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Highly Efficient Organosulfur and Lithium‐Metal Hosts Enabled by C@Fe 3 N Sponge
Abstract Lithium‐organosulfur (Li‐OS) batteries, despite possessing high theoretical specific capacity, encounter a few practical challenges, including unsatisfactory lifespan and low active material utilization under realistic conditions. Here, diisoropyl xanthogen polysulfide (DIXPS) has been selected as a model organosulfur compound to investigate the practical feasibility of Li‐OS batteries under realistic conditions. A well‐designed freestanding carbon sponge decorated with Fe 3 N nanoparticles (C@Fe 3 N) is introduced into the Li‐OS cells as a scaffold for both Li and DIXPS. The lithiophilic property of the C@Fe 3 N host guides uniform lithium deposition at the anode, and the catalysis of the DIXPS conversion reaction promotes the kinetics at the cathode. Impressively, the synergistic effect of C@Fe 3 N leads to an extremely stable cycling performance over 1 000 cycles in a Li‐OS full cell under realistic conditions.
Lithium‐Containing Hybrid SEI Layer Enabling High Mass Loading and Anode‐Less Sodium Metal Batteries
Abstract The continuous rupturing and rebuilding of unstable solid electrolyte interphase (SEI) layer during cycling would block Na + diffusion and induce Na dendrite formation, ultimately limiting the practical application of high‐energy‐density sodium metal batteries. Herein, a hybrid SEI layer containing Li‐species is dexterously constructed on the surface of sodium metal anode. Li‐containing inorganic components (Li 3 N, LiF, and Li 2 CO 3 ) are introduced to stabilize the Na/electrolyte interface and enhance the mechanical and diffusion kinetic properties of the SEI layer, which can reduce the side reactions and gas generation, regulate Na + flux during cycling and promote rapid Na + migration for uniform dendrite‐free Na deposition. As a result, the constructed Na symmetric cells achieve low overpotential and long cycle life of 5900, 1800, and 500 h at current densities of 3, 10, and 30 mA cm −2 , respectively. Furthermore, the full cells paired with the Na₃V₂(PO₄)₃ cathode demonstrate high specific capacity and excellent cycle stability, even at an ultra‐high cathode loading of 39.3 mg cm −2 and a low N/P ratio (negative/positive electrode capacity ratio of 1.21).
Highly Efficient Organosulfur and Lithium-Metal Hosts Enabled by C@Fe 3 N Sponge
Lithium-organosulfur (Li-OS) batteries, despite possessing high theoretical specific capacity, encounter a few practical challenges, including unsatisfactory lifespan and low active material utilization under realistic conditions. Here, diisoropyl xanthogen polysulfide (DIXPS) has been selected as a model organosulfur compound to investigate the practical feasibility of Li-OS batteries under realistic conditions. A well-designed freestanding carbon sponge decorated with Fe 3 N nanoparticles (C@Fe 3 N) is introduced into the Li-OS cells as a scaffold for both Li and DIXPS. The lithiophilic property of the C@Fe 3 N host guides uniform lithium deposition at the anode, and the catalysis of the DIXPS conversion reaction promotes the kinetics at the cathode. Impressively, the synergistic effect of C@Fe 3 N leads to an extremely stable cycling performance over 1000 cycles in a Li-OS full cell under realistic conditions.
Lithium‐Containing Hybrid SEI Layer Enabling High Mass Loading and Anode‐Less Sodium Metal Batteries
The continuous rupturing and rebuilding of unstable solid electrolyte interphase (SEI) layer during cycling would block Na + diffusion and induce Na dendrite formation, ultimately limiting the practical application of high-energy-density sodium metal batteries. Herein, a hybrid SEI layer containing Li-species is dexterously constructed on the surface of sodium metal anode. Li-containing inorganic components (Li 3 N, LiF, and Li 2 CO 3 ) are introduced to stabilize the Na/electrolyte interface and enhance the mechanical and diffusion kinetic properties of the SEI layer, which can reduce the side reactions and gas generation, regulate Na + flux during cycling and promote rapid Na + migration for uniform dendrite-free Na deposition. As a result, the constructed Na symmetric cells achieve low overpotential and long cycle life of 5900, 1800, and 500 h at current densities of 3, 10, and 30 mA cm −2 , respectively. Furthermore, the full cells paired with the Na₃V₂(PO₄)₃ cathode demonstrate high specific capacity and excellent cycle stability, even at an ultra-high cathode loading of 39.3 mg cm −2 and a low N/P ratio (negative/positive electrode capacity ratio of 1.21).
Lithium–Metal Batteries via Suppressing Li Dendrite Growth and Improving Coulombic Efficiency
Lithium–metal batteries (LMB) are recognized as one of the most promising candidates for the next generation of batteries due to their high energy density. Extensive studies have been refocused on the field in the past decade to make the technology commercially viable. Unfortunately, despite exciting progress that has been made, the practical application of LMBs is still hampered by the uncontrollable Li plating morphology and inferior Coulombic efficiency (CE) during cycling. Herein, first, the relevant research that has been carried out in the past decade (2010–2021) is briefly summarized and then the Li plating behaviors, mechanistic understanding of these behaviors, and strategies to suppress Li dendrite growth are discussed. Finally, the methods and techniques to improve Coulombic efficiency (CE) is discussed, especially the design of liquid electrolytes, and possible research directions for the future development of LMBs.
Microstructure and defect engineering of graphite anodes by pulsed laser annealing for enhanced performance of lithium-ion batteries
We report nanosecond pulsed laser annealing significantly improves cyclability and current carrying capacity of lithium-ion batteries (LIBs). This improvement is achieved by engineering of microstructure and defect contents present in graphite in a controlled way by using pulsed laser annealing (PLA) to increase the number density of Li + ion trapping sites. The PLA treatment causes the following changes: (1) creates surface steps and grooves between the grains to improve Li + ion charging and intercalation rates; (2) removes inactive polyvinylidene difluoride (PVDF) binder from the top of graphite grains and between the grains which otherwise tends to block the Li + migration; and (3) produces carbon vacancies in (0001) planes which can provide Li + charging sites. From X-ray diffraction data, we find upshift in diffraction peak or reduction in planar spacing, from which vacancy concentration was estimated to be about 1.0%, which is higher than the thermodynamic equilibrium concentration of vacancies. The laser treatment creates single and multiple C vacancies which provide sites for Li + ions, and it also produces steps and grooves for Li + ions to enter the intercalating sites. It is envisaged that the formation of these sites enhances Li+ ion absorption during charge and discharge cycles. The current capacity increases from an average 360 mAh/g to 430 mAh/g, and C–V shows significant reduction in SEI layer formation after the laser treatment. If the vacancy concentration is too high and charge-discharge cycles are long, then trapping of electrons by Li + may occur, which can lead to Li 0 formation and Li plating causing reduction in current capacity.
Unveiling the thermite-driven lithium fire ignition in solid-state batteries
Here, this study challenges the assumption of the non-flammability of lithium metal all-solid-state batteries (LiSSBs) and other lithium metal batteries without flammable electrolytes. Through thermodynamic calculations and ex situ experiments, we reveal for the first time the risk of thermite reactions between lithium metal and LiFePO 4 in both charged and discharged states. Reactivity is worsened by excess lithium metal in the cell, reaching final maximum adiabatic temperatures of 2,500°C in the charged state, which is hot enough to boil lithium. The thermite reaction triggers spontaneously at 500°C, with poor surface contact, while increasing surface contact through mixing initiates the reaction at room temperature in an inert environment. Despite its fast kinetics, this reaction is transport limited due to lithium passivation, leading to long burn times and reignition risks. Given the risk of lithium metal contacting the cathode during failure, understanding these reactions is crucial for ensuring the safe deployment of LiSSBs.
Preparation and electrochemical properties of high-entropy oxide Li x (CrMnCoNiZn) 3-x O 4
High-entropy oxides (HEOs) have gained significant attention as anode materials for lithium-ion batteries (LIBs) due to their high theoretical specific capacity, synergistic effects of constituent elements, and enhanced structural stability induced by high entropy. Here, this study investigates the electrochemical properties of a novel series of HEOs, Li x (CrMnCoNiZn) 3-x O 4 , synthesized via the sol-gel method. As lithium content increases, the electrochemical lithium storage performance of the HEOs improves, attributed to the rise in high-valence states and oxygen vacancies. The high valence state of elements facilitates greater electron transfer, enhancing the specific capacity during lithium insertion. Additionally, a higher concentration of oxygen vacancies boosts ionic conductivity and lithium ion diffusion kinetics, leading to superior electrochemical performance. Among the synthesized materials, Li 0.11 (CrMnCoNiZn) 2.89 O 4 exhibited the best performance, delivering a discharge capacity of 365 mAh·g −1 after 100 cycles at 100 mA·g −1 , 257 mAh·g −1 after 1000 cycles at 1 A·g −1 , and a rate capacity of 196 mAh·g −1 at 2 A·g −1 . The Li + diffusion coefficient reached 2.78 × 10 −15 cm 2 ·s −1 . This work not only deepens the understanding of HEOs' electrochemical behavior in LIBs but also provides insights into the impact of lithium ion substitution on their performance.
Sweeping potential regulated structural and chemical evolution of solid-electrolyte interphase on Cu and Li as revealed by cryo-TEM
A fundamental understanding of solid-electrolyte interphase (SEI) is paramount importance for controlling the cycling performance of rechargeable lithium metal batteries. The structural and chemical evolution of SEI with respect to electrochemical operating condition remains barely established. Here we develop a unique method for imaging the evolution of SEI formed on the Cu foil under sweeping electrochemical potential. By using cryogenic TEM imaging combined with energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy electronic structure analyses, we reveal that, for the vinylene carbonate (VC)-free electrolyte, the SEI formed at 1.0 V is a monolithic amorphous structure, which evolves to amorphous matrix embedded with Li 2 O particles as the voltage decreases to 0 V. In the case of VC-containing electrolyte, the SEI is featured by an amorphous matrix with Li 2 O particles from 1.0 V to 0 V. The thickness of SEI formed on Cu foil increases with decreasing voltage. Associated with the localized charge modulation by the surface topographic feature and defects in the Cu foil, the SEI layer shows direct spatial correlation with these structural defects in the Cu. In addition, upon Li deposition, the SEI formed on the Li metal has similar thickness with, but different composition from the SEI formed on the Cu foil at 0 V. Furthermore, those results provide insight toward SEI engineering for enhanced cycling stability of Li metal.
Kinetic versus Thermodynamic Stability of LLZO in Contact with Lithium Metal
Li 7 La 3 Zr 2 O 12 (LLZO) garnet-based oxides are a promising class of solid electrolytes used as the separator in all-solid-state batteries (ASSBs). While LLZO is considered to have a wide electrochemical stability window, its intrinsic stability in contact with lithium metal is not sufficiently well understood, and there is still a debate on the key question of whether LLZO does or does not form passivation layers before and during cycling. Utilizing both in situ and operando X-ray photoelectron spectroscopy techniques, in this work we reveal the presence of a kinetic barrier to the reduction of LLZO by Li metal, with the extent of oxygen-deficient interphase (ODI) formation depending sensitively on the energetics of Li metal arriving at the Li vertical bar LLZO interface. Despite the clear presence of a kinetic barrier to reduction, the electrochemical response of the Li vertical bar LLZO interface is unchanged by the presence of the ODI, indicating that ODI formation during electrochemical cycling does not hinder charge transfer across the Li vertical bar LLZO interface. Overall, these results reveal that the reactivity of LLZO with Li metal depends not only on the material properties of the adjoining phases (i.e., surface purity and active contact) and their resulting thermodynamic stability but also on the energy input at the interface and the resulting reaction kinetics. Furthermore, the presence of a kinetic barrier to reduction highlights the additional complexities governing the reactivity of solid-state interfaces in ASSBs and underscores the importance of operando characterization of interfacial stability to design more robust, high-performance protection strategies for solid electrolytes in contact with reactive electrodes.
Low-Temperature Processing of Pyrolysis Bio-Oil for Sustainable Biographite Production
Catalytic graphitization of pyrolysis bio-oil with iron (Fe) can produce an anode material for lithium-ion batteries (LIBs) at a moderate temperature. The key challenge to scaling up the process is foaming, which occurs due to the oxidation of Fe by the organic acids present in bio-oil. This study explored five different pathways to control foaming in bio-oil upon Fe addition, including (i) defoamers use, (ii) use of iron oxide (Fe2O3) as graphitization catalyst, (iii) pH adjustment of bio-oil, (iv) bio-oil coking (300-500 degrees C), and (v) low-temperature pretreatment of bio-oil (150-200 degrees C). The low-temperature pretreatment successfully avoided foaming by removing the volatile acids in bio-oil. The bio-oil was solidified and powdered for even mixing with the Fe catalyst. The biographite catalytically prepared at 1500 degrees C following this pathway demonstrated nearly theoretical specific gravimetric capacity (~370 mAh/g), high initial Coulombic efficiency (90.03%), and minimal capacity fading after 50 cycles in LIB half-cells. The low-temperature pretreatment pathway also addressed the viscosity, swelling, and aging issues associated with bio-oil processing and will make scale-up endeavors more attainable.
A Polymer-in-Salt Electrolyte with Enhanced Oxidative Stability for Lithium Metal Polymer Batteries
Lithium (Li) metal polymer batteries (LMPBs) are a promising candidate of solid-state batteries with high safety. However, rare progress has been demonstrated so far in high voltage stability of polyethylene oxide (PEO) based polymer electrolytes for LMPBs. Herein, we revived the polymer-in-salt electrolyte (PISE) strategy based on the PEO-LiFSI system with EO/Li = 8 through a dry process to avoid the contamination of the residual solvent. The obtained PISEs exhibit quite different morphologies and coordination structures which greatly enhance the oxidative stability of polymer electrolytes. P(EO)1LiFSI has a low melting temperature, a high ionic conductivity at 60 ?C and an oxidative stability of ~4.5 V vs. Li/Li+ (overcoming the inherent low oxidative stability of PEO). With an effective interphase rich in inorganic species, in combination with good stability of the hybrid polymer electrolyte towards Li metal, the cycling stability of Li||LiNi1/3Co1/3Mn1/3O2 is greatly improved. The LMPB can retain 74.4% of capacity after 186 cycles at 60 ?C under the charge cutoff voltage of 4.3 V. The findings point out a promising strategy to develop high-voltage stable polymer electrolytes for high energy-density and safe LMPBs.
Selecting the Optimal Fluorinated Ether Co-Solvent for Lithium Metal Batteries
To guide the selection of a suitable fluorinated ether (FE) co -solvent for lithium metal batteries, it is crucial to understand the relationship between the organic structures of the FEs and the electrochemical performance of an FE-containing electrolyte. In this work, 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane (FEE), 1,1,2,2-tetrafluoro-3-(1,1,2,2-tetrafluoroethoxy)-propane (TTE), and 1,2-bis(1,1,2,2-tetrafluoroethoxy)ethane (OFDEE) were chosen as representative FE co-solvents because of their distinct structural properties. The structure-activity relationship between the FEs and the electrochemical performance of Li||LiNi 0.6 Mn 0.2 Co 0.2 O 2 (Li||NMC622) cells was correlated and quantified by Fourier-transform infrared and multi-dimensional nuclear magnetic resonance techniques. Sand's model was also employed to assess the extent of lithium dendrite formation in the cells using various FE electrolytes. The cycling performance of Li||NMC622 cells using different FE co-solvents follows the order FEE > TTE > OFDEE. Further, since the direct measurement of Sand's time is difficult, we introduced relative Sand's time to probe the diffusion behavior of each electrolyte, and the results showed that the best performance was obtained in the electrolyte with the longest relative Sand's time. Moreover, the lithium metal cell using the electrolyte with FEE co-solvent showed similar capacity retention compared with the baseline electrolyte at room temperature, but it demonstrated significantly improved low-temperature performance. The results indicate that FEE is a promising co-solvent candidate for improving the low-temperature performance of lithium metal batteries because it possesses not only non-solvating behavior but also very low viscosity and non-flammability. The advanced electrolyte LiPF 6 -FEC-DMC-FEE enables very stable cycling of lithium metal batteries at various temperatures.
MX Anti-MXenes from Non-van der Waals Bulks for Electrochemical Applications: The Merit of Metallicity and Active Basal Plane
Two-dimensional transition-metal compounds (2DTMCs) are promising materials for electrochemical applications, but 2DTMCs with metallicity and active basal planes are rare. In this work, we proposed a simple and effective strategy to extract 2DTMCs from non-van der Waals bulk materials and established a material library of 79 2DTMCs, which we named as anti-MXenes since they are composed of one M atomic layer sandwiched by two X atomic layers. By means of density functional theory computations, 24 anti-MXenes were confirmed to be thermodynamically, dynamically, mechanically, and thermally stable. The metallicity and active basal plane endow these anti-MXenes with potential as excellent electrode materials, for example, as electrocatalysts for hydrogen evolution reactions (HER). Among the noble-metal free anti-MXenes with favorable H-binding, CuS can boost HER at the whole range of H coverages, while CoSi, FeB, CoB, and CoP show promise for HER at some specific H coverages. The active sites are the tetra-coordinating nonmetal atoms at the basal planes, thus rendering a very high density of active sites for these materials. CoB is also a promising anode material for lithium-ion batteries, showing low Li diffusion energy barriers, a very high capacity, and a suitable open circuit voltage. Overall, this work promotes the “computational exfoliation” of 2D materials from non-van der Waals bulks and exemplifies the applications of anti-MXenes in various electrochemical processes.
Cation-disorder zinc blende Zn 0.5 Ge 0.5 P compound and Zn 0.5 Ge 0.5 P–TiC–C composite as high-performance anodes for Li-ion batteries
Zn 0.5 Ge 0.5 P shows superior crystal and band structure as anode material for lithium-ion batteries, and Zn 0.5 Ge 0.5 P–TiC–C exhibits excellent electrochemical performance.
The early-stage growth and reversibility of Li electrodeposition in Br-rich electrolytes
Significance Spatial variations in chemical composition and transport properties of the material phases (interphases) formed on reactive metals in liquid electrolytes are thought to be responsible for the propensity of metal battery electrodes to electrodeposit in irregular, nonplanar morphologies. Equilibrium theoretical calculations using joint density functional analysis in vacuum and generic liquid media indicate that in-plane transport at such interphases is enhanced substantially if LiX (X = Br > Cl > F) species predominate. This study employs optical visualization experiments and nucleation theory to experimentally investigate nucleation and early-stage growth dynamics of metallic lithium in electrolytes enriched with LiBr. It is shown that the Li-Br–rich interphases formed profoundly alter the morphology of Li electrodeposits by enhancing Li-ion surface diffusion.