Fundamentals, status and challenges of direct recycling technologies for lithium ion batteries.

Advancement in energy storage technologies is closely related to social development. However, a significant conflict has arisen between the explosive growth in battery demand and resource availability. Facing the upcoming large-scale disposal problem of spent lithium-ion batteries (LIBs), their recycling technology development has become key. Emerging direct recycling has attracted widespread attention in recent years because it aims to 'repair' the battery materials, rather than break them down and extract valuable products from their components. To achieve this goal, a profound understanding of the failure mechanisms of spent LIB electrode materials is essential. This review summarizes the failure mechanisms of LIB cathode and anode materials and the direct recycling strategies developed. We systematically explore the correlation between the failure mechanism and the required repair process to achieve efficient and even upcycling of spent LIB electrode materials. Furthermore, we systematically introduce advanced in situ characterization techniques that can be utilized for investigating direct recycling processes. We then compare different direct recycling strategies, focussing on their respective advantages and disadvantages and their applicability to different materials. It is our belief that this review will offer valuable guidelines for the design and selection of LIB direct recycling methods in future endeavors. Finally, the opportunities and challenges for the future of battery direct recycling technology are discussed, paving the way for its further development.

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.

Mitigating Jahn-Teller Effect in Layered Cathode Material Via Interstitial Doping for High-Performance Sodium-Ion Batteries.

Layered transition metal oxides are promising cathode materials for sodium-ion batteries due to their high energy density and appropriate operating potential. However, the poor structural stability is a major drawback to their widespread application. To address this issue, B3+ is successfully introduced into the tetrahedral site of Na0.67 Fe0.5 Mn0.5 O2 , demonstrating the effectiveness of small-radius ion doping in improving electrochemical performance. The obtained Na0.67 Fe0.5 Mn0.5 B0.04 O2 exhibits excellent cycling performance with 88.8% capacity retention after 100 cycles at 1 C and prominent rate performance. The structure-property relationship is constructed subsequently by neutron powder diffraction, in situ X-ray diffraction and X-ray absorption spectroscopy, which reveal that the Jahn-Teller distortion and the consequent P2-P2' phase transformation are effectively mitigated because of the occupancy of B3+ at the interstitial site. Furthermore, it is found that the transition metal layers are stabilized and the transition metal dissolution are suppressed, resulting in excellent cycling performance. Besides, the prominent rate performance is attributed to the enhanced diffusion kinetics associated with the rearrangement of Na+ . This work provides novel insight into the action mechanism of interstitial site doping and demonstrates a universal approach to improve the electrochemical properties of P2-type manganese-based sodium cathode materials.

Promoting Surface Electric Conductivity for High-Rate LiCoO2.

The cathode materials work as the host framework for both Li+ diffusion and electron transport in Li-ion batteries. The Li+ diffusion property is always the research focus, while the electron transport property is less studied. Herein, we propose a unique strategy to elevate the rate performance through promoting the surface electric conductivity. Specifically, a disordered rock-salt phase was coherently constructed at the surface of LiCoO2 , promoting the surface electric conductivity by over one magnitude. It increased the effective voltage (Veff ) imposed in the bulk, thus driving more Li+ extraction/insertion and making LiCoO2 exhibit superior rate capability (154 mAh g-1 at 10 C), and excellent cycling performance (93 % after 1000 cycles at 10 C). The universality of this strategy was confirmed by another surface design and a simulation. Our findings provide a new angle for developing high-rate cathode materials by tuning the surface electron transport property.

A Multifunctional Amino Acid Enables Direct Recycling of Spent LiFePO4 Cathode Material.

Lithium iron phosphate (LiFePO4 , LFP) batteries are extensively used in electric vehicles and energy storage due to their good cycling stability and safety. However, the finite service life of lithium-ion batteries leads to significant amounts of retired LFP batteries, urgently required to be recycled by environmentally friendly and effective methods. Here, a direct regeneration strategy using natural and low-cost L-threonine as a multifunctional reductant is proposed. The hydroxyl groups and amino groups in L-threonine act as electron donors and nitrogen sources, respectively. The reductive environment created by L-threonine not only aids in converting the degraded FePO4 phase back to a single LFP phase but also facilitates the elimination of detrimental Li-Fe anti-site defects; thus, reconstructing fast Li+ diffusion channels. Meanwhile, N atoms derived from amino groups are able to dope into carbon layers, generating more active sites and enhancing the conductive properties of LFP particles. The regenerated LFP shows great electrochemical performance with a discharge capacity of 147.9 mAh g-1 at 1 C and a capacity retention of 86% after 500 cycles at 5 C. Further, this approach is also feasible for LFP black mass sourced from practical industrial dismantling lines, providing considerable prospects for the large-scale recycling of LFP batteries.

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.

Sustainable upcycling of mixed spent cathodes to a high-voltage polyanionic cathode material.

Sustainable battery recycling is essential for achieving resource conservation and alleviating environmental issues. Many open/closed-loop strategies for critical metal recycling or direct recovery aim at a single component, and the reuse of mixed cathode materials is a significant challenge. To address this barrier, here we propose an upcycling strategy for spent LiFePO4 and Mn-rich cathodes by structural design and transition metal replacement, for which uses a green deep eutectic solvent to regenerate a high-voltage polyanionic cathode material. This process ensures the complete recycling of all the elements in mixed cathodes and the deep eutectic solvent can be reused. The regenerated LiFe0.5Mn0.5PO4 has an increased mean voltage (3.68 V versus Li/Li+) and energy density (559 Wh kg-1) compared with a commercial LiFePO4 (3.38 V and 524 Wh kg-1). The proposed upcycling strategy can expand at a gram-grade scale and was also applicable for LiFe0.5Mn0.5PO4 recovery, thus achieving a closed-loop recycling between the mixed spent cathodes and the next generation cathode materials. Techno-economic analysis shows that this strategy has potentially high environmental and economic benefits, while providing a sustainable approach for the value-added utilization of waste battery materials.

Homogeneous Repair of Highly Degraded Ni-Rich Cathode Material with Spent Lithium Anode.

Direct regeneration of spent lithium-ion batteries has received wide attention owing to its potential for resource reuse and environmental benefits. The repair effect of direct regeneration methods undergoing heterogeneous repair process is usually inferior, while homogenous repair process plays a vital role to achieve satisfactory repair results. However, the practical applications of current homogeneous repair methods are challenged by the complex operations and relatively high costs owing to the requirement of additional heating or pressurization. Herein, this work proposes a simple strategy to achieve homogeneous repair of spent cathode materials under relatively mild conditions by uniformly precoating lithium source at room temperature and atmospheric pressure. Followed by annealing, highly degraded LiNi0.83Co0.12Mn0.05O2 with severe Li deficiency and irreversible phase transition is repaired to have an initial capacity of 181.6 mAh g-1 and capacity retention of 80.7% after 150 cycles at 0.5 C. The lithium source used in this strategy is from the spent lithium anode. Moreover, this strategy is suitable for the direct regeneration of various layer oxide cathode materials with different failure degrees. This work provides both theoretical guidance and practical examples for the straightforward, effective, and universally applicable direct regeneration methods.

Subtractive transformation of cathode materials in spent Li-ion batteries to a low-cobalt 5 V-class cathode material.

Adding extra raw materials for direct recycling or upcycling is prospective for battery recycling, but overlooks subtracting specific components beforehand can facilitate the recycling to a self-sufficient mode of sustainable production. Here, a subtractive transformation strategy of degraded LiNi0.5Co0.2Mn0.3O2 and LiMn2O4 to a 5 V-class disordered spinel LiNi0.5Mn1.5O4-like cathode material is proposed. Equal amounts of Co and Ni from degraded materials are selectively extracted, and the remaining transition metals are directly converted into Ni0.4Co0.1Mn1.5(CO3)2 precursor for preparing cathode material with in-situ Co doping. The cathode material with improved conductivity and bond strength delivers high-rate (10 C and 20 C) and high-temperature (60 °C) cycling stability. This strategy with no extra precursor input can be generalized to practical degraded black mass and reduces the dependence of current cathode production on rare elements, showing the potential of upcycling from the spent to a next-generation 5 V-class cathode material for the sustainable Li-ion battery industry.

Dual Modification of P3-Type Layered Cathodes to Achieve High Capacity and Long Cyclability for Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) have garnered extensive attentions in recent years as a low-cost alternative to lithium-ion batteries. However, achieving both high capacity and long cyclability in cathode materials remains a challenge for SIB commercialization. P3-type Na0.67Ni0.33Mn0.67O2 cathodes exhibit high capacity and prominent Na+ diffusion kinetics but suffer from serious capacity decay and structural deterioration due to stress accumulation and phase transformations upon cycling. In this work, a dual modification strategy with both morphology control and element doping is applied to modify the structure and optimize the properties of the P3-type Na0.67Ni0.33Mn0.67O2 cathode. The modified Na0.67Ni0.26Cu0.07Mn0.67O2 layered cathode with hollow porous microrod structure exhibits an excellent reversible capacity of 167.5 mAh g-1 at 150 mA g-1 and maintains a capacity above 95 mAh g-1 after 300 cycles at 750 mA g-1. For one thing, the specific morphology shortens the Na+ diffusion pathway and releases stress during cycling, leading to excellent rate performance and high cyclability. For another, Cu doping at the Ni site reduces the Na+ diffusion energy barrier and mitigates unfavorable phase transitions. This work demonstrates that the electrochemical performance of P3-type cathodes can be significantly improved by applying a dual modification strategy, resulting in reduced stress accumulation and optimized Na+ migration behavior for high-performance SIBs.

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.

Collaborative and privacy-preserving retired battery sorting for profitable direct recycling via federated machine learning.

Unsorted retired batteries with varied cathode materials hinder the adoption of direct recycling due to their cathode-specific nature. The surge in retired batteries necessitates precise sorting for effective direct recycling, but challenges arise from varying operational histories, diverse manufacturers, and data privacy concerns of recycling collaborators (data owners). Here we show, from a unique dataset of 130 lithium-ion batteries spanning 5 cathode materials and 7 manufacturers, a federated machine learning approach can classify these retired batteries without relying on past operational data, safeguarding the data privacy of recycling collaborators. By utilizing the features extracted from the end-of-life charge-discharge cycle, our model exhibits 1% and 3% cathode sorting errors under homogeneous and heterogeneous battery recycling settings respectively, attributed to our innovative Wasserstein-distance voting strategy. Economically, the proposed method underscores the value of precise battery sorting for a prosperous and sustainable recycling industry. This study heralds a new paradigm of using privacy-sensitive data from diverse sources, facilitating collaborative and privacy-respecting decision-making for distributed systems.

Synergistic activation of anionic redox via cosubstitution to construct high-capacity layered oxide cathode materials for sodium-ion batteries.

As a potential substitute for lithium-ion battery, sodium-ion batteries (SIBs) have attracted a tremendous amount of attention due to their advantages in terms of cost, safety and sustainability. Nevertheless, further improvement of the energy density of cathode materials in SIBs remains challenging and requires the activation of anion redox reaction (ARR) activity to provide additional capacity. Herein, we report a high-performance Mn-based sodium oxide cathode material, Na0.67Mg0.1Zn0.1Mn0.8O2 (NMZMO), with synergistic activation of ARR by cosubstitution. This material can deliver an ultra-high capacity of âˆ¼233 mAh/g at 0.1 C, which is significantly higher than their single-cation-substituted counterparts and among the best in as-reported MgMn or ZnMn-based cathodes. Various spectroscopic techniques were comprehensively employed and it was demonstrated that the higher capacity of NMZMO originated from the enhanced ARR activity. Neutron pair distribution function and resonant inelastic X-ray scattering experiments revealed that out-of-plane migration of Mg/Zn occurred upon charging and oxygen anions in the form of molecular O2 were trapped in vacancy clusters in the fully-charged-state. In NMZMO, Mg and Zn mutually interacted with each other to migrate toward tetrahedral sites, which provided a prerequisite for further ARR activity enhancement to form more trapped molecular O2. These findings provide unique insight into the ARR mechanism and can guide the development of high-performance cathode materials through ARR enhancement strategies.

Gas sensing mechanisms of metal oxide semiconductors: a focus review.

In recent years, gas sensors have been increasingly used in industrial production and daily life. Metal oxide semiconductor gas sensing materials are favoured for their outstanding physical and chemical properties, low cost and simple preparation methods. However, the gas sensing mechanisms of metal oxide semiconductors have not been considered by researchers, resulting in omissions and errors in the interpretation of gas sensing mechanisms in many articles. This review organizes and introduces several common gas sensing mechanisms of metal oxide semiconductors in detail and classifies them into two categories. The scope and relationship of these mechanisms are clarified. In addition, this review selects four strategies for enhancing the gas sensing properties of metal oxide semiconductors and analyses the gas sensing mechanisms to highlight the importance of the gas sensing mechanism. Finally, some perspectives for future investigations on the gas sensing mechanisms of metal oxide semiconductors are discussed as well.