Sluggish Dynamics Research Articles

Screening Na-Excess Cation-Disordered Rocksalt Cathodes with High Performance.

The practical application of Na-ion cathode materials is currently restricted by their low energy density and sluggish dynamics, while the cation-disordered rocksalt (DRX) structures offer a possible solution to the challenge. In this study, among the 24 candidates containing d0 elements, we use mixing temperature as a descriptor to screen the synthesizable Na-excess DRX, and we have identified Na1.2Mn0.4Mo0.4O2 as the most promising candidate that exhibits a Na percolating fraction of 53%, which is higher than that of Li1.2Mn0.4Ti0.4O2 (35%) proposed in the previous study due to the larger lattice constant in Na-excess DRX cathodes. More importantly, Na1.2Mn0.4Mo0.4O2 is predicted to have a capacity of 228 mAh/g with an energy density of 552 Wh/kg derived from percolation theory and cluster-expansion Monte Carlo simulations, which is higher than that of Na1.3Nb0.3Mn0.4O2 and Na1.14Mn0.57Ti0.29O2 synthesized recently. For a better understanding, the redox mechanism is explored, which involves Mo4+/Mo6+, Mn3+/Mn4+, and O2-/On- (0 < n < 2), indicating the participation of anionic redox. Meanwhile, the Na+ diffusion prefers a divacancy mechanism via an o-t-o diffusion channel with a low diffusion barrier of 0.29 eV. This study expands the family of DRX for the cathode of Na-ion batteries with enhanced performance.

Interface Synergistic Effect of NiFe-LDH/3D GA Composites on Efficient Electrocatalytic Water Oxidation.

Currently, NiFe-LDH exhibits an excellent oxygen evolution reaction (OER) due to the interaction of the two metal elements on the layered double hydroxide (LDH) platform. However, such interaction is still insufficient to compensate for its poor electrical conductivity, limited number of active sites and sluggish dynamics. Herein, a feasible two-step hydrothermal strategy that involves coupling low-conductivity NiFe-LDH with 3D porous graphene aerogel (GA) is proposed. The optimized NiFe-LDH/GA (1:1) produced possesses a 257 mV (10 mA cm-2) overpotential and could operate stably for 56 h in an OER. Our investigation demonstrates that the NiFe-LDH/GA has a three-dimensional mesoporous structure, and that there is synergistic interaction between LDH and GA and interfacial reconstruction of NiOOH. Such an interface synergistic coupling effect promotes fast mass transfer and facilitates OER kinetics, and this work offers new insights into designing efficient and stable GA-based electrocatalysts.

Construction of ternary hierarchical heterostructures with favorable interfacial compatibility for ultrahigh photocatalytic H2O2 production

Sluggish charge transfer dynamics are still the key issue limiting the development of photocatalysis. In this study, CdS/ZnIn2S4/MIL-53-NH2 ternary hierarchical heterostructures were constructed via a building block approach, where ZnIn2S4 lamellae first grow on MIL-53-NH2 followed by CdS nanoparticle deposition. The favorable interfacial compatibility and ternary heterostructures contribute to rapid and multistep spatial charge transfer, which suppresses charge recombination. Therefore, ultrahigh H2O2 production of 1792 μmol·L−1 was obtained over CdS/Znln2S4/MIL-53-NH2 composites with visible light, pure water and ambient air, which is not only higher than that of each monomer and binary heterostructure but also better than those of most reported references. Notably, the apparent quantum yield reached 4.5 % at 400 nm, and the solar-to-H2O2 conversion efficiency was 0.081 % in pure water and ambient air. Additionally, H2O2 generation over CdS/Znln2S4/MIL-53-NH2 composites involves two-electron O2 reduction with ·O2- as an intermediate. This work may encourage heterostructure design for efficient photocatalytic H2O2 production.

Enhanced interfacial electric field via sulfur vacancies modified ZnIn2S4-Vs@NiIn2S4 S-scheme photocatalysts for simultaneous H2 evolution and benzyl alcohol oxidation

Designing and developing efficient photocatalysts for H2 evolution and simultaneous oxidation of benzyl alcohol (BA) in aqueous environments provides a cutting-edge strategy for green synthesis. Nevertheless, the photocatalysts suffer from the low photoconversion efficiency because of the sluggish dynamics and repaid recombination of photogenerated charge carriers, which hindering their widespread applications. To address the limitation, a multifunctionnal sulfur vacancies (SVs) modified ZIS-Vs@NIS S-scheme heterojunction with a strong interfacial electric field effect was synthesized to use photocatalytic H2 production and BA oxidation, simultaneously. Experimental analysis supports that the synergistic effect of SVs and S-scheme heterojunction engineering result in a suitable energy band structure alignment and larger Fermi level potential difference. Those factors can realize effective charge transfer and separation, and enhance the photocatalytic performance. As anticipated, ZIS-Vs@NIS exhibited a superior photocatalytic performance with H2 and benzaldehyde (BAD) yields up to 168.1 and 146.1 μmol under the simulated solar-light irradiation for 1.0 h, respectively, which are approximately 13.3 and 11.8 times higher than pristine ZIS. Moreover, the photocatalytic H2 evolution coupled with BA oxidative dehydrogenation mechanism via S-scheme heterojunction over ZIS-Vs@NIS is also demonstrated in detail.

Tuning built-in potential of NiP/NiFe LDH p-n junction towards efficient electrocatalytic water and urea oxidation

Oxygen evolution reaction (OER) and urea oxidation reaction (UOR) are critical half-reactions to realize sustainable hydrogen production. However, the sluggish dynamics derived from the multi-electron pathways necessitate the exploration for efficient catalysts. Herein, a p-n junction nanorod array composed of Mo doped NiP nanorod and ultrathin NiFe LDH nanosheets (NiMoP/NiFe LDH) is proposed to regulate charge distribution of interface for triggering decomposition of water and urea. The p-n junction with a powerful built-in potential (EBI) of 1.2 V at the interface facilitates the adsorption and fracture of chemical group in water and urea molecules. Consequently, the heterostructured electrode demonstrates exceptional electrochemical performance with ultralow potentials of 1.43 and 1.33 V (vs. RHE) at 10 mA cm−2 for OER and UOR, respectively. The overall urea electrolysis driven by NiMoP/NiFe LDH needs only 1.51 V to deliver 100 mA cm−2. This work demonstrates a promising strategy to regulate the EBI of semiconductor heterostructure for energy conversion and sewage treatment.

Unveiling the Reactivity and the Li‐Ion Exchange at the PEO‐Li6PS5Cl Interphase: Insights from Solid‐State NMR

Li6PS5Cl (LPSCl) argyrodites offer high room temperature ionic conductivity (&gt;1 mS cm−1) and are among the most promising solid electrolytes. However, their chemical instability against Li metal compromises the long‐term cyclability. Using PEO‐LiTFSI as an interlayer or as a matrix for composite electrolytes is a promising strategy to address this issue. Nevertheless, the interphase of PEO‐LiTFSI and LPSCl requires further detailed investigations. This work explores the interfacial reactions between these phases using solid‐state nuclear magnetic resonance. Results show that PEO facilitates the formation of a complex with LiCl and Li3PS4 from LPSCl, resulting in an interphase material with limited local mobility, thus impeding ion transport. Although the addition of Br as a dopant can improve the ionic conductivity of LPSCl by inducing disorder and generating the Li vacancies, it makes the LPSCl more susceptible to PEO and increases the extent of the interfacial reaction. 6Li–6Li EXSY experiments demonstrate spontaneous Li‐ion exchange between the PEO and the LPSCl, yet this exchange is significantly hindered by reaction products within the PEO‐LPSCl interphase, attributable to their sluggish local dynamics. This study sheds light on the complex interfacial interaction between PEO‐LiTFSI and sulfide argyrodite, providing insights into designing solid electrolytes for the new generation of electrochemical devices.

Two-dimensional boron-rich BxN as a potential electrode for synergistic immobilization and catalysis of lithium polysulfides: A first-principles investigation

Lithium-sulfur batteries show high promise as the next-generation energy storage systems due to their impressive energy density, cost-effectiveness, and environmentally friendly characteristics. However, the well-known shuttle effect and the sluggish conversion dynamics of lithium polysulfides (LiPSs) during discharging and charging processes hinder their practical application. Herein, we investigate the potential of two-dimensional boron-rich BxN (x=2, 3, and 5) as a viable additive to enhance the anchoring of soluble LiPSs and improve the LiPSs conversion dynamics by harnessing the flexible B-N cooperative interactions. Through density functional calculations, we demonstrate that these BxN electrodes exhibit desirable anchoring ability towards soluble lithium polysulfides (LiPSs) in a realistic solution environment by employing explicit solvent molecules in conjunction with an implicit solvent model. Furthermore, B3N and B5N exhibit robust electrocatalytic activity in both the sulfur reduction and LiPSs decomposition reactions. Intriguingly, a novel cross-sheet mechanism was discovered in B2N, characterized by an Ebarrier of 0.27, 0.20, 0.40, 0.37 and 0.49 eV for the decomposition of Li2S, Li2S2, Li2S4, Li2S6 and Li2S8, attributed to its distinctive configuration with a large eight-ring structure. Additionally, the introduction of BxN can significantly alleviates the volumetric changes experienced by the sulfur cathode during the charging and discharging processes. BxN is a promising catalyst for boosting the electrochemical conversion processes of LiPSs in Li-S batteries and exhibit desirable anchoring ability for inhibiting the shuttle effect induced by soluble LiPSs. These findings offer an alternative approach for the development of advanced sulfur cathode catalysts with reduced shuttle effects and improved rate performance.

In Situ Hydroxide Growth over Nickel-Iron Phosphide with Enhanced Overall Water Splitting Performances.

In this work, three dimensional (3D) self-supported Ni-FeOH@Ni-FeP needle arrays with core-shell heterojunction structure are fabricated via in situ hydroxide growth over Ni-FeP surface. The as-prepared electrodes show an outstanding oxygen evolution reaction (OER) performance, only requiring the low overpotential of 232mV to reach 200mAcm-2 with the Tafel slop of 40mVdec-1. For overall water splitting, an alkaline electrolyzer with these electrodes only requires a cell voltage of 2.14V to reach 1Acm-2. Mechanistic investigations for such excellent electrocatalytic performances are utilized by in situ Raman spectroscopy in conjunction with density functional theory (DFT) calculations. The computation results present that Ni-FeOH@Ni-FeP attains better intrinsic conductivity and the D-band center (close to that of the ideal catalyst), thus giving superior excellent catalytic performances. Likewise, the surface Ni-FeOH layer can improve the structural stability of Ni-FeP cores and attenuate the eventual formation of irreversible FeOOH products. More importantly, the appearance of FeOOH intermediates can effectively decrease the energy barrier of NiOOH intermediates, and then rapidly accelerate the sluggish reaction dynamics, as well as further enhance the electrocatalytic activities, reversibility and cycling stability.

Construction of g-C3N4/Ti3CN MXene Schottky heterojunctions for boosting photocatalytic hydrogen production

Converting solar energy into clean hydrogen (H2) fuel via photocatalytic hydrogen production technology is a promising strategy for sustainable social development. Graphitic carbon nitride (g-C3N4) has attracted much attention due to its unique visible light activity and excellent tunable atomic structure. However, bulk g-C3N4 suffers from challenges such as sluggish charge carrier dynamics and limited active catalytic sites, resulting in lower solar-to-hydrogen conversion efficiency. Herein, we prepare defective ultrathin g-C3N4 nanosheets and subsequently construct 2D g-C3N4/2D Ti3CN MXene heterojunction via electrostatic-driven assembly. The optimized composite CM-2 exhibits the highest hydrogen evolution rate of 7630.5 µmol g−1 h−1. The increase in the hydrogen production rate is attributed to the effective coupling of two materials to form Schottky heterojunctions, which may inhibit the recombination of electron-hole pairs. Additionally, this work explores the pathway of electron transfer in Schottky photocatalyst, and further unveils the synergy of defects and built-in electric field in accelerating photo-induced charge transport as well as enhancing the hydrogen-evolving activity, thereby providing valuable insights for the rational design of highly efficient photocatalytic materials.

3D Bismuth@N-Doped carbon microflowers for ultrahigh rate and stable sodium storage

Sodium-ion batteries (SIBs) are gaining attention in the energy storage market due to their high theoretical capacity and affordability. However, challenges such as volume expansion and sluggish dynamics during sodiation/desodiation hinder their practical application. A 3D bismuth@N-doped carbon microflowers (Bi@NC) anode was successfully prepared to address these issues. The Bi nanosheets expedite Na ions and electrons transport and inhibit particle pulverization, while the N-doped carbon layer maintains electrode stability and improves electronic conductivity. The Bi@NC anode exhibits ultrahigh rate (336.7 mAh/g at 20 A/g) and stable performance (92.9% capacity retention after 2500 cycles at 5 A/g).

Molybdenum diselenide/polymeric carbon nitride dual-homojunction photocatalyst with multi-step charge transfer for efficient catalytic carbon dioxide reduction

Due to the high dissociation energy of carbon dioxide (CO2) and sluggish charge transfer dynamics, photocatalytic CO2 reduction with high performance remains a huge challenge. Herein, we report a novel dual-homojunction photocatalyst comprising of cyano/cyanamide groups co-modified carbon nitride (CN-TH) intramolecular homojunction and 1 T/2H-MoSe2 homojunction (denoted as 1 T/2H-MoSe2/CN-TH) for enhanced photocatalytic CO2 reduction. In this dual-homojunction photocatalyst, the intramolecular CN-TH homojunction could promote the intralayer charge separation and transfer owing to the strong electron-withdrawing capabilities of the two-type cyanamide, while the 1 T/2H-MoSe2 homojunction mainly contributes to a promote interlayer charge transport of CN-TH. This could consequently induce a tandem multi-step charge transfer and accelerate the charge transfer dynamics, resulting in enhanced CO2 reduction activities. Thanks to this tandem multi-step charge transfer, the optimized 1 T/2H-MoSe2/CN-TH dual-homojunction photocatalyst presented a high CO yield of 27.36 μmol·g−1·h−1, which is 3.58 and 2.87 times higher than those of 1 T/2H-MoSe2/CN and 2H-MoSe2/CN-TH single homojunctions, respectively. This work provides a novel strategy for efficient CO2 reduction via achieving a tandem multi-step charge transfer through designing dual-homojunction photocatalyst.

Full-Space Electric Field in Mo-Decorated Zn2In2S5 Polarization Photocatalyst for Oriented Charge Flow and Efficient Hydrogen Production.

Integration of photocatalytic hydrogen (H2) evolution with oxidative organic synthesis presents a highly attractive strategy for the simultaneous production of clean H2 fuel and high-value chemicals. However, the sluggish dynamics of photogenerated charge carriers across the photocatalysts result in low photoconversion efficiency, hindering the wide applications of such a technology. Herein, this work overcomes this limitation by inducing the full-space electric field via charge polarization engineering on a Mo cluster-decorated Zn2In2S5 (Mo-Zn2In2S5) photocatalyst. Specifically, this full-space electric field arises from a cascade of the bulk electric field (BEF) and local surface electric field (LSEF), triggering the oriented migration of photogenerated electrons from [Zn-S] regions to [In-S] regions and eventually to Mo cluster sites, ensuring efficient separation of bulk and surface charge carriers. Moreover, the surface Mo clusters induce a tip enhancement effect to optimize charge transfer behavior by augmenting electrons and proton concentration around the active sites on the basal plane of Zn2In2S5. Notably, the optimized Mo1.5-Zn2In2S5 catalyst achieves exceptional H2 and benzaldehyde production rates of 34.35 and 45.31mmol gcat -1 h-1, respectively, outperforming pristine ZnIn2S4 by 3.83- and 4.15-fold. These findings mark a significant stride in steering charge flow for enhanced photocatalytic performance.

Internal electric field and oxygen vacancies synergistically boost S-scheme VO/BiOCl-TiO2 heterojunction film for photocatalytic degradation of norfloxacin

Sluggish interfacial dynamics and weak redox properties make the degradation of antibiotics by photocatalysts still a great challenge. Herein, constructing S-scheme heterojunction between BiOCl and TiO2 nanorod arrays (TNA) by hydrothermal method, and the synergistic effect of oxygen vacancies (VO) and Internal Electric Field (IEF) on improving the performance of the photocatalysts was revealed by adjusting the VO. The VO modified BiOCl-TiO2 (VBiTNA) exhibited excellent photocatalytic activities for norfloxacin, achieving a degradation efficiency of up to 90.2 % in just 60 min, and the rate constant was as high as 3.67 × 10-2 min−1. In addition, it also showed great photocatalytic degradation performance of NOR in a wide pH range, complex ionized water environment and real water source. The degradation intermediates and degradation pathway of NOR were predicted with LC-MS technology and Fukui function. Combined with free radical capture, electron paramagnetic resonance, relevant electrochemical testing, and DFT calculations reveals the mechanism of the enhanced photocatalytic performance of VBiTNA. The performance enhancement can be attributed to the expansion of the light absorption range, enhanced adsorption of O2 and effective activation to generate ·O2–, while improving the separation efficiency of electron-hole pairs and maintaining a strong redox capacity. This research focusing on VO and IEF mechanisms will help to advance the rational design of high-performance defective photocatalysts.

H*ads dynamics engineering via bimetallic Pd–Cu@MXene catalyst for enhanced electrocatalytic hydrodechlorination

Electrocatalytic hydrodechlorination (EHDC) is a promising approach to safely remove halogenated emerging contaminants (HECs) pollutants. However, sluggish production dynamics of adsorbed atomic H (H*ads) limit the applicability of this green process. In this study, bimetallic Pd–Cu@MXene catalysts were synthesized to achieve highly efficient removal of HECs. The alloy electrode (Pd–Cu@MX/CC) exhibited better EHDC performance in comparison to Pd@MX/CC electrode, resulting in diclofenac degradation efficiency of 93.3 ± 0.1%. The characterization analysis revealed that the Pd0/PdII ratio decreased by forming bimetallic Pd–Cu alloy. Density functional theory calculations further demonstrated the electronic configuration modulation of the Pd–Cu@MXene catalysts, optimizing binging energies for H* and thereby facilitating H*ads production and tuning the reduction capability of H*ads. Noteably, the amounts and reduction potential of H*ads for Pd–Cu@MXene catalysts were 1.5 times higher and 0.37 eV lower than those observed for the mono Pd electrode. Hence, the introduction of Cu into the Pd catalyst optimized the dynamics of H*ads production, thereby conferring significant advantages to EHDC reactions. This augmentation was underscored by the successful application of the alloy catalysts supported by MXene in EHDC experiments involving other HECs, which represented a new paradigm for EHDC for efficient recalcitrant pollutant removal by H*ads.

High conductivity of 2D hydrogen substituted graphyne nanosheets for fast recovery NH3 gas sensors at room temperature

The current two-dimensional (2D) material based NH3 sensors generally suffer from low response values and sluggish recovery dynamics, which is resulted from their inferior conductivity. Herein, high conductivity (0.045 S/m) of 2D hydrogen substituted graphyne (HsGY) nanosheets are successfully synthesized employing aqueous/organic interface method and using them for the first time for the detection of NH3 at room temperature. The resultant gas sensing performance shows that the 2D HsGY nanosheets exhibit a high gas response value (4.9) to 100 ppm NH3 and fast recovery time (108 s) at the room temperature. The NH3 gas sensing mechanism is discussed by utilizing density functional theory (DFT) calculations. The present study provides novel gas sensing material for the development of high-performance room temperature NH3 sensors.

Construction of carbonized polymer dots/potassium doped carbon nitride nanosheets Van der Waals heterojunction by ball milling method for facilitating photocatalytic CO2 reduction performance in pure water

When the advancement of conventional heterojunctions is restricted by lattice matching of materials, Van der Waals heterojunctions formed by interlayer Van der Waals force present enormous development prospects with the revolution of graphene and graphene-like materials. Ascribed to similar graphene-like structures, carbonized polymer dots (CPDs) and potassium-doped carbon nitride nanosheets (KCNNS) were stacked by the ball milling method to form a novel Van der Waals heterojunction. Experimental analysis and density functional theory (DFT) calculations demonstrate that the constructed CPDs/KCNNS heterojunctions can effectively suppress sluggish reaction dynamics. CPDs/KCNNS-2 composites demonstrate enhanced CO2 photoreduction performance (78.98 μmol g−1∙h−1) with 100% CO selectivity in pure water, which is 13.71 times higher than that of KCNNS. In-situ FT-IR spectra were employed to identify the intermediates formed in the CO evolution process of CPDs/KCNNS composites. The manuscript provides a scientific reference for the stacking of Van der Waals heterojunction based on C3N4 in the artificial photosynthesis field.

Acceleration of Solvation Free Energy Calculation via Thermodynamic Integration Coupled with Gaussian Process Regression and Improved Gelman-Rubin Convergence Diagnostics.

The determination of the solvation free energy of ions and molecules holds profound importance across a spectrum of applications spanning chemistry, biology, energy storage, and the environment. Molecular dynamics simulations are powerful tools for computing this critical parameter. Nevertheless, the accurate and efficient calculation of the solvation free energy becomes a formidable endeavor when dealing with complex systems characterized by potent Coulombic interactions and sluggish ion dynamics and, consequently, slow transition across various metastable states. In the present study, we expose limitations stemming from the conventional calculation of the statistical inefficiency g in the thermodynamic integration method, a factor that can hinder the determination of convergence of the solvation free energy and its associated uncertainty. Instead, we propose a robust scheme based on Gelman-Rubin convergence diagnostics. We leverage this improved estimation of uncertainties to introduce an innovative accelerated thermodynamic integration method based on the Gaussian Process regression. This methodology is applied to the calculation of the solvation free energy of trivalent rare-earth elements immersed in ionic liquids, a scenario in which the aforementioned challenges render standard approaches ineffective. The proposed method proves to be effective in computing solvation free energy in situations where traditional thermodynamic integration methods fall short.

Pairing Non‐Solvating Cosolvent with Weakly Solvating Solvents for Facile Desolvation to Enable EC‐Free and High‐Rate Electrolyte for Lithium Ion Batteries

AbstractThe advancement of lithium‐ion batteries (LIBs) calls for superior electrolyte design to satisfy the booming demands of energy storage markets. Despite being typically indispensable in modern electrolytes, ethylene carbonate (EC) exhibits strong affinity with Li+ and derives organic‐rich SEI, leading to sluggish interfacial dynamics and unsatisfied rate capability. Here, we construct a kinetically favorable electrolyte based on linear carbonates (DMC) and fluoroethylene carbonate (FEC) with functional non‐solvating cosolvent, fluorobenzene (FB). Specifically, DMC and FEC, as weak binding solvents, show facile interfacial kinetics. FB enables a loose coordination chemistry through dipole‐dipole interaction, further lubricating Li+ desolvation and transport through SEI at interphase, which accelerates electrochemical kinetics and enables improved rate performance (257 mA h g−1 is achieved for graphite at 6 C). Moreover, the optimized electrolyte shows decent graphite compatibility, long‐term stability (75 % capacity retention after 350 cycles for NCM622/graphite pouch cells at 1 C) and wide‐temperature adaptability (−40~160 °C). This work reveals that dipole‐dipole interaction between non‐solvating cosolvents and solvents can effectively lower desolvation energy barrier and ultimately enable good rate capability, which provides a new avenue for designing EC‐free electrolyte in high‐rate LIBs.

Efficient BiVO4 Photoanode with an Excellent Hole Transport Layer of CuSCN for Solar Water Oxidation

AbstractBismuth vanadate (BiVO4) is reported as a key material in photoelectrocatalysis owing to high theoretical efficiency, relatively narrow band gap of 2.4 eV, and favorable conduction band edge position for hydrogen evolution. However, the sluggish hole transport dynamics lead to slow photogenerated charge separation and transport efficiencies, which result in charge recombination due to aggregation. Herein, a novel hole transport layer of copper(I) thiocyanate (CuSCN) with the aim of significantly enhancing the efficiency of charge transport and stability of BiVO4 photoanodes is reported. The introduction of the hole transport layer could provide an appropriate intermediate energy level for photogenerated hole transfer and avoid charge recombination and trapping. After a photoassisted electrodeposition process of NiCoFe‐Bi catalysis, the obtained photoanode achieves a photocurrent density of 5.6 mA cm−2 at 1.23 V versus reversible hydrogen electrode under AM 1.5 G simulated solar radiation, and an applied bias photon to current efficiency of 2.31%. With the CuSCN layer, BiVO4 photoanode presented impressive stable photocurrent during 50 h continuous illumination. Meanwhile, the unbiased tandem device of the NiCoFe‐Bi/CuSCN/BiVO4 photoanode and the Si solar cell exhibit a solar‐to‐hydrogen efficiency of 5.75% and excellent stability for 14 h.

Dual-Salt Electrolyte Additive Enables High Moisture Tolerance and Favorable Electric Double Layer for Lithium Metal Battery.

The carbonate electrolyte chemistry is a primary determinant for the development of high-voltage lithium metal batteries (LMBs). Unfortunately, their implementation is greatly plagued by sluggish electrode interfacial dynamics and insufficient electrolyte thermodynamic stability. Herein, lithium trifluoroacetate-lithium nitrate (LiTFA-LiNO3 ) dual-salt additive-reinforced carbonate electrolyte (LTFAN) is proposed for stabilizing high-voltage LMBs. We reveal that 1) the in situ generated inorganic-rich electrode-electrolyte interphase (EEI) enables rapid interfacial dynamics, 2) TFA- preferentially interacts with moisture over PF6 - to strengthen the moisture tolerance of designed electrolyte, and 3) NO3 - is found to be noticeably enriched at the cathode interface on charging, thus constructing Li+ -enriched, solvent-coordinated, thermodynamically favorable electric double layer (EDL). The superior moisture tolerance of LTFAN and the thermodynamically stable EDL constructed at cathode interface play a decisive role in upgrading the compatibility of carbonate electrolyte with high-voltage cathode. The LMBs with LTFAN realize 4.3 V-NCM523/4.4 V-NCM622 superior cycling reversibility and excellent rate capability, which is the leading level of documented records for carbonate electrode.