In Situ Construction of a Multifunctional Interphase Enabling Continuous Capture of Unstable Lattice Oxygen Under Ultrahigh Voltages.

The use of nickel-rich layered materials as cathodes can boost the energy density of lithium batteries. However, developing a safe and long-term stable nickel-rich layered cathode is challenging primarily due to the release of lattice oxygen from the cathode during cycling, especially at high voltages, which will cause a series of adverse effects, leading to battery failure and thermal runaway. Surface coating is often considered effective in capturing active oxygen species; however, its process is rather complicated, and it is difficult to maintain intact on the cathode with large volume changes during cycling. Here, we propose an in situ construction of a multifunctional cathode/electrolyte interphase (CEI), which is easy to prepare, repairable, and, most importantly, capable of continuously capturing active oxygen species during the entire life span. This unique protective mechanism notably improves the cycling stability of Li||LiNi0.8Co0.1Mn0.1O2 (NCM811) cells at rigorous working conditions, including ultrahigh voltage (4.8 V), high temperature (60 °C), and fast charging (10 C). An industrial 1 A h graphite||NCM811 pouch cell achieved stable operation of 600 cycles with a capacity retention of 79.6% at 4.4 V, exhibiting great potential for practical use. This work provides insightful guidance for constructing a multifunctional CEI to bypass limitations associated with high-voltage operations of nickel-rich layered cathodes.

A locally solvent-tethered polymer electrolyte for long-life lithium metal batteries.

Solid polymer electrolytes exhibit enhanced Li+ conductivity when plasticized with highly dielectric solvents such as N,N-dimethylformamide (DMF). However, the application of DMF-containing electrolytes in solid-state batteries is hindered by poor cycle life caused by continuous DMF degradation at the anode surface and the resulting unstable solid-electrolyte interphase. Here we report a composite polymer electrolyte with a rationally designed Hofmann-DMF coordination complex to address this issue. DMF is engineered on Hofmann frameworks as tethered ligands to construct a locally DMF-rich interface which promotes Li+ conduction through a ligand-assisted transport mechanism. A high ionic conductivity of 6.5 × 10-4 S cm-1 is achieved at room temperature. We demonstrate that the composite electrolyte effectively reduces the free shuttling and subsequent decomposition of DMF. The locally solvent-tethered electrolyte cycles stably for over 6000 h at 0.1 mA cm-2 in Li | |Li symmetric cell. When paired with sulfurized polyacrylonitrile cathodes, the full cell exhibits a prolonged cycle life of 1000 cycles at 1 C. This work will facilitate the development of practical polymer-based electrolytes with high ionic conductivity and long cycle life.

Fast Li Replenishment Channels-Assisted Recycling of Degraded Layered Cathodes with Enhanced Cycling Performance and Thermal Stability.

The direct recycling of cathode materials in lithium-ion batteries is important for environmental protection and resource conservation. The key regeneration processes are composition replenishment and atom rearrangement, both of which depend on the migration and diffusion of atoms. However, for the direct recycling of degraded LiNi0.5Co0.2Mn0.3O2 (D-NCM523) cathode, the irreversible phase transitions that accumulate during the long-term cycles block the Li diffusion channels with a high diffusion energy barrier, making it difficult to fully repair the layered structure and resulting in rapid capacity decay. To address the challenge, fast Li replenishment channels are rebuilt to regulate the surface phase and effectively assist the regeneration process with a reduced energy barrier. This method reduces the amount of Li supplement by >75% and shortens the sintering time (only 2 h) to fully regenerate D-NCM523, compared to general direct recycling methods. The regenerated NCM523 (LCMB-NCM523) exhibits a satisfactory repaired specific capacity of 160 mAh g-1 and excellent cycling stability, retaining 78% of its capacity after 300 cycles. In addition, LCMB-NCM523 is recycled with improved thermal decomposition peak temperature and enables 200 cycles even at 60 °C, greatly improving safety. This work proposes a promising way for the large-scale direct regeneration of layered cathodes.

Degradation Mechanisms of Electrodes Promotes Direct Regeneration of Spent Li-Ion Batteries: A Review.

The rapid growth of electric vehicle use is expected to cause a significant environmental problem in the next few years due to the large number of spent lithium-ion batteries (LIBs). Recycling spent LIBs will not only alleviate the environmental problems but also address the challenge of limited natural resources shortages. While several hydro- and pyrometallurgical processes are developed for recycling different components of spent batteries, direct regeneration presents clear environmental, and economic advantages. The principle of the direct regeneration approach is restoring the electrochemical performance by healing the defective structure of the spent materials. Thus, the development of direct regeneration technology largely depends on the formation mechanism of defects in spent LIBs. This review systematically details the degradation mechanisms and types of defects found in diverse cathode materials, graphite anodes, and current collectors during the battery's lifecycle. Building on this understanding, principles and methodologies for directly rejuvenating materials within spent LIBs are outlined. Also the main challenges and solutions for the large-scale direct regeneration of spent LIBs are proposed. Furthermore, this review aims to pave the way for the direct regeneration of materials in discarded lithium-ion batteries by offering a theoretical foundation and practical guidance.

Self-Assembly of Ultrathin, Ultrastrong Layered Membranes by Protic Solvent Penetration.

Flexible membranes with ultrathin thickness and excellent mechanical properties have shown great potential for broad uses in solid polymer electrolytes (SPEs), on-skin electronics, etc. However, an ultrathin membrane (<5 µm) is rarely reported in the above applications due to the inherent trade-off between thickness and antifailure ability. We discover a protic solvent penetration strategy to prepare ultrathin, ultrastrong layered films through a continuous interweaving of aramid nanofibers (ANFs) with the assistance of simultaneous protonation and penetration of a protic solvent. The thickness of a pure ANF film can be controlled below 5 µm, with a tensile strength of 556.6 MPa, allowing us to produce the thinnest SPE (3.4 µm). The resultant SPEs enable Li-S batteries to cycle over a thousand times at a high rate of 1C due to the small ionic impedance conferred by the ultrathin characteristic and regulated ionic transportation. Besides, a high loading of the sulfur cathode (4 mg cm-2) with good sulfur utilization was achieved at a mild temperature (35 °C), which is difficult to realize in previously reported solid-state Li-S batteries. Through a simple laminating process at the wet state, the thicker film (tens of micrometers) obtained exhibits mechanical properties comparable to those of thin films and possesses the capability to withstand high-velocity projectile impacts, indicating that our technique features a high degree of thickness controllability. We believe that it can serve as a valuable tool to assemble nanomaterials into ultrathin, ultrastrong membranes for various applications.

Unraveling the Coupling Effect between Cathode and Anode toward Practical Lithium-Sulfur Batteries.

The localized reaction heterogeneity of the sulfur cathode and the uneven Li deposition on the Li anode are intractable issues for lithium-sulfur (Li-S) batteries under practical operation. Despite impressive progress in separately optimizing the sulfur cathode or Li anode, a comprehensive understanding of the highly coupled relationship between the cathode and anode is still lacking. In this work, inspired by the Butler-Volmer equation, a binary descriptor (IBD ) assisting the rational structural design of sulfur cathode by simultaneously considering the mass-transport index (Imass ) and the charge-transfer index (Icharge ) is identified, and subsequently the relationship between IBD and the morphological evolution of Li anode is established. Guided by the IBD , a scalable electrode providing interpenetrated flow channels for efficient mass/charge transfer, full utilization of active sulfur, and mechanically elastic support for aggressive electrochemical reactions under practical conditions is reported. These characteristics induce a homogenous distribution of local current densities and reduced reaction heterogeneity on both sides of the cathode and anode. Impressive energy density of 318 Wh kg-1 and 473 Wh L-1 in an Ah-level pouch cell can be achieved by the design concept. This work offers a promising paradigm for unlocking the interaction between cathode and anode and designing high-energy practical Li-S batteries.

Regulating the Spin State Configuration in Bimetallic Phosphorus Trisulfides for Promoting Sulfur Redox Kinetics.

Lithium-sulfur (Li-S) batteries suffer from sluggish kinetics due to the poor conductivity of sulfur cathodes and polysulfide shutting. Current studies on sulfur redox catalysis mainly focus on the adsorption and catalytic conversion of lithium polysulfides but ignore the modulation of the electronic structure of the catalysts which involves spin-related charge transfer and orbital interactions. In this work, bimetallic phosphorus trisulfides embedded in Prussian blue analogue-derived nitrogen-doped hollow carbon nanocubes (FeCoPS3/NCs) were elaborately synthesized as a host to reveal the relationship between the catalytic activity and the spin state configuration for Li-S batteries. Orbital spin splitting in FeCoPS3 drives the electronic structure transition from low-spin to high-spin states, generating more unpaired electrons on the 3d orbit. Specifically, the nondegenerate orbitals involved in the high-spin configuration of FeCoPS3 result in the upshift of energy levels, generating more active electronic states. Such tailored electronic structure increases the charge transfer, influences the d-band center, and further modifies the adsorption energy with lithium polysulfides and the potential reaction pathways. Consequently, the cell with FeCoPS3/NC host exhibits an ultralow capacity decay of 0.037% per cycle over 1000 cycles. This study proposed a general strategy for sculpting geometric configurations to enable spin and orbital topology regulation in Li-S battery catalysts.

A Semisolvated Sole-Solvent Electrolyte for High-Voltage Lithium Metal Batteries.

Lithium metal batteries (LMBs) coupled with a high-voltage Ni-rich cathode are promising for meeting the increasing demand for high energy density. However, aggressive electrode chemistry imposes ultimate requirements on the electrolytes used. Among the various optimized electrolytes investigated, localized high-concentration electrolytes (LHCEs) have excellent reversibility against a lithium metal anode. However, because they consist of thermally and electrochemically unstable solvents, they have inferior stability at elevated temperatures and high cutoff voltages. Here we report a semisolvated sole-solvent electrolyte to construct a typical LHCE solvation structure but with significantly improved stability using one bifunctional solvent. The designed electrolyte exhibits exceptional stability against both electrodes with suppressed lithium dendrite growth, phase transition, microcracking, and transition metal dissolution. A Li||Ni0.8Co0.1Mn0.1O2 cell with this electrolyte operates stably over a wide temperature range from -20 to 60 °C and has a high capacity retention of 95.6% after the 100th cycle at 4.7 V, and ∼80% of the initial capacity is retained even after 180 cycles. This new electrolyte indicates a new path toward future electrolyte engineering and safe high-voltage LMBs.

Uncoordinated chemistry enables highly conductive and stable electrolyte/filler interfaces for solid-state lithium-sulfur batteries.

Composite-polymer-electrolytes (CPEs) embedded with advanced filler materials offer great promise for fast and preferential Li+ conduction. The filler surface chemistry determines the interaction with electrolyte molecules and thus critically regulates the Li+ behaviors at the interfaces. Herein, we probe into the role of electrolyte/filler interfaces (EFI) in CPEs and promote Li+ conduction by introducing an unsaturated coordination Prussian blue analog (UCPBA) filler. Combining scanning transmission X-ray microscope stack imaging studies and first-principle calculations, fast Li+ conduction is revealed only achievable at a chemically stable EFI, which can be established by the unsaturated Co-O coordination in UCPBA to circumvent the side reactions. Moreover, the as-exposed Lewis-acid metal centers in UCPBA efficiently attract the Lewis-base anions of Li salts, which facilitates the Li+ disassociation and enhances its transference number (tLi+). Attributed to these superiorities, the obtained CPEs realize high room-temperature ionic conductivity up to 0.36 mS cm-1 and tLi+ of 0.6, enabling an excellent cyclability of lithium metal electrodes over 4,000 h as well as remarkable capacity retention of 97.6% over 180 cycles at 0.5 C for solid-state lithium-sulfur batteries. This work highlights the crucial role of EFI chemistry in developing highly conductive CPEs and high-performance solid-state batteries.

Topotactic Transformation of Surface Structure Enabling Direct Regeneration of Spent Lithium-Ion Battery Cathodes.

Recycling spent lithium-ion batteries (LIBs) has become an urgent task to address the issues of resource shortage and potential environmental pollution. However, direct recycling of the spent LiNi0.5Co0.2Mn0.3O2 (NCM523) cathode is challenging because the strong electrostatic repulsion from a transition metal octahedron in the lithium layer provided by the rock salt/spinel phase that is formed on the surface of the cycled cathode severely disrupts Li+ transport, which restrains lithium replenishment during regeneration, resulting in the regenerated cathode with inferior capacity and cycling performance. Here, we propose the topotactic transformation of the stable rock salt/spinel phase into Ni0.5Co0.2Mn0.3(OH)2 and then back to the NCM523 cathode. As a result, a topotactic relithiation reaction with low migration barriers occurs with facile Li+ transport in a channel (from one octahedral site to another, passing through a tetrahedral intermediate) with weakened electrostatic repulsion, which greatly improves lithium replenishment during regeneration. In addition, the proposed method can be extended to repair spent NCM523 black mass, spent LiNi0.6Co0.2Mn0.2O2, and spent LiCoO2 cathodes, whose electrochemical performance after regeneration is comparable to that of the commercial pristine cathodes. This work demonstrates a fast topotactic relithiation process during regeneration by modifying Li+ transport channels, providing a unique perspective on the regeneration of spent LIB cathodes.

Ultrahigh-Voltage LiCoO2 at 4.7 V by Interface Stabilization and Band Structure Modification.

Lithium cobalt oxide (LCO) is widely used in Li-ion batteries due to its high volumetric energy density, which is generally charged to 4.3 V. Lifting the cut-off voltage of LCO from 4.3 V to 4.7 V will increase the specific capacity from 150 to 230 mAh g-1 with a significant improvement of 53%. However, LCO suffers serious problems of H1-3/O1 phase transformation, unstable interface between cathode and electrolyte, and irreversible oxygen redox reaction at 4.7 V. Herein, interface stabilization and band structure modification are proposed to strengthen the crystal structure of LCO for stable cycling of LCO at an ultrahigh voltage of 4.7 V. Gradient distribution of magnesium and uniform doping of nickel in Li layers inhibit the harmful phase transitions of LCO, while uniform LiMgx Ni1- x PO4 coating stabilizes the LCO-electrolyte interface during cycles. Moreover, the modified band structure improves the oxygen redox reaction reversibility and electrochemical performance of the modified LCO. As a result, the modified LCO has a high capacity retention of 78% after 200 cycles at 4.7 V in the half cell and 63% after 500 cycles at 4.6 V in the full cell. This work makes the capacity of LCO one step closer to its theoretical specific capacity.

Stable Operation of Lithium Metal Batteries with Aggressive Cathode Chemistries at 4.9†V.

High-voltage lithium metal batteries (LMBs) pose severe challenges for the matching of electrolytes with aggressive electrodes, especially at low temperatures. Here, we report a rational modification of the Li+ solvation structure to extend the voltage and temperature operating ranges of conventional electrolytes. Ion-ion and ion-dipole interactions as well as the electrochemical window of solvents were tailored to improve oxidation stability and de-solvation kinetics of the electrolyte. Meanwhile, robust and elastic B and F-rich interphases are formed on both electrodes. Such optimization enables Li||LiNi0.5 Mn1.5 O4 cells (90.2 % retention after 400 cycles) and Li||LiNi0.6 Co0.2 Mn0.2 O2 (NCM622) cells (74.0 % retention after 200 cycles) to cycle stably at an ultra-high voltage of 4.9 V. Moreover, NCM622 cells deliver a considerable capacity of 143.5 mAh g-1 at -20 °C, showing great potential for practical uses. The proposed strategy sheds light on further optimization for high-voltage LMBs.

Rational Design of Flexible Zn-Based Batteries for Wearable Electronic Devices.

The advent of 5G and the Internet of Things has spawned a demand for wearable electronic devices. However, the lack of a suitable flexible energy storage system has become the "Achilles' Heel" of wearable electronic devices. Additional problems during the transformation of the battery structure from conventional to flexible also present a severe challenge to the battery design. Flexible Zn-based batteries, including Zn-ion batteries and Zn-air batteries, have long been considered promising candidates due to their high safety, eco-efficiency, substantial reserve, and low cost. In the past decade, researchers have come up with elaborate designs for each portion of flexible Zn-based batteries to improve the ionic conductivities, mechanical properties, environment adaptabilities, and scalable productions. It would be helpful to summarize the reported strategies and compare their pros and cons to facilitate further research toward the commercialization of flexible Zn-based batteries. In this review, the current progress in developing flexible Zn-based batteries is comprehensively reviewed, including their electrolytes, cathodes, and anodes, and discussed in terms of their synthesis, characterization, and performance validation. By clarifying the challenges in flexible Zn-based battery design, we summarize the methodology from previous investigations and propose challenges for future development. In the end, a research paradigm of Zn-based batteries is summarized to fit the burgeoning requirement of wearable electronic devices in an iterative process, which will benefit the future development of Zn-based batteries.

Long-Life Regenerated LiFePO4 from Spent Cathode by Elevating the d-Band Center of Fe.

A large amount of spent LiFePO4 (LFP) has been produced in recent years because it is one of the most widely used cathode materials for electric vehicles. The traditional hydrometallurgical and pyrometallurgical recycling methods are doubted because of the economic and environmental benefits; the direct regeneration method is considered a promising way to recycle spent LFP. However, the performance of regenerated LFP by direct recycling is not ideal due to the migration of Fe ions during cycling and irreversible phase transition caused by sluggish Li+ diffusion. The key to addressing the challenge is to immobilize Fe atoms in the lattice and improve the Li+ migration capability during cycling. In this work, spent LFP is regenerated by using environmentally friendly ethanol, and its cycling stability is promoted by elevating the d-band center of Fe atoms via construction of a heterogeneous interface between LFP and nitrogen-doped carbon. The FeO bonding is strengthened and the migration of Fe ions during cycling is suppressed due to the elevated d-band center. The Li+ diffusion kinetics in the regenerated LFP are improved, leading to an excellent reversibility of the phase transition. Therefore,  the regenerated LFP exhibits an ultrastable cycling performance at a high rate of 10 C with ≈80% capacity retention after 1000 cycles.

A Review on Regulating Li+ Solvation Structures in Carbonate Electrolytes for Lithium Metal Batteries.

Lithium metal batteries (LMBs) are considered promising candidates for next-generation battery systems due to their high energy density. However, commercialized carbonate electrolytes cannot be used in LMBs due to their poor compatibility with lithium metal anodes. While increasing cut-off voltage is an effective way to boost the energy density of LMBs, conventional ethylene carbonate-based electrolytes undergo a number of side reactions at high voltages. It is therefore critical to upgrade conventional carbonate electrolytes, the performance of which is highly influenced by the solvation structure of lithium ions (Li+ ). This review provides a comprehensive overview of the strategies to regulate the solvation structure of Li+ in carbonate electrolytes for LMBs by better understanding the science behind the Li+ solvation structure and Li+ behavior. Different strategies are systematically compared to help select better electrolytes for specific applications. The remaining scientific and technical problems are pointed out, and directions for future research on carbonate electrolytes for LMBs are proposed.

Suppressed Lattice Oxygen Release via Ni/Mn Doping from Spent LiNi0.5Mn0.3Co0.2O2 toward High-Energy Layered-Oxide Cathodes.

LiCoO2 has suffered from poor stability under high voltage as a result of insufficient Co-O bonding that causes lattice oxygen release and lattice distortions. Herein, we fabricated a high-voltage LiCoO2 at 4.6 V by doping with Ni/Mn atoms, which are obtained from spent LiNi0.5Mn0.3Co0.2O2 cathode materials. The as-prepared high-voltage LiCoO2 with Ni/Mn substitutional dopants in the Co layer enhances Co-O bonding that suppresses oxygen release and harmful phase transformation during delithiation, thus stabilizing the layered structure and leading to a superior electrochemical performance at 4.6 V. The pouch cell of modified LiCoO2 exhibits a capacity retention of 85.1% over 100 cycles at 4.5 V (vs graphite). We found that our strategy is applicable for degraded LiCoO2, and the regenerated LiCoO2 using this strategy exhibits excellent capacity retention (84.1%, 100 cycles) at 4.6 V. Our strategy paves the way for the direct conversion of spent batteries into high-energy-density batteries.

Constructing a Stable Interface Layer by Tailoring Solvation Chemistry in Carbonate Electrolytes for High-Performance Lithium-Metal Batteries.

Lithium-metal batteries (LMBs) are considered as promising next-generation batteries due to their high energy density. However, commercial carbonate electrolytes cannot be used in LMBs due to their poor compatibility with the lithium-metal anode and detrimental hydrogen fluoride (HF) generation by lithium hexafluorophosphate decomposition. By introducing lithium nitrate additive and a small amount of tetramethylurea as a multifunctional cosolvent to a commercial carbonate electrolyte, NO3 - , which is usually insoluble, can be introduced into the solvation structure of Li+ to form a conductive and stable solid electrolyte interface. At the same time, HF generation is suppressed by manipulating the solvation structure and a scavenging effect. As a result, the Coulombic efficiency (CE) of Li||Cu half cells using the designed carbonate electrolyte can reach 98.19% at room temperature and 96.14% at low temperature (-15 °C), and Li||LiFePO4 cells deliver a high capacity retention of 94.9% with a high CE of 99.6% after 550 cycles. This work provides a simple and effective way to extend the use of commercial carbonate electrolytes for next-generation battery systems.

Graphene-Based Materials for Flexible Lithium-Sulfur Batteries.

The increasing demand for wearable electronic devices necessitates flexible batteries with high stability and desirable energy density. Flexible lithium-sulfur batteries (FLSBs) have been increasingly studied due to their high theoretical energy density through the multielectron chemistry of low-cost sulfur. However, the implementation of FLSBs is challenged by several obstacles, including their low practical energy density, short life, and poor flexibility. Various graphene-based materials have been applied to address these issues. Graphene, with good conductivity and flexibility, exhibits synergistic effects with other active/catalytic/flexible materials to form multifunctional graphene-based materials, which play a pivotal role in FLSBs. This review summarizes the recent progress of graphene-based materials that have been used as various FLSB components, including cathodes, interlayers, and anodes. Particular attention is focused on the precise nanostructures, graphene efficacy, interfacial effects, and battery layout for realizing FLSBs with good flexibility, energy density, and cycling stability.