-TiO2 compact layer showed an efficiency of 15.45%. This work can contribute to the studies on the electron transport layer and interface engineering for the further development of perovskite solar cells.

MoS2 nanodot decorated In2S3 nanoplates: a novel heterojunction with enhanced photoelectrochemical performance.

MoS2 nanodot decorated In2S3 nanoplates were successfully synthesized via a modified one-pot method. The In2S3/MoS2 heterojunction nanocomposite exhibits superior optical and photoelectrochemical performance to the bare ones, owing to the synergistic effect.

Kesterite Cu2ZnSn(S,Se)4 Solar Cells with beyond 8% Efficiency by a Sol-Gel and Selenization Process.

A facile sol-gel and selenization process has been demonstrated to fabricate high-quality single-phase earth abundant kesterite Cu2ZnSn(S,Se)4 (CZTSSe) photovoltaic absorbers. The structure and band gap of the fabricated CZTSSe can be readily tuned by varying the [S]/([S] + [Se]) ratios via selenization condition control. The effects of [S]/([S] + [Se]) ratio on device performance have been presented. The best device shows 8.25% total area efficiency without antireflection coating. Low fill factor is the main limitation for the current device efficiency compared to record efficiency device due to high series resistance and interface recombination. By improving film uniformity, eliminating voids, and reducing the Mo(S,Se)2 interfacial layer, a further boost of the device efficiency is expected, enabling the proposed process for fabricating one of the most promising candidates for kesterite solar cells.