Real-time tracking of electron transfer at catalytically active interfaces in lithium-ion batteries.

Transition metals and related compounds are known to exhibit high catalytic activities in various electrochemical reactions thanks to their intriguing electronic structures. What is lesser known is their unique role in storing and transferring electrons in battery electrodes which undergo additional solid-state conversion reactions and exhibit substantially large extra capacities. Here, a full dynamic picture depicting the generation and evolution of electrochemical interfaces in the presence of metallic nanoparticles is revealed in a model CoCO3/Li battery via an in situ magnetometry technique. Beyond the conventional reduction to a Li2CO3/Co mixture under battery operation, further decomposition of Li2CO3 is realized by releasing interfacially stored electrons from its adjacent Co nanoparticles, whose subtle variation in the electronic structure during this charge transfer process has been monitored in real time. The findings in this work may not only inspire future development of advanced electrode materials for next-generation energy storage devices but also open up opportunities in achieving in situ monitoring of important electrocatalytic processes in many energy conversion and storage systems.

Unique insights into the design of low-strain single-crystalline Ni-rich cathodes with superior cycling stability.

Micro-sized single-crystalline Ni-rich cathodes are emerging as prominent candidates owing to their larger compact density and higher safety compared with poly-crystalline counterparts, yet the uneven stress distribution and lattice oxygen loss result in the intragranular crack generation and planar gliding. Herein, taking LiNi0.83Co0.12Mn0.05O2 as an example, an optimal particle size of 3.7 µm is predicted by simulating the stress distributions at various states of charge and their relationship with fracture free-energy, and then, the fitted curves of particle size with calcination temperature and time are further built, which guides the successful synthesis of target-sized particles (m-NCM83) with highly ordered layered structure by a unique high-temperature short-duration pulse lithiation strategy. The m-NCM83 significantly reduces strain energy, Li/O loss, and cationic mixing, thereby inhibiting crack formation, planar gliding, and surface degradation. Accordingly, the m-NCM83 exhibits superior cycling stability with highly structural integrity and dual-doped m-NCM83 further shows excellent 88.1% capacity retention.

Steering lithium and potassium storage mechanism in covalent organic frameworks by incorporating transition metal single atoms.

Organic electrodes mainly consisting of C, O, H, and N are promising candidates for advanced batteries. However, the sluggish ionic and electronic conductivity limit the full play of their high theoretical capacities. Here, we integrate the idea of metal-support interaction in single-atom catalysts with π-d hybridization into the design of organic electrode materials for the applications of lithium (LIBs) and potassium-ion batteries (PIBs). Several types of transition metal single atoms (e.g., Co, Ni, Fe) with π-d hybridization are incorporated into the semiconducting covalent organic framework (COF) composite. Single atoms favorably modify the energy band structure and improve the electronic conductivity of COF. More importantly, the electronic interaction between single atoms and COF adjusts the binding affinity and modifies ion traffic between Li/K ions and the active organic units of COFs as evidenced by extensive in situ and ex situ characterizations and theoretical calculations. The corresponding LIB achieves a high reversible capacity of 1,023.0 mA h g-1 after 100 cycles at 100 mA g-1 and 501.1 mA h g-1 after 500 cycles at 1,000 mA g-1. The corresponding PIB delivers a high reversible capacity of 449.0 mA h g-1 at 100 mA g-1 after 150 cycles and stably cycled over 500 cycles at 1,000 mA g-1. This work provides a promising route to engineering organic electrodes.

Densified vertically lamellar electrode architectures for compact energy storage.

As one of the most compact electrochemical energy storage systems, lithium-ion batteries (LIBs) are playing an indispensable role in the process of vehicle electrification to accelerate the shift to sustainable mobility. Making battery electrodes thicker is a promising strategy for improving the energy density of LIBs which is essential for applications with weight or volume constraints, such as electric-powered transportation; however, their power densities are often significantly restricted due to elongated and tortuous charge traveling distances. Here, we propose an effective methodology that couples bidirectional freeze-casting and compression-induced densification to create densified vertically lamellar electrode architectures for compact energy storage. The vertically lamellar architectures not only overcome the critical thickness limit for conventional electrodes but also facilitate and redistribute the lithium-ion flux enabling both high rate capability and stable cyclability. Furthermore, this proposed methodology is universal as demonstrated in various electrochemical active material systems. This study offers a facile approach that realizes simultaneous high energy and high power in high-loading battery electrodes and provides useful rationales in designing electrode architectures for scalable energy storage systems.

Mechanochemical upcycling of spent LiCoO2 to new LiNi0.80Co0.15Al0.05O2 battery: An atom economy strategy.

The use of strong acids and low atom efficiency in conventional hydrometallurgical recycling of spent lithium-ion batteries (LIBs) results in significant secondary wastes and CO2 emissions. Herein, we utilize the waste metal current collectors in spent LIBs to promote atom economy and reduce chemicals consumption in a conversion process of spent Li1-xCoO2 (LCO) → new LiNi0.80Co0.15Al0.05O2 (NCA) cathode. Mechanochemical activation is employed to achieve moderate valence reduction of transition metal oxides (Co3+→Co2+,3+) and efficient oxidation of current collector fragments (Al0→Al3+, Cu0→Cu1+,2+), and then due to stored internal energy from ball-milling, the leaching rates of Li, Co, Al, and Cu in the ≤4 mm crushed products uniformly approach 100% with just weak acetic acid. Instead of corrosive precipitation reagents, larger Al fragments (≥4 mm) are used to control the oxidation/reduction potential (ORP) in the aqueous leachate and induce the targeted removal of impurity ions (Cu, Fe). After the upcycling of NCA precursor solution to NCA cathode powders, we demonstrate excellent electrochemical performance of the regenerated NCA cathode and improved environmental impact. Through life cycle assessments, the profit margin of this green upcycling path reaches about 18%, while reducing greenhouse gas emissions by 45%.

Sulfion oxidation assisting self-powered hydrogen production system based on efficient catalysts from spent lithium-ion batteries.

Converting spent lithium-ion batteries (LIBs) and industrial wastewater into high-value-added substances by advanced electrocatalytic technology is important for sustainable energy development and environmental protection. Here, we propose a self-powered system using a home-made sulfide fuel cell (SFC) to power a two-electrode electrocatalytic sulfion oxidation reaction (SOR)-assisted hydrogen (H2) production electrolyzer (ESHPE), in which the sulfion-containing wastewater is used as the liquid fuel to produce clean water, sulfur, and hydrogen. The catalysts for the self-powered system are mainly prepared from spent LIBs to reduce the cost, such as the bifunctional Co9S8 catalyst was prepared from spent LiCoO2 for SOR and hydrogen evolution reaction (HER). The Fe-N-P codoped coral-like carbon nanotube arrays encapsulated Fe2P (C-ZIF/sLFP) catalyst was prepared from spent LiFePO4 for oxygen reduction reaction. The Co9S8 catalyst shows excellent catalytic activities in both SOR and HER, evidenced by the low cell voltage of 0.426 V at 20 mA cm-2 in ESHPE. The SFC with Co9S8 as anode and C-ZIF/sLFP as cathode exhibits an open-circuit voltage of 0.69 V and long discharge stability for 300 h at 20 mA cm-2. By integrating the SFC and ESHPE, the self-powered system delivers an impressive hydrogen production rate of 0.44 mL cm-2 min-1. This work constructs a self-powered system with high-performance catalysts prepared from spent LIBs to transform sulfion-containing wastewater into purified water and prepare hydrogen, which is promising to achieve high economic efficiency, environmental remediation, and sustainable development.

Assembled MXene-Liquid Metal Cages on Silicon Microparticles as Self-Healing Battery Anodes.

In pursuit of higher energy density in lithium-ion batteries, silicon (Si) has been recognized as a promising candidate to replace commercial graphite due to its high theoretical capacity. However, the pulverization issue of Si microparticles during lithiation/delithiation results in electrical contact loss and increased side reactions, significantly limiting its practical applications. Herein, we propose to utilize liquid metal (LM) particles as the bridging agent, which assemble conductive MXene (Ti3C2Tx) sheets via coordination chemistry, forming cage-like structures encapsulating mSi particles as self-healing high-energy anodes. Due to the integration of robust Ti3C2Tx sheets and deformable LM particles as conductive buffering cages, simultaneously high-rate capability and cyclability can be realized. Post-mortem analysis revealed the cage structural integrity and the maintained electrical percolating network after cycling. This work introduces an effective approach to accommodate structural change via a resilient encapsulating cage and offers useful interface design considerations for versatile battery electrodes.

New Insight into Bulk Structural Degradation of High-Voltage LiCoO2 at 4.55 V.

The aggravated mechanical and structural degradation of layered oxide cathode materials upon high-voltage charging invariably causes fast capacity fading, but the underlying degradation mechanisms remain elusive. Here we report a new type of mechanical degradation through the formation of a kink band in a Mg and Ti co-doped LiCoO2 cathode charged to 4.55 V (vs Li/Li+). The local stress accommodated by the kink band can impede crack propagation, improving the structural integrity in a highly delithiated state. Additionally, machine-learning-aided atomic-resolution imaging reveals that the formation of kink bands is often accompanied by the transformation from the O3 to O1 phase, which is energetically favorable as demonstrated by first-principles calculations. Our results provide new insights into the mechanical degradation mechanism of high-voltage LiCoO2 and the coupling between electrochemically triggered mechanical failures and structural transition, which may provide valuable guidance for enhancing the electrochemical performance of high-voltage layered oxide cathode materials for lithium-ion batteries.

Fast-Charging, Binder-Free Lithium Battery Cathodes Enabled via Multidimensional Conductive Networks.

To meet the growing demands in both energy and power densities of lithium ion batteries, electrode structures must be capable of facile electron and ion transport while minimizing the content of electrochemically inactive components. Herein, binder-free LiFePO4 (LFP) cathodes are fabricated with a multidimensional conductive architecture that allows for fast-charging capability, reaching a specific capacity of 94 mAh g-1 at 4 C. Such multidimensional networks consist of active material particles wrapped by 1D single-walled carbon nanotubes (CNTs) and bound together using 2D MXene (Ti3C2Tx) nanosheets. The CNTs form a porous coating layer and improve local electron transport across the LFP surface, while the Ti3C2Tx nanosheets provide simultaneously high electrode integrity and conductive pathways through the bulk of the electrode. This work highlights the ability of multidimensional conductive fillers to realize simultaneously superior electrochemical and mechanical properties, providing useful insights into future fast-charging electrode designs for scalable electrochemical systems.

A Gradient Composite Structure Enables a Stable Microsized Silicon Suboxide-Based Anode for a High-Performance Lithium-Ion Battery.

The practical application of microsized anodes is hindered by severe volume changes and fast capacity fading. Herein, we propose a gradient composite strategy and fabricate a silicon suboxide-based composite anode (d-SiO@SiOx/C@C) consisting of a disproportionated microsized SiO inner core, a homogeneous composite SiOx/C interlayer (x ≈ 1.5), and a highly graphitized carbon outer layer. The robust SiOx/C interlayer can realize a gradient abatement of stress and simultaneously connect the inner SiO core and carbon outer layer through covalent bonds. As a result, d-SiO@SiOx/C@C delivers a specific capacity of 1023 mAh/g after 300 cycles at 1 A/g with a retention of >90% and an average Coulombic efficiency of >99.7%. A full cell assembled with a LiNi0.8Co0.15Al0.05O2 cathode displays a remarkable specific energy density of 569 Wh/kg based on total active materials as well as excellent cycling stability. Our strategy provides a promising alternative for designing structurally and electrochemically stable microsized anodes with high capacity.

A novel closed-loop biotechnology for recovery of cobalt from a lithium-ion battery active cathode material.

In recent years, the demand for lithium-ion batteries (LIBs) has been increasing rapidly. Conventional recycling strategies (based on pyro- and hydrometallurgy) are damaging for the environment and more sustainable methods need to be developed. Bioleaching is a promising environmentally friendly approach that uses microorganisms to solubilize metals. However, a bioleaching-based technology has not yet been applied to recover valuable metals from waste LIBs on an industrial scale. A series of experiments was performed to improve metal recovery rates from an active cathode material (LiCoO2; LCO). (i) Direct bioleaching of ≤0.5 % LCO with two prokaryotic acidophilic consortia achieved >80 % Co and 90 % Li extraction. Significantly lower metal recovery rates were obtained at 30 °C than at 45 °C. (ii) In contrast, during direct bioleaching of 3 % LCO with consortia adapted to elevated LCO levels, the 30 °C consortium performed significantly better than the 45 °C consortium, solubilizing 73 and 93 % of the Co and Li, respectively, during one-step bioleaching, and 83 and 99 % of the Co and Li, respectively, during a two-step process. (iii) The adapted 30°C consortium was used for indirect leaching in a low-waste closed-loop system (with 10 % LCO). The process involved generation of sulfuric acid in an acid-generating bioreactor (AGB), 2-3 week leaching of LCO with the biogenic acid (pH 0.9), selective precipitation of Co as hydroxide, and recirculation of the metal-free liquor back into the AGB. In total, 58.2 % Co and 100 % Li were solubilized in seven phases, and >99.9 % of the dissolved Co was recovered after each phase as a high-purity Co hydroxide. Additionally, Co nanoparticles were generated from the obtained Co-rich leachates, using Desulfovibrio alaskensis, and Co electrowinning was optimized as an alternative recovery technique, yielding high recovery rates (91.1 and 73.6% on carbon felt and roughened steel, respectively) from bioleachates that contained significantly lower Co concentrations than industrial hydrometallurgical liquors. The closed-loop system was highly dominated by the mixotrophic archaeon Ferroplasma and sulfur-oxidizing bacteria Acidithiobacillus caldus and Acidithiobacillus thiooxidans. The developed system achieved high metal recovery rates and provided high-purity solid products suitable for a battery supply chain, while minimizing waste production and the inhibitory effects of elevated concentrations of dissolved metals on the leaching prokaryotes. The system is suitable for scale-up applications and has the potential to be adapted to different battery chemistries.

Effect of Oxidative Synthesis Conditions on the Performance of Single-Crystalline LiMn2- x Mx O4 (M = Al, Fe, and Ni) Spinel Cathodes in Lithium-Ion Batteries.

LiMn2 O4 (LMO) spinel cathode materials attract much interest due to the low price of manganese and high power density for lithium-ion batteries. However, the LMO cathodes suffer from the Mn dissolution problem at particle surfaces, which accelerates capacity fade. Herein, the authors report that the oxidative synthesis condition is a key factor in the cell performance of single-crystalline LiMn2- x Mx O4 (0.03 ≤ x ≤ 0.1, M = Al, Fe, and Ni) cathode materials prepared at 1000 °C. The use of oxygen flow during the spinel-phase formation minimizes the presence of oxygen vacancies generated at 1000 °C, thereby yielding a stoichiometrically doped LMO product; otherwise, the spinel cathode prepared in atmospheric air readily loses capacity due to the oxygen vacancies in the structure. As a way of circumventing the use of oxygen flow, a one-pot, two-step heating in air at 1000 °C and subsequently at 600 °C is used to yield the stoichiometric LMO product. The lithiation heating at 1000-600 °C resulted in a significant improvement in the cycling stability of the prepared LMO cathode in graphite-based full cells. This study on oxidative synthesis conditions also confirms the advantage of minimizing the surface area of the cathode particles.

Yolk-Shell Gradient-Structured SiOx Anodes Derived from Periodic Mesoporous Organosilicas Enable High-Performance Lithium-Ion Batteries.

Gradient-structured materials hold great promise in the areas of batteries and electrocatalysis. Here, yolk-shell gradient-structured SiOx -based anode (YSG-SiOx /C@C) derived from periodic mesoporous organosilica spheres (PMOs) through a selective etching method is reported. Capitalizing on the poor hydrothermal stability of inorganic silica in organic-inorganic hybrid silica spheres, the inorganic silica component in the hybrid spheres is selectively etched to obtain yolk-shell-structured PMOs. Subsequently, the yolk-shell PMOs are coated with carbon to fabricate YSG-SiOx /C@C. YSG-SiOx /C@C is comprised of a core with uniform distribution of SiOx and carbon at the atomic scale, a middle void layer, and outer layers of SiOx and amorphous carbon. This unique gradient structure and composition from inside to outside not only enhances the electrical conductivity of the SiOx anode and reduces the side reactions, but also reserves void space for the expansion of SiOx , thereby effectively mitigating the stress caused by volumetric effect. As a result, YSG-SiOx /C@C exhibits exceptional cycling stability and rate capability. Specifically, YSG-SiOx /C@C maintains a specific capacity of 627 mAh g-1 after 400 cycles at 0.5 A g-1 , and remains stable even after 550 cycles at current density of 2 A g-1 , achieving a specific capacity of 519 mAh g-1 .

Interface Engineering Enables Wide-Temperature Li-Ion Storage in Commercial Silicon-Based Anodes.

Silicon-based materials have been considered potential anode materials for next-generation lithium-ion batteries based on their high theoretical capacity and low working voltage. However, side reactions at the Si/electrolyte interface bring annoying issues like low Coulombic efficiency, sluggish ionic transport, and inferior temperature compatibility. In this work, the surface Al2 O3 coating layer is proposed as an artificial solid electrolyte interphase (SEI), which can serve as a physical barrier against the invasion of byproducts like HF(Hydrogen Fluoride) from the decomposition of electrolyte, and acts as a fast Li-ion transport pathway. Besides, the intrinsically high mechanical strength can effectively inhibit the volume expansion of the silicon particles, thus promoting the cyclability. The as-assembled battery cell with the Al2 O3 -coated Si-C anode exhibits a high initial Coulombic efficiency of 80% at RT and a capacity retention ratio up to ≈81.9% after 100 cycles, which is much higher than that of the pristine Si-C anode (≈74.8%). Besides, the expansion rate can also be decreased from 103% to 50%. Moreover, the Al2 O3 -coated Si-C anode also extends the working temperature from room temperature to 0 °C-60 °C. Overall, this work provides an efficient strategy for regulating the interface reactions of Si-based anode and pushes forward the practical applications at real conditions.

Dual-Modified Electrospun Fiber Membrane as Separator with Excellent Safety Performance and High Operating Temperature for Lithium-Ion Batteries.

Polyacrylonitrile/Boric acid/Melamine/the delaminated BN nanosheets electrospun fiber membrane (PB3N1BN) with excellent mechanical property, high thermal stability, superior flame-retardant performance, and good wettability are fabricated by electrospinning PAN/DMF/H3BO3/C3H6N6/ the delaminated BN nanosheets (BNNSs) homogeneous viscous suspension and followed by a heating treatment. BNNSs are obtained by delaminating the bulk h-BN in isopropyl alcohol (IPA) with an assistance of Polyvinylpyrrolidone (PVP). Benefiting from the cross-linked pore structure and high-temperature stability of BNNSs, PB3N1BN electrospun fiber membrane delivers high thermal dimensional stability (almost no size contraction at 200 °C), excellent mechanical property (19.1 MPa), good electrolyte wettability (contact angle about 0°), and excellent flame retardancy (minimum total heat release of 3.2 MJ m-2). Moreover, the assembled LiFePO4/PB3N1BN/Li asymmetrical battery using LiFePO4 as the cathode and Li as the anode has a high capacity (169 mAh g-1 at 0.5 C), exceptional rate capability (129 mAh g-1 at 5 C), the prominent cycling stability without obvious decay after 400 cycles, and a good discharge capacity of 152 mAh g-1 at a high temperature of 80 °C. This work offers a new structural design strategy toward separators with excellent mechanical performance, good wettability, and high thermal stability for lithium-ion batteries.

Tailored Yolk-Shell Design to Silicon Microparticles via Scalable and Template-Free Synthesis for Superior Lithium Storage.

Micrometer-sized Si particles are beneficial to practical lithium-ion batteries in regard to low cost and high volumetric energy density in comparison with nanostructured Si anodes. However, both the issues of electrical contact loss and overgrowth of solid electrolyte interface for microscale Si induced by colossal volume change still remain to be addressed. Herein, a scalable and template-free method is introduced to fabricate yolk-shell structured Si anode from commercially available Si microparticles. The void is created via a one-step alkali etching process with the remaining silicon core as the yolk, and a double-walled shell is formed from simultaneous in situ growth of the conformal native oxide layer and subsequent carbon coating. In this configuration, the well-defined void spaces allow the Si core to expand without compromising structural integrity, while the double-walled shell acts as a static capsule to confine silicon fragments despite likely particle fracture. Therefore, electrical connectivity is maintained on both the particle and electrode level during deep galvanostatic cycling, and the solid-electrolyte interface is stabilized on the shell surface. Owing to the benefits of tailored design, excellent cycling stability (capacity retention of 95% after 100 cycles) and high coulombic efficiency (99.5%) are realized in a practical full-cell demonstration.

Grafting a Polymer Coating Layer onto Li1.2 Ni0.13 Co0.13 Mn0.54 O2 Cathode by Benzene Diazonium Salts to Facilitate the Cycling Performance and High-Voltage Stability.

Li-rich Mn-based cathodes have been regarded as promising cathodes for lithium-ion batteries because of their low cost of raw materials (compared with Ni-rich layer structure and LiCoO2 cathodes) and high energy density. However, for practical application, it needs to solve the great drawbacks of Li-rich Mn-based cathodes like capacity degradation and operating voltage decline. Herein, an effective method of surface modification by benzene diazonium salts to build a stable interface between the cathode materials and the electrolyte is proposed. The cathodes after modification exhibit excellent cycling performance (the retention of specific capacity is 84.2% after 350 cycles at the current density of 1 C), which is mainly attributed to the better stability of the structure and interface. This work provides a novel way to design the coating layer with benzene diazonium salts for enhancing the structural stability under high voltage condition during cycling.

Interphase Engineering Enhanced Electro-chemical Stability of Prelithiated Anode.

Prelithiation is an essential technology to compensate for the initial lithium loss of lithium-ion batteries due to the formation of solid electrolyte interphase (SEI) and irreversible structure change. However, the prelithiated materials/electrodes become more reactive with air and electrolyte resulting in unwanted side reactions and contaminations, which makes it difficult for the practical application of prelithiation technology. To address this problem, herein, interphase engineering through a simple solution treatment after chemical prelithiation is proposed to protect the prelithiated electrode. The used solutions are carefully selected, and the composition and nanostructure of the as-formed artificial SEIs are revealed by cryogenic electron microscopy and X-ray photoelectron spectroscopy. The electrochemical evaluation demonstrates the unique merits of this artificial SEI, especially for the fluorinated interphase, which not only enhances the interfacial ion transport but also increases the tolerance of the prelithiated electrode to the air. The treated graphite electrode shows an initial Coulombic efficiency of 129.4%, a high capacity of 170 mAh g-1 at 3 C, and negligible capacity decay after 200 cycles at 1 C. These findings not only provide a facile, universal, and controllable method to construct an artificial SEI but also enlighten the upgrade of battery fabrication and the alternative use of advanced electrolytes.

Tuning the Cathode-Electrolyte Interphase Chemistry with Multifunctional Additive for High-Voltage Li-Ion Batteries.

The utilization of layered oxides as cathode materials has significantly contributed to the advancement of the lithium-ion batteries (LIBs) with high energy density and reliability. However, the structural and interfacial instability triggered by side reactions when charged to high voltage has plagued their practical applications. Here, this work reports a novel multifunctional additive, id est, 7-Anilino-3-diethylamino-6-methyl fluoran (ADMF), which exhibits unique characteristics such as preferential adsorption, oxygen scavenging, and electropolymerization protection for high-voltage cathodes. The ADMF demonstrates the capability to ameliorate the growth of cathode-electrolyte interphase (CEI), effectively diminishing the dissolution of transition metal (TM) ions, reducing the interface impedance, and facilitating the Li+ transport. As a result, ADMF additive with side reaction-blocking ability significantly enhances the cycling stability of MCMB||NCM811 full-cells at 4.4 V and MCMB||LCO full-cells at 4.55 V, as evidenced by the 80% retention over 600 cycles and 87% retention after 750 cycles, respectively. These findings highlight the potential of the additive design strategy to modulate the CEI chemistry, representing a new paradigm with profound implications for the development of next-generation high-voltage LIBs.

Reinforcement of Positive Electrode-Electrolyte Interface without Using Electrolyte Additives Through Thermoelectrochemical Oxidation of LiPF6 for Lithium Secondary Batteries.

Owing to the limited electrochemical stability window of carbonate electrolytes, the initial formation of a solid electrolyte interphase and surface film on the negative and positive electrode surfaces by the decomposition of the electrolyte component is inevitable for the operation of lithium secondary batteries. The deposited film on the surface of the active material is vital for reducing further electrochemical side reactions at the surface; hence, the manipulation of this formation process is necessary for the appropriate operation of the assembled battery system. In this study, the thermal decomposition of LiPF6 salt is used as a surface passivation agent, which is autocatalytically formed during high-temperature storage. The thermally formed difluorophosphoric acid is subsequently oxidized on the partially charged high-Ni positive electrode surface, which improves the cycleability of lithium metal cells via phosphorus- and fluorine-based surface film formation. Moreover, the improvement in the high-temperature cycleability is demonstrated by controlling the formation process in the lithium-ion pouch cell with a short period of high-temperature storage before battery usage.