Coulombic Efficiency Research Articles

Electrolyte Design Enables Stable and Energy-dense Potassium-ion Batteries.

Free from strategically important elements such as lithium, nickel, cobalt, and copper, potassium-ion batteries (PIBs) are heralded as promising low-cost and sustainable electrochemical energy storage systems that complement the existing lithium-ion batteries (LIBs). However, the reported electrochemical performance of PIBs is still suboptimal, especially under practically relevant battery manufacturing conditions. The primary challenge stems from the lack of electrolytes capable of concurrently supporting both the low-voltage anode and high-voltage cathode with satisfactory Coulombic efficiency (CE) and cycling stability. Herein, we report a promising electrolyte that facilitates the commercially mature graphite anode (> 3 mAh cm-2) to achieve an initial CE of 91.14% (with an average cycling CE around 99.94%), fast redox kinetics, and negligible capacity fading for hundreds of cycles. Meanwhile, the electrolyte also demonstrates good compatibility with the 4.4 V (vs. K+/K) high-voltage K2Mn[Fe(CN)6] (KMF) cathode. Consequently, the KMF||graphite full-cell without precycling treatment of both electrodes can provide an average discharge voltage of 3.61 V with a specific energy of 316.5 Wh kg-1-(KMF+graphite), comparable to the LiFePO4||graphite LIBs, and maintain 71.01% capacity retention after 2000 cycles.

Electrosynthesis of Amino Acids from Biomass and Nitrate at Industrial Current Densities Using Porous PbBi Electrodes.

Electrosynthesis is a rising and attractive method for efficient amino acid production. However, industrial-grade electrosynthesis of high-value amino acids from simple carbon and nitrogen substrates is confronted with a great challenge. Herein, we design a dual-site PbBi alloy catalyst for various amino acids' electrosynthesis from keto acids and nitrate. An alanine Faradaic efficiency of 59.7% is delivered at -1.5 V vs SCE, reaching the industrial current density of 570 mA cm-2 with high catalytic durability of the porous Pb1Bi0.1 catalyst. In the tandem reaction process, nitrate is first converted to NH2OH via electrochemical reduction mainly over the Bi site. Then the obtained NH2OH integrates with the α-keto acid to form the oxime intermediate. Lastly, the Pb site facilitates the electroreduction of oxime to the final amino acids. More importantly, over 10 kinds of α-amino acids can be successfully synthesized in excellent FE and high yield at high current density, indicating the superior catalytic activity and wide universality of our strategy. In short, this work opens up a novel approach to realize the one-pot electrosynthesis of various amino acids from renewable biomass feedstocks and nitrate waste industrially.

Cluster-Cation Pairs Mediated Assembly of Subnanometer Polyoxometalates Superstructures.

Superstructures assembled by subnanometer polyoxometalate (POM) clusters are interesting for their attractive structures and excellent properties. However, the complex interactions between clusters and cations make it challenging to control the assembly of POM clusters at the subnanometer scale. Here, 20 cluster-assembled superstructures built by two types of MP2W17O61 (M = La-Lu) clusters are successfully synthesized. The precise structures and configurations of the subnanostructures, including nanowires, tetragonal nanosheets, and rectangular nanosheets, are characterized and presented. Molecular dynamics (MD) simulations reveal that the difference in interactions of POM clusters and cations leads to the formation of distinct superstructures. Two mechanisms of superstructure formation are proposed. Furthermore, the EuP2W17 nanosheet behaves with a high Faradaic efficiency of 90.2% and selectivity of 87.3% for glycolic acid in the electrocatalytic ethylene glycol oxidation reaction, which is much higher than that of isolated cluster components. This work connects the cluster topologies and cluster-cation pairs to the superstructures of cluster assemblies, providing general guidelines for the supramolecular self-assembly of POM clusters.

Engineering interfacial molecular interactions on Ag Hollow fibre gas diffusion electrodes for high efficiency in CO2 conversion to CO.

The electrochemical CO2 reduction reaction (CO2RR) occurs at the nanoscale interface of the electrode-electrolyte. Therefore, tailoring the interfacial properties in the interface microenvironment provides a powerful strategy to optimise the activity and selectivity of electrocatalysts towards the desired products. Here, the microenvironment at the electrode-electrolyte interface of the flow-through Ag-based hollow fibre gas diffusion electrode (Ag HFGDE) is modulated by introducing surfactant cetyltrimethylammonium bromide (CTAB) as the electrolyte additive. The porous hollow fibre configuration and gas penetration mode facilitate the CO2 mass transfer and the formation of the triple-phase interface. Through the ordered arrangement of hydrophobic long-alkyl chains, CTAB molecules at the electrode/electrolyte interface promoted CO2 penetration to active sites and repelled water to reduce the activity of competitive hydrogen evolution reaction (HER). By applying CTAB-containing catholyte, Ag HFGDE achieved a high CO Faradaic efficiency (FE) of over 95 % in a wide potential range and double the partial current density of CO. The enhancement of CO selectivity and suppression of hydrogen was attributed to the improvement of charge transfer and the CO2/H2O ratio enhancement. These findings highlight the importance of adjusting the local microenvironment to enhance the reaction kinetics and product selectivity in the electrochemical CO2 reduction reaction CO2RR.

Rapid Fabrication of N-, Cu-, and Co-Doped Electrodes with Strong Electronic Coupling by Cold Plasma for Electrocatalytic Reduction of Nitrate to Ammonia.

Electrochemical NOx- reduction (NOxRR) is a sustainable technology for ammonia synthesis. The development of a simple, fast, and economical catalytic electrode preparation technique is crucial for large-scale ammonia synthesis. Herein, we propose a plate-to-plate DBD plasma strategy to synthesize the catalytic electrodes M-N/CP (M = Cu, Co, Ni, CuCo, and CuNi), achieving in suit codoping of N and bimetals on carbon paper (CP) at room temperature within 3 h. N-doping improves the metal loading and the NOxRR performance by forming N-M bonds. The electronic coupling and synergistic effect of Cu and Co sites facilitate the relay conversion of NO3- to NO2- to NH3. Notably, the NO3- removal efficiency of CuCo-N/CP reaches 82%, with NH3 yield rate of 346 μg h-1 cm-2, and the faradaic efficiency is as high as 86% at -0.58 V vs RHE, which remains competitive in terms of NOxRR performance. Importantly, wet flue gas denitrification and desulfurization coupled with electrocatalytic reduction can convert NOx and SO2 to (NH4)2SO4, Additionally, the maneuverability of plasma technology offers the potential for batch preparation of CuCo-N/CP electrodes for electrochemically driven wet denitrification wastewater valorization.

P-Block Aluminum Single-Atom Catalyst for Electrocatalytic CO2 Reduction with High Intrinsic Activity.

Atomically dispersed transition metal sites on nitrogen-doped carbon catalysts hold great potential for the electrochemical CO2 reduction reaction (CO2RR) to CO due to their encouraging selectivity. However, their intrinsic activity is restricted by the hurdle of the high energy barrier of either *COOH formation or *CO desorption due to the scaling relationship. Herein, we discover a p-block aluminum single-atom catalyst (Al-NC) featuring an Al-N4 site that enables disentangling this hurdle, which endows a moderate reaction kinetic barrier for *COOH formation and *CO desorption, as validated by in situ attenuated total reflection infrared spectroscopy and theoretical simulations. As a result, the developed Al-NC shows a CO Faradaic efficiency (FECO) of up to 98.76% at -0.65 V vs RHE and an intrinsic catalytic turnover frequency of 3.60 s-1 at -0.99 V vs RHE, exceeding those of the state-of-the-art Ni-NC and Fe-NC counterparts. Moreover, it also delivers a partial CO current of 309 mA·cm-2 at 93.65% FECO and 605 mA at >85% FECO in a flow cell and membrane electrode assembly (MEA), respectively. Strikingly, when using low-concentration CO2 (30%) as the feedstock, this catalyst can still deliver a partial CO current of 240 mA at >80% FECO in the MEA. Considering the earth-abundant character of the Al element and the high intrinsic activity of the Al-NC catalyst, it is a promising alternative to today's transition metal-based single-atom catalysts.

In‐Situ Self‐respiratory Solid‐to‐hydrogel Electrolyte Interface Evoked Well‐Distributed Deposition on Zinc Anode for Highly Reversible Zinc‐ion Batteries

The aqueous zinc‐ion batteries (AZIB) have emerged as a promising technology in the realm of electrochemical energy storage. Despite its potential advantages in terms of safety, cost‐effectiveness, and inherent safety, AZIB faces significant challenges. Issues attributed to unsupported thermodynamics and non‐uniform potential distribution and deposition, present formidable obstacles that necessitate resolution. To tackle these challenges, a novel strategy adapting hybrid organic‐inorganic in‐situ derived solid‐to‐hydrogel electrolyte interface (StHEI) has been developed from coordination reactions and self‐respiratory process, establishing uniform diffusion channels by ion bridges and accelerating ion transport. Self‐respiratory pattern of StHEI realized through in‐situ inorganic component conversion further prolongs the protecting duration, which effectively mitigates corrosion and passivation but enhance the mechanical properties of the StHEI measured through Young’s modulus. This novel StHEI promotes well‐distributed potential lines within the Helmholtz regions. Zn2+ are finally induced to deposit and nucleate in a compact, fine, and uniform manner. Asymmetrical batteries assembled with the modified Zn electrode and bare Zn exhibit exceptional stability over 3000 h (1 mA cm‐2‐ 0.5 mAh cm‐2). The asymmetrical Cu//Zn cell achieved an outstanding average Coulombic efficiency (CE) of 99.6% over 1200 cycles.

Bi Doped In2O3 Nanofiber for Efficient Electrocatalytic CO2 Reduction

Electrocatalytic carbon dioxide reduction reaction (CO2RR) to formic acid (HCOOH) is attracted for superfluous CO2 removal and HCOOH production under ambient conditions. Indium based catalysts has considered as a good candidate material for CO2RR‐to‐HCOOH due to their environmentally friendly features. However, the catalytic efficiency is limited by the poor HCOOH Faradaic efficiency (FE) and high reaction overpotential of electrocatalyst, and the activity and stability of indium based catalysts are unsatisfactory, especially in industrial current density that is critical for commercialization. Herein, a fiber Bi‐doped In2O3 was synthesized through electrospinning method, and it demonstrate a FEHCOOH of 88.2% at ‐1.5 V vs. RHE (Reversible Hydrogen Electrode) with partial current density of ‐21.8 mA cm‐2 in H type cell. Specially, the Bi‐In electrocatalyst reach the industrial current density standard, which can work at ‐400 mA cm‐2 current density with FEHCOOH of 92.7% (yield of HCOOH is 6.9 mmol h‐1) in home‐made Flow cell. Importantly, Bi‐In shows 24 hours long‐term stability test in ‐300 mA cm‐2. The improvement catalytic activity of Bi‐In catalyst is ascribed to the optimized electronic structure of In site, and the reduced work function value of Bi‐In is beneficial for reducing the formation energy of the key *OCHO intermediates.

In-Situ Self-respiratory Solid-to-hydrogel Electrolyte Interface Evoked Well-Distributed Deposition on Zinc Anode for Highly Reversible Zinc-ion Batteries.

The aqueous zinc-ion batteries (AZIB) have emerged as a promising technology in the realm of electrochemical energy storage. Despite its potential advantages in terms of safety, cost-effectiveness, and inherent safety, AZIB faces significant challenges. Issues attributed to unsupported thermodynamics and non-uniform potential distribution and deposition, present formidable obstacles that necessitate resolution. To tackle these challenges, a novel strategy adapting hybrid organic-inorganic in-situ derived solid-to-hydrogel electrolyte interface (StHEI) has been developed from coordination reactions and self-respiratory process, establishing uniform diffusion channels by ion bridges and accelerating ion transport. Self-respiratory pattern of StHEI realized through in-situ inorganic component conversion further prolongs the protecting duration, which effectively mitigates corrosion and passivation but enhance the mechanical properties of the StHEI measured through Young's modulus. This novel StHEI promotes well-distributed potential lines within the Helmholtz regions. Zn2+ are finally induced to deposit and nucleate in a compact, fine, and uniform manner. Asymmetrical batteries assembled with the modified Zn electrode and bare Zn exhibit exceptional stability over 3000 h (1 mA cm-2- 0.5 mAh cm-2). The asymmetrical Cu//Zn cell achieved an outstanding average Coulombic efficiency (CE) of 99.6% over 1200 cycles.

Two-dimensional Boridene Nanosheets for Efficient Electrochemical Nitrogen Fixation under Ambient Conditions.

The carbon-free electrocatalytic nitrogen reduction reaction (NRR) is an alternative technology to the current Haber-Bosch method, that can be conducted under ambient conditions, and directly converting water and nitrogen (N₂) into ammonia (NH₃). However, the limited activity and selectivity of NH₃ electrosynthesis hinder the practical applications of NRR. In this study, we present a novel type of electrocatalyst called boridene nanosheets enriched with metal vacancies that are specifically designed for efficient electrocatalytic NRR under ambient conditions. Electrochemical testing in a 0.1 M phosphate-buffered saline (PBS) electrolyte demonstrates that boridene exhibits a high Faradaic efficiency of 66.7% for NH₃ production at -0.2 V vs. RHE, with a maximum NH₃ yield rate of 23.6 µg h-1 mg cat-1 at -0.4 V vs. RHE. Durability tests show that boridene maintains significant stability throughout multiple cycles of NRR. Mechanistic insights are obtained through in situ FTIR spectroscopy, revealing that boridene exhibits a preference for the distal pathway during the process of NRR. These findings highlight the potential of boridene as an efficient and stable catalyst for sustainable NH₃ synthesis.

In‐Situ Constructing a Mixed‐Conductive Interfacial Protective Layer for Ultra‐Stable Lithium Metal Anodes

Lithium metal batteries are the most promising next‐generation energy storage technologies due to their high energy density. However, their practical application is impeded by serious interfacial side reactions and uncontrolled dendrite growth of lithium metal anode. Herein, copper 2,4,5‐trifluorophenylacetate is designed and explored to stabilize lithium metal anode by in‐situ constructing a dense and mixed‐conductive interfacial protective layer. The formed passivated layer not only significantly inhibits interfacial side reactions by avoiding direct contact between lithium metal anode and electrolyte but also effectively suppresses lithium dendrite growth due to the unique inorganic‐rich compositions and mixed‐conductive properties. As a result, the copper 2,4,5‐trifluorophenylacetate‐treated lithium metal anodes show greatly improved cycle stability under both high current density and high areal deposition capacity. Notably, the assembled liquid symmetrical cells with copper 2,4,5‐trifluorophenylacetate‐treated lithium metal anodes can stably work for more than 3000, 5000, and 4800 h at 1.0 mA cm−2–1.0 mAh cm−2, 2.0 mA cm−2–5.0 mAh cm−2, and 10 mA cm−2–5.0 mAh cm−2, respectively. Furthermore, the assembled liquid full cell with a high LiFePO4 loading (~16.9 mg cm−2) shows a significantly enhanced cycle life of 250 cycles with stable Coulombic efficiencies (>99.1%). Moreover, the assembled all‐solid‐state lithium metal battery with a high LiNi0.6Co0.2Mn0.2O2 loading (~5.0 mg cm−2) also exhibits improved cycle stability. These findings underline that the copper 2,4,5‐trifluorophenylacetate‐treated lithium metal anodes show great promise for high‐performance lithium metal batteries.

Effect of puffing on electrochemical properties of sorghum seed based porous carbon materials in supercapacitors

Biomass-based carbon materials are renewable, affordable and environmentally friendly, possessing great potential in electrochemical energy storage as electrode materials in supercapacitors due to their large specific surface area and self-doped heteroatoms. However, the electrochemical properties of these carbon materials may be influenced to some extent by pretreatment procedures of carbon precursors. For this research, a range of porous carbon materials based on unpuffed and puffed sorghum seeds were synthesized under various pre‑carbonization and activation temperatures. Among them, the puffed sorghum seed-based porous carbon (PH-R6A7), prepared through pre‑carbonization at 600 °C and KOH activation at 700 °C, exhibits a higher graphitization degree, increased N and O content, as well as a greater variety of nitrogen-containing groups and significant increasing graphite nitrogen compared to unpuffed sorghum seed-based porous carbon (PC-R6A7) fabricated under similar conditions. These improvements result in enhanced conductivity and wettability of electrode materials, thereby boosting their electrochemical properties. In a three-electrode setup employing a 6 M solution of KOH, PH-R6A7 demonstrates an exceptional specific capacitance of 523.84 F g−1 at 1 A g−1 compared with PC-R6A7 of 366.00 F g−1; even at a high current density of 20 A g−1 it maintains a high level of capacitance at 387.94 F g−1. When employed in a double-electrode configuration at the same current density (i.e., 1 A g−1), PH-R6A7 also achieves higher specific capacitance of 357.83 F g−1 than PC-R6A7 (286.89 F g−1), accompanied by an increased energy density of 12.35 Wh kg−1 and 8.85 Wh kg−1 at a power density of 249.97 W kg−1 and 4.98 kW kg−1, respectively. Furthermore, after undergoing 10,000 cycles at 2 A g−1, PH-R6A7 demonstrates a superior capacitance retention of 99.68 % and coulomb efficiency of 99.91 %. PH-R6A7 fabricated through the combination method of puffing pretreatment and carbonization activation merits acknowledgment as an electrode material of superior performance and notable practical importance.

Oxophilic Sn to promote glucose oxidation to formic acid in Ni nanoparticles.

The electrochemical glucose oxidation reaction (GOR) presents an opportunity to produce hydrogen and high-value chemical products. Herein, we investigate the effect of Sn in Ni nanoparticles for the GOR to formic acid (FA). Electrochemical results show that the maximum activity is related to the amount of Ni, as Ni sites are responsible for catalyzing GOR via the NiOOH/Ni(OH)2 pair. However, the GOR kinetics increases with the amount of Sn, associated with an enhancement of the OH- supply to the catalyst surface for Ni(OH)2 reoxidation to NiOOH. NiSn nanoparticles supported on carbon nanotubes (NiSn/CNT) exhibit excellent current densities and direct GOR via C-C cleavage mechanism, obtaining FA with a Faradaic efficiency (FE) of 93% at 1.45 V vs. reversible hydrogen electrode. GOR selectivity is further studied by varying the applied potential, glucose concentration, reaction time, and temperature. FE toward FA production decreases due to formic overoxidation to carbonates at low glucose concentrations and high applied potentials, while acetic and lactic acids are obtained with high selectivity at high glucose concentrations and 55 °C. Density functional theory calculations show that the SnO2 facilitates the adsorption of glucose on the surface of Ni and promotes the formation of the catalytic active Ni3+ species.

Enhanced Methanol Electrooxidation and Supercapacitive Performance via Compositional Engineering of Colloidal Ni-Co Alloying Nanoparticles.

Among renewable energy technologies, particular attention is paid to electrochemically transforming methanol into valuable formate and storing energy into supercapacitors. In this study, we detailed a simple colloidal-based protocol for synthesizing a series of alloy nanoparticles with tuned Ni/Co atomic ratios, thereby optimizing their electrochemical performance. With the addition of 1 M methanol in 1 M KOH, the optimized composition was able to electrochemically produce formate at 0.149 mmol cm-2 h-1 with a Faradaic efficiency up to 95.1% at 0.6 V versus Hg/HgO within a 22-hour testing period. In 1 M KOH solution without methanol, the supercapacitive performance was achieved at a specific capacitance of over 1500 F g-1, and outstanding cycling stability with only approximately 20% decay after continuous 10000 charging-discharging cycles. These results underscore that the prepared Ni-Co alloy nanoparticles serve as multi-functional electrodes for electrochemical energy conversion and storage, particularly in the MOR and supercapacitors applications.

MnO2@Fe2O3 Cathode for Aqueous Zinc/Manganese Batteries: Enhanced Discharge Capacity and Stability through Forming FeMnO3

Abstract Rechargeable Zn/MnO2 batteries suffer from limited cycle life and low capacity. We utilized MnO2@Fe2O3 as the cathode material, achieving a discharge capacity of 290mAh g-1 at 1A g-1. The Zn/MnO2@Fe2O3 battery maintained over 90% coulombic efficiency after 1800 cycles at 1A g-1. Even at 5 A g-1, it reached 154mAh g-1. The addition of Fe2O3 changed the reaction mechanism and realized the MnO2@Fe2O3 transformation between MnO2@Fe2O3 and MnOOH, FeMnO3 based on the co-doping and conversion of H+/Fe(III). This study underscores the immense potential of the MnO2@Fe2O3 electrode in energy storage applications and highlights the significance of Fe2O3 in enhancing cathode cycling stability and discharge capacity.

Boron-Doping Engineering in AgCd Bimetallic Catalyst Enabling Efficient CO2 Electroreduction to CO and Aqueous Zn-CO2 Batteries.

The limited adsorption and activation of CO2 on catalyst and the high energy barrier for intermediate formation hinder the development of electrochemical CO2 reduction reactions (CO2RR). Herein, this work reports a boron (B) doping engineering in AgCd bimetals to alleviate the above limitations for efficient CO2 electroreduction to CO and aqueous Zn-CO2 batteries. Specifically, the B-doped AgCd bimetallic catalyst (AgCd-B) is prepared via a simple reduction reaction at room temperature. A combination of in situ experiments and density functional theory (DFT) calculations demonstrates that B-doping simultaneously enhances the adsorption and activation of CO2 and reduces the binding energy of the intermediates by moderating the electronic structure of bimetals. As a result, the AgCd-B catalyst exhibits a high CO Faraday efficiency (FECO) of 99% at -0.8V versus reversible hydrogen electrode (RHE). Additionally, it maintains a FECO over 92% at a wide potential window of 600mV (-0.6 to -1.1V versus RHE). Furthermore, the AgCd-B catalyst coupled with the Zn anode to assemble aqueous Zn-CO2 batteries shows a power density of 20.18mW cm-2 and a recharge time of 33h.

Efficient Electrocatalytic Oxidation of Glycerol to Formate Coupled with Nitrate Reduction over Cu-Doped NiCo Alloy Supported on Nickel Foam.

Electrooxidation of biomass-derived glycerol which is regarded as a main byproduct of industrial biodiesel production, is an innovative strategy to produce value-added chemicals, but currently showcases slow kinetics, limited Faraday efficiency, and unclear catalytic mechanism. Herein, we report high-efficiency electrooxidation of glycerol into formate via a Cu doped NiCo alloy catalyst supported on nickel foam (Cu-NiCo/NF) in a coupled system paired with nitrate reduction. The designed Cu-NiCo/NF delivers only 1.23 V vs. RHE at 10 mA cm-2, and a record Faraday efficiency of formate of 93.8 %. The superior performance is ascribed to the rapid generation of NiIII-OOH and CoIII-OOH species and favorable coupling of surface *O with reactive intermediates. Using Cu-NiCo/NF as a bifunctional catalyst, the coupled system synchronously produces NH3 and formate, showing 290 mV lower than the coupling of hydrogen evolution reaction, together with excellent long-term stability for up to 144 h. This work lays out new guidelines and reliable strategies from catalyst design to system coupling for biomass-derived electrochemical refinery.

Efficient Electrocatalytic Oxidation of Glycerol to Formate Coupled with Nitrate Reduction over Cu‐Doped NiCo Alloy Supported on Nickel Foam

AbstractElectrooxidation of biomass‐derived glycerol which is regarded as a main byproduct of industrial biodiesel production, is an innovative strategy to produce value‐added chemicals, but currently showcases slow kinetics, limited Faraday efficiency, and unclear catalytic mechanism. Herein, we report high‐efficiency electrooxidation of glycerol into formate via a Cu doped NiCo alloy catalyst supported on nickel foam (Cu−NiCo/NF) in a coupled system paired with nitrate reduction. The designed Cu−NiCo/NF delivers only 1.23 V vs. RHE at 10 mA cm−2, and a record Faraday efficiency of formate of 93.8 %. The superior performance is ascribed to the rapid generation of NiIII−OOH and CoIII−OOH species and favorable coupling of surface *O with reactive intermediates. Using Cu−NiCo/NF as a bifunctional catalyst, the coupled system synchronously produces NH3 and formate, showing 290 mV lower than the coupling of hydrogen evolution reaction, together with excellent long‐term stability for up to 144 h. This work lays out new guidelines and reliable strategies from catalyst design to system coupling for biomass‐derived electrochemical refinery.

Long‐lifespan 522 Wh kg‐1 Lithium Metal Pouch Cell Enabled by Compound Additives Engineering

Matching high‐voltage cathodes with lithium metal anodes represents the most viable technological approach for developing secondary batteries with ultra‐high energy density exceeding 500 Wh kg‐1. Nevertheless, the instability of electrolyte/electrode interface film and commercial electrolytes with cut‐off voltage above 4.3 V is still a major concern. Herein, we present that excellent cycling stability with an ultra‐high cut‐off voltage of up to 5.0 V can be obtained by using three‐component additives containing fluoroethylene carbonate (FEC), hexadecyl trimethylammonium chloride (CTAC), and tri(pentafluorophenyl)borane (TPFPB). Excellent ionic conductivity, robust interfacial films on both electrodes, and long‐lasting uniform Li+ regulation ability can be obtained in the modifying electrolyte. Consequently, using a high plating/stripping capacity of 3 mAh cm‐2 under the current density of 1 mA cm‐2, lithium symmetric cells demonstrate stable cycling performance exceeding 800 hours. Meanwhile, the 7.3 Ah‐class Li[NixCoyMn1‐x‐y]O2 (x=0.83, NCM83)| Li pouch cells are assembled, which show a high energy density of 522 Wh kg‐1 and present excellent stability over 178 cycles with a high initial coulombic efficiency (CE) of 98.0%.

Long-lifespan 522 Wh kg-1 Lithium Metal Pouch Cell Enabled by Compound Additives Engineering.

Matching high-voltage cathodes with lithium metal anodes represents the most viable technological approach for developing secondary batteries with ultra-high energy density exceeding 500 Wh kg-1. Nevertheless, the instability of electrolyte/electrode interface film and commercial electrolytes with cut-off voltage above 4.3 V is still a major concern. Herein, we present that excellent cycling stability with an ultra-high cut-off voltage of up to 5.0 V can be obtained by using three-component additives containing fluoroethylene carbonate (FEC), hexadecyl trimethylammonium chloride (CTAC), and tri(pentafluorophenyl)borane (TPFPB). Excellent ionic conductivity, robust interfacial films on both electrodes, and long-lasting uniform Li+ regulation ability can be obtained in the modifying electrolyte. Consequently, using a high plating/stripping capacity of 3 mAh cm-2 under the current density of 1 mA cm-2, lithium symmetric cells demonstrate stable cycling performance exceeding 800 hours. Meanwhile, the 7.3 Ah-class Li[NixCoyMn1-x-y]O2 (x=0.83, NCM83)| Li pouch cells are assembled, which show a high energy density of 522 Wh kg-1 and present excellent stability over 178 cycles with a high initial coulombic efficiency (CE) of 98.0%.