Stable Cycling of All-Solid-State Lithium Metal Batteries Enabled by Salt Engineering of PEO-Based Polymer Electrolytes

Poly(ethylene oxide)(PEO)-based polymer electrolytes show the prospect in all-solid-state lithium metal batteries;however,they present limitations of low room-temperature ionic conductivity,and interfacial incompatibility with high voltage cathodes.Therefore,a salt engineering of 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide lithium salt(LiHFDF)/LiTFSI system was developed in PEO-based electrolyte,demonstrating to effectively regulate Li ion transport and improve the interfacial stability under high voltage.We show,by manipulating the interaction between PEO matrix and TFSI^(-)-HFDF^(-),the optimized solid-state polymer electrolyte achieves maximum Li+conduction of 1.24×10^(-4)S cm^(-1)at 40℃,which is almost 3 times of the baseline.Also,the optimized polymer electrolyte demonstrates outstanding stable cycling in the LiFePO_(4)/Li and LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)/Li(3.0-4.4 V,200 cycles)based all-solid-state lithium batteries at 40℃.

Stable Cycling of All-Solid-State Lithium Batteries Enabled by Cyano-Molecular Diamond Improved Polymer Electrolytes

The interfacial instability of the poly(ethylene oxide)(PEO)-based electrolytes impedes the long-term cycling and further application of all-solid-state lithium metal batter-ies.In this work,we have shown an effective additive 1-adaman-tanecarbonitrile,which con-tributes to the excellent per-formance of the poly(ethylene oxide)-based electrolytes.Owing to the strong interaction of the 1-Adamantanecarboni-trile to the polymer matrix and anions,the coordination of the Li^(+)-EO is weakened,and the binding effect of anions is strengthened,thereby improving the Li^(+)conductivity and the electrochemical stability.The diamond building block on the surface of the lithium anode can sup-press the growth of lithium dendrites.Importantly,the 1-Adamantanecarbonitrile also regulates the formation of LiF in the solid electrolyte interface and cathode electrolyte interface,which contributes to the interfacial stability(especially at high voltages)and protects the electrodes,enabling all-solid-state batteries to cycle at high voltages for long periods of time.Therefore,the Li/Li symmetric cell undergoes long-term lithium plating/stripping for more than 2000 h.1-Adamantanecarbonitrile-poly(ethylene oxide)-based LFP/Li and 4.3 V Ni_(0.8)Mn_(0.1)Co_(0.1)O_(2)/Li all-solid-state batteries achieved stable cycles for 1000 times,with capacity retention rates reaching 85%and 80%,respectively.

Resist Thermal Shock Through Viscoelastic Interface Encapsulation in Perovskite Solar Cells

Enhancing the lifetime of perovskite solar cells(PSCs)is one of the essential challenges for their industrialization.Although the external encapsulation protects the perovskite device from the erosion of moisture and oxygen under various harsh conditions.However,the perovskite devices still undergo static and dynamic thermal stress during thermal and thermal cycling aging,respectively,resulting in irreversible damage to the morphology,component,and phase of stacked materials.Herein,the viscoelastic polymer polyvinyl butyral(PVB)material is designed onto the surface of perovskite films to form flexible interface encapsulation.After PVB interface encapsulation,the surface modulus of perovskite films decreases by nearly 50%,and the interface stress range under the dynamic temperature field(−40 to 85°C)drops from−42.5 to 64.8 MPa to−14.8 to 5.0 MPa.Besides,PVB forms chemical interactions with FA+cations and Pb^(2+),and the macroscopic residual stress is regulated and defects are reduced of the PVB encapsulated perovskite film.As a result,the optimized device's efficiency increases from 22.21%to 23.11%.Additionally,after 1500 h of thermal treatment(85°C),1000 h of damp heat test(85°C&85%RH),and 250 cycles of thermal cycling test(−40 to 85°C),the devices maintain 92.6%,85.8%,and 96.1%of their initial efficiencies,respectively.

Vacancy healing for stable perovskite solar cells via bifunctional potassium tartrate

Perovskite solar cell has gained widespread attention as a promising technology for renewable energy.However, their commercial viability has been hampered by their long-term stability and potential Pb leakage. Herein, we demonstrate a bifunctional passivator of the potassium tartrate(PT) to address both challenges. PT minimizes the Pb leakage in perovskites and also heals cationic vacancy defects, resulting in improved device performance and stability. Benefiting from PT modification, the power conversion efficiency(PCE) is improved to 23.26% and the Pb leakage in unencapsulated films is significantly reduced to 9.79 ppm. Furthermore, the corresponding device exhibits no significant decay in PCE after tracking at the maximum power point(MPP) for 2000 h under illumination(LED source, 100 mW cm^(-2)).

Unrevealing the effects of low temperature on cycling life of 21700-type cylindrical Li-ion batteries

The low-temperature performance of Li-ion batteries(LIBs) has important impacts on their commercial applications. Besides the metallic lithium deposition, which is regarded as one of the main failure mechanisms of the LIBs at low temperatures, the synergistic effects originating from the cathode, anode, electrolyte, and separators to the batteries are still not clear. Here, the 21700-type cylindrical batteries were evaluated at a wide range of temperatures to investigate the failure mechanism of batteries. Voltage relaxation, and the post-mortem analysis combined with the electrochemical tests, unravel that the capacity degradation of batteries at low temperature is related to the lithium plating at graphite anodes,the formation of unsatisfied solid deposited/decomposed electrolyte mixture phase on the anode, the precipitation of solvent in the electrolytes and the block of separator pores, and the uneven dissolved transition metal-ions from the cathode. We hope this finding may open up a new avenue to alleviate the capacity degradation of advanced LIBs at low temperatures and shed light on the development of outstanding low-temperature LIBs via simultaneous optimization of all the components including electrodes, electrolytes and separators.

Stable cycling of LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)/lithium metal batteries enabled by synergistic tuning the surface stability of cathode/anode

Ni-rich layered oxides(LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2))show great potential in long-range and low-cost lithiumion batteries.However,due to the high surface sensitivity,their practical application is hindered by interfacial instability with electrolytes under high voltage for long cyclic life.Herein,by combining both firstprinciple calculations and time-of-flight secondary ion mass spectrometry(TOF-SIMS),a novel surface fluorinated reconstruction(SFR)mechanism is proposed to improve the interfacial stability under high voltage,which could effectively regulate the surface fluoride species to desensitize the LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)interface.We demonstrate here that by tuning the ratio of fluoride species,the LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)/Li battery could achieve excellent long-term and high voltage performance(163.5 mA h g^(-1)at 0.5 C for 300 cycles under 4.4 V),while the controlled sample decayed to 125.4 mA h g^(-1)after 300 cycles.Moreover,the favorable cross-talk effect induced by SFR further facilitates the incorporation of suitable amounts of Ni ions into the construction of stable solid electrolyte interface(SEI)layer for anode surface.Therefore,the ultra-long cycling stability under high voltage can be achieved by the robust cathode/electrolyte and Li/electrolyte interfaces,which results in excellent interfacial stability after long cycling.This work provides new insights into the surface design of cathode materials and improves the stability of the electrode-electrode interface under high voltage.

含离子液体热塑性聚氨酯弹性体复合材料的制备及阻燃性能

制备了咪唑型离子液体/热塑性聚氨酯弹性体(TPU)复合材料,分析了离子液体的种类、含量对聚氨酯弹性体氧指数、热释放、烟释放及热稳定性的影响。结果表明,与1-乙基-3-甲基咪唑六氟磷酸盐(EmimPF_(6))、1-十六烷基-3-甲基咪唑六氟磷酸盐(C_(16)mimPF_(6))相比,1-乙基-3-甲基咪唑溴盐(EmimBr)对TPU的阻燃效果更好,且其添加量存在最适量,过高或过低都不利于其在TPU阻燃中的适配性,当质量分数为3%时,阻燃效果最好,可使氧指数达24.3%、热释放峰值降低23.9%、烟释放峰值降低37.5%,高温下的热稳定性也得到改善。

Electronic and thermal properties of Ag-doped single crystal zinc oxide via laser-induced technique

The doping of ZnO has attracted lots of attention because it is an important way to tune the properties of ZnO.Postdoping after growth is one of the efficient strategies.Here,we report a unique approach to successfully dope the single crystalline ZnO with Ag by the laser-induced method,which can effectively further post-treat grown samples.Magnetron sputtering was used to coat the Ag film with a thickness of about 50 nm on the single crystalline ZnO.Neodymium-doped yttrium aluminum garnet(Nd:YAG)laser was chosen to irradiate the Ag-capped ZnO samples,followed by annealing at700℃for two hours to form ZnO:Ag.The three-dimensional(3D)information of the elemental distribution of Ag in ZnO was obtained through time-of-flight secondary ion mass spectrometry(TOF-SIMS).TOF-SIMS and core-level x-ray photoelectron spectroscopy(XPS)demonstrated that the Ag impurities could be effectively doped into single crystalline ZnO samples as deep as several hundred nanometers.Obvious broadening of core level XPS profiles of Ag from the surface to depths of hundred nms was observed,indicating the variance of chemical state changes in laser-induced Ag-doped ZnO.Interesting features of electronic mixing states were detected in the valence band XPS of ZnO:Ag,suggesting the strong coupling or interaction of Ag and ZnO in the sample rather than their simple mixture.The Ag-doped ZnO also showed a narrower bandgap and a decrease in thermal diffusion coefficient compared to the pure ZnO,which would be beneficial to thermoelectric performance.

空间选择性缺陷管理制备高性能碳基CsPbI_(3)钙钛矿太阳能电池

Defects formed at the surface,buried interface and grain boundaries(GB)of CsPbI_(3)perovskite films considerably limit photovoltaic performance.Such defects could be passivated effectively by the most prevalent post modification strategy without compromising the photoelectric properties of perovskite films,but it is still a great challenge to make this strategy comprehensive to different defects spatially distributed throughout the films.Herein,a spatially selective defect management(SSDM)strategy is developed to roundly passivate various defects at different locations within the perovskite film by a facile one-step treatment procedure using a piperazine-1,4-diium tetrafluoroborate(PZD(BF_(4))_(2))solution.The small-size PZD^(2+)cations could penetrate into the film interior and even make it all the way to the buried interface of CsPbI_(3)perovskite films,while the BF_(4)^(-)anions,with largely different properties from I^(-)anions,mainly anchor on the film surface.Consequently,virtually all the defects at the surface,buried interface and grain boundaries of CsPbI_(3)perovskite films are effectively healed,leading to significantly improved film quality,enhanced phase stability,optimized energy level alignment and promoted carrier transport.With these films,the fabricated CsPbI_(3)PSCs based on carbon electrode(C-PSCs)achieve an efficiency of18.27%,which is among the highest-reported values for inorganic C-PSCs,and stability of 500 h at 85℃with 65%efficiency maintenance.

Surface engineering of 1D nanocatalysts for value-added selective electrooxidation of organic chemicals

Electrolytic water splitting by renewable energy is a technology with great potential for producing hydrogen(H_(2))without carbon emission,but this technical route is hindered by its huge energy(electricity)cost,which is mainly wasted by the anode oxygen evolution reaction(OER)while the value of the anode product(oxygen)is very limited.Replacing the high-energy-cost OER with a selective organic compound electrooxidation carried out at a relatively lower potential can reduce the electricity cost while producing value-added chemicals.Currently,H_(2) generation coupled with synthesis of value-added organic compounds faces the challenge of low selectivity and slow generation rate of the anodic products.One-dimensional(1D)nanocatalysts with a unique morphology,well-defined active sites,and good electron conductivity have shown excellent performance in many electrocatalytic reactions.The rational design and regulation of 1D nanocatalysts through surface engineering can optimize the adsorption energy of intermediate molecules and improve the selectivity of organic electrooxidation reactions.Herein,we summarized the recent research progress of 1D nanocatalysts applied in different organic electrooxidation reactions and introduced several different fabrication strategies for surface engineering of 1D nanocatalysts.Then,we focused on the relationship between surface engineering and the selectivity of organic electrooxidation reaction products.Finally,future challenges and development prospects of 1D nanocatalysts in the coupled system consisting of organic electrooxidation and hydrogen evolution reactions are briefly outlined.

Electrolyte design for Li-conductive solid-electrolyte interphase enabling benchmark performance for all-solid-state lithium-metal batteries

Sulfide-based solid-state electrolytes (SSEs) with high Li+ conductivity (δLi^(+)) and trifling grain boundaries have great potential for all-solid-state lithium-metal batteries (ASSLMBs). Nonetheless, the in-situ development of mixed ionic-electronic conducting solid-electrolyte interphase (SEI) at sulfide electrolyte/Li-metal anode interface induces uneven Li electrodeposition, which causes Li-dendrites and void formation, significantly severely deteriorating ASSLMBs. Herein, we propose a dual anionic, e.g., F and N, doping strategy to Li7P3S11, tuning its composition in conjunction with the chemistry of SEI. Therefore, novel Li_(6.58)P_(2.76)N_(0.03)S_(10.12)F_(0.05) glass-ceramic electrolyte (Li_(7)P_(3)S_(11-5)LiF-3Li_(3)N-gce) achieved superior ionic (4.33 mS·cm^(−1)) and lowest electronic conductivity of 4.33 × 10^(−10) S·cm^(−1) and thus, offered superior critical current density of 0.90 mA·cm^(−2) (2.5 times 】Li7P3S11) at room temperature (RT). Notably, Li//Li cell with Li6.58P2.76N0.03S10.12F0.05-gce cycled stably over 1000 and 600 h at 0.2 and 0.3 mA·cm^(−2) credited to robust and highly conductive SEI (in-situ) enriched with LiF and Li3N species. Li3N’s wettability renders SEI to be highly Li+ conductive, ensures an intimate interfacial contact, blocks reductive reactions, prevents Li-dendrites and facilitates fast Li+ kinetics. Consequently, LiNi0.8Co0.15Al0.05O_(2) (NCA)/Li_(6.58)P_(2.76)N_(0.03)S_(10.12)F_(0.05)-gce/Li cell exhibited an outstanding first reversible capacity of 200.8/240.1 mAh·g^(−1) with 83.67% Coulombic efficiency, retained 85.11% of its original reversible capacity at 0.3 mA·cm^(−2) over 165 cycles at RT.

Revealing the vertical structure of in-situ fabricated perovskite nanocrystals films toward efficient pure red light-emitting diodes

The development of efficient perovskite light-emitting diodes(PeLEDs)relies strongly on the fabrication of perovskite films with rationally designed structures(grain size,composition,surface,etc.).Therefore,an understanding of structure-performance relationships is of vital importance for developing high-performance perovskite devices,particularly for devices with in-situ fabricated perovskite nanocrystal films.In this study,we reveal the vertical structure of an in-situ fabricated quasi-two-dimensional perovskite film.By combining time-of-flight secondary ion mass spectrometry,energy dispersive spectroscopy,grazing incidence wide-angle X-ray scattering(GIWAXS),and low-temperature photoluminescence spectra,we illustrate that the resulting in-situ fabricated DPPA_(2)Cs_(n-1)Pb_(n)(Br_(0.3)I_(0.7))_(3n+1)(DPPA^(+):3,3-diphenylpropylammonium)film has a gradient structure with a very thin layer of ligands on the surface,predominantly small-n domains at the top,and predominantly large-n domains at the bottom owing to the solubility difference of the precursors.In addition,GIWAXS measurements show that the domain of n=2 on the top layer has an ordered in-plane alignment.Based on the understanding of the film structure,we developed an in-situ fabrication process with ligand exchange to achieve efficient pure red PeLEDs at 638 nm with an average external quantum efficiency(EQE)of 7.4%.The optimized device had a maximum luminance of 623 cd/m^(2) with a peak EQE of 9.7%.

Tailored Carrier Transport Path by Interpenetrating Networks in Cathode Composite for High Performance All‑Solid‑State Li‑SeS_(2) Batteries

All-solid-state Li-SeS_(2) batteries(ASSLSs)are more attractive than traditional liquid Li-ion batteries due to superior thermal stability and higher energy density.However,various factors limit the practical application of all-solid-state Li-SeS_(2) batteries,such as the low ionic conductivity of the solid-state electrolyte and the poor kinetic property of the cathode composite,resulting in unsatisfactory rate capability.Here,we employed a traditional ball milling method to design a Li_(7)P_(2.9)W_(0.05)S_(10.85) glass–ceramic electrolyte with high conductivity of 2.0 mS cm^(−1) at room temperature.In order to improve the kinetic property,an interpenetrating network strategy is proposed for rational cathode composite design.Signifcantly,the disordered cathode composite with an interpenetrating network could promote electronic and ionic conduction and intimate contacts between the electrolyte–electrode particles.Moreover,the tortuosity factor of the carrier transport channel is considerably reduced in electrode architectures,leading to superior kinetic performance.Thus,assembled ASSLS exhibited higher capacity and better rate capability than its counterpart.This work demonstrates that an interpenetrating network is essential for improving carrier transport in cathode composite for high rate all-solid-state Li-SeS_(2) batteries.

Removing the Intrinsic NiO Phase and Residual Lithium for High-Performance Nickel-Rich Materials

Layered Ni-rich materials for lithium-ion batteries exhibit high discharge capacities but degraded cyclability at the same time.The limited cycling stability originates from many aspects.One of the critical factors is the intrinsic insulating residual lithium compounds and the rock-salt(NiO)phase on the surface of particles.In this work,LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) material is etched with a trace amount of boric acid and used as a model to demonstrate the influences of weak acid treatment on the surface phase regulations.After the etching process,the pH of the material is reduced from 12.08 to 11.82,along with a lower cation mixing degree and promoting electrochemical performances.Corresponding measurements demonstrate that weak acids such as H_(3)BO_(3) can also etch the NiO phase on the surface to adjust the surface of the particles to a pure layered structure.This process improves the lithium-ion diffusion and electron transport in the interface between material and electrolyte,consequently leading to better cycling performance and rate capability.This study provides a novel strategy and comprehensive understanding of acid modification and surface phase regulation process of Ni-rich cathode materials for lithium-ion batteries.

The Active Sites and Corresponding Stability Challenges of the M-N-C Catalysts for Proton Exchange Membrane Fuel Cell

Proton exchange membrane fuel cells(PEMFCs)as promising alternatives to traditional internal combustion engines have attracted massive concerns to promote their wide application in society.However,the biggest challenge to the commercialization of PEMFCs remains the high cost due to the adoption of the platinum group metal(PGM)catalysts in the cathode.