A Materials Perspective on Direct Recycling of Lithium-Ion Batteries: Principles,Challenges and Opportunities

As the dominant means of energy storage technology today, the widespread deployment of lithium-ion batteries (LIBs) would inevitably generate countless spent batteries at their end of life. From the perspectives of environmental protection and resource sustainability, recycling is a necessary strategy to manage end-of-life LIBs. Compared with traditional hydrometallurgical and pyrometallurgical recycling methods, the emerging direct recycling technology, rejuvenating spent electrode materials via a non-destructive way, has attracted rising attention due to its energy efficient processes along with increased economic return and reduced CO₂ footprint. This review investigates the state-of-the-art direct recycling technologies based on effective relithiation through solid-state, aqueous, eutectic solution and ionic liquid mediums and thoroughly discusses the underlying regeneration mechanism of each method regarding different battery chemistries. It is concluded that direct regeneration can be a more energy-efficient, cost-effective, and sustainable way to recycle spent LIBs compared with traditional approaches. Additionally, it is also identified that the direct recycling technology is still in its infancy with several fundamental and technological hurdles such as efficient separation, binder removal and electrolyte recovery. In addressing these remaining challenges, this review proposes an outlook on potential technical avenues to accelerate the development of direct recycling toward industrial applications.     

Electrochemically Induced Crystalline-to-Amorphous Transition of Dinuclear Polyoxovanadate for High-Rate Lithium-Ion Batteries

Polyoxometalates are intriguing high-capacity anode materials for alkali-metal-ion storage due to their multi-electron redox capabilities and flexible structure. However, their poor electrical conductivity and high working voltage severely restrict their practical application. Herein, the dinuclear polyoxovanadate Sr₂V₂O₇·H₂O with unusually high electrical conductivity is reported as a promising anode material for lithium-ion batteries. During the initial lithiation process, the Sr₂V₂O₇·H₂O anode experiences an electrochemically induced crystalline-to-amorphous transition. The resulting amorphous structure provides high redox activity and fast reaction kinetics via reversible V^4.9+/V^2.8+ redox couple through the intercalation mechanism. Furthermore, when coupled with the LiFePO₄ cathode, the strong V O bonds of the amorphous anode provide excellent structural stability, with the full-cell capable of performing >12 000 cycles with a capacity retention of 72%. Another advantage of Sr_2xV₂O_7-δ·yH₂O (0.5 ≤ x ≤ 1.0) is its composition adjustability, which enables delicately regulating the Sr vacancy content without destroying the structure. The defect Sr_2xV₂O_7-δ·yH₂O (x = 0.5) electrodes show significantly improved specific capacity and rate capability without sacrificing other key properties, delivering a high specific capacity of 479 mAh g^-1 at 0.1 mA cm^-2 and 41.9% of its capacity in 2 min. Overall, the preliminary study points the way forward for the facile preparation of high-quality polyoxometalates for advanced energy storage applications and beyond.     

Sufficient Utilization of Mn2+/Mn3+/Mn4+ Redox in NASICON Phosphate Cathodes towards High-Energy Na-Ions Batteries

Na superionic conductor of Na₃MnTi(PO₄)₃ only containing high earth-abundance elements is regarded as one of the most promising cathodes for the applicable Na-ion batteries due to its desirable cycling stability and high safety. However, the voltage hysteresis caused by Mn²⁺ ions resided in Na⁺ vacancies has led to significant capacity loss associated with Mn reaction centers between 2.5–4.2 V. Herein, the sodium excess strategy based on charge compensation is applied to suppress the undesirable voltage hysteresis, thereby achieving sufficient utilization of the Mn²⁺/Mn³⁺ and Mn³⁺/Mn⁴⁺ redox couples. These findings indicate that the sodium excess Na_3.5MnTi_0.5Ti_0.5(PO₄)₃ cathode with Ti⁴⁺ reduction has a lowest Mn²⁺ occupation on the Na⁺ vacancies in its initial composition, which can improve the kinetics properties, finally contributing to a suppressed voltage hysteresis. Based on these findings, it is further applied the sodium excess route on a Mn-richer phosphate cathode, which enables the suppressed voltage hysteresis and more reversible capacity. Consequently, this developed Na_3.6Mn_1.15Ti_0.85(PO₄)₃ cathode achieved a high energy density over 380 Wh kg⁻¹ (based on active substance mass of cathode) in full-cell configurations, which is not only superior to most of the phosphate cathodes, but also delivers more application potential than the typical oxides cathodes for Na-ion batteries.     

Direct and Rapid High-Temperature Upcycling of Degraded Graphite

Recycling the degraded graphite is becoming increasingly important, which can helped conserve natural resources, reduce waste, and provide economic and environmental benefits. However, current regeneration methods usually suffer from the use of harmful chemicals, high energy and time consumption, and poor scalability. Herein, we report a continuously high-temperature heating (≈2000 K) process to directly and rapidly upcycle degraded graphite containing impurities. A sloped carbon heater is designed to provide the continuous heating source, which enables robust control over the temperature profile, eliminating thermal barrier for heat transfer compared to conventional furnace heating. The upcycling process can be completed within 0.1 s when the degraded graphite rolls down the sloped heater, allowing us to produce the upcycled graphite on a large scale. High-temperature heating removes impurities and enhances the graphitization degree and (002) interlayer spacing, making the upcycled graphite more suitable for lithium intercalation and deintercalation. The assembled upcycled graphite||Li cell displays a high reversible capacity of ≈320 mAh g⁻¹ at 1 C with a capacity retention of 96% after 500 cycles, comparable to current state-of-the-art recycled graphite. The method is a chemical-free, rapid, and scalable way to upcycle degraded graphite, and is adaptable to recycle other electrode materials.     

Regulating Fe Aggregation State via Unique Fe?N?V Pre-Coordination to Optimize the Adsorption-Catalysis Effect in High-Performance Lithium-Sulfur Batteries

Lithium-sulfur batteries (LSBs) suffer from uncontrollable shuttling behavior of lithium polysulfides (LiPSs: Li₂S_x, 4 ≤ x ≤8) and the sluggish reaction kinetics of bidirectional liquid-solid transformations, which are commonly coped through a comprehensive adsorption-catalysis strategy. Herein, a unique Fe N V pre-coordination is introduced to regulate the content of “dissociative Fe³⁺” in liquid phase, realizing the successful construction of N-doped micro-mesoporous “urchin-like” hollow carbon nanospheres decorated with single atom Fe-N₄ sites and VN nanoparticles (denoted as SA-Fe/VN@NMC). The strong chemisorption ability toward LiPSs and catalyzed Li₂S decomposition behavior on VN, along with the boosted reaction kinetics for sulfur reduction on SA-Fe sites are experimentally and theoretically evidenced. Moreover, the nanoscale-neighborhood distribution of VN and SA-Fe active sites presents synergistic effect for the anchoring-reduction-decomposition process of sulfur species. Thus SA-Fe/VN@NMC presents an optimized adsorption-catalysis effect for the whole sulfur conversion. Therefore, the SA-Fe/VN@NMC based Li-S cells exhibit high cyclic stability (a low decay of 0.024% per cycle over 700 cycles at 1 C, sulfur content: 70 wt%) and considerable rate performance (683.2 mAh g⁻¹ at 4 C). Besides, a high areal capacity of 5.06 mAh cm⁻² is retained after 100 cycles under the high sulfur loading of 5.6 mg cm⁻². This work provides a new perspective to design the integrated electrocatalysts comprising hetero-formed bimetals in LSBs.     

In Situ Conversion Reaction Triggered Alloy@Antiperovskite Hybrid Layers for Lithiophilic and Robust Lithium/Garnet Interfaces

Garnet-type electrolytes demonstrate promising prospects in the field of solid-state lithium batteries owing to their superior ionic conductivity and high (electro)chemical stability toward Li metal, whereas the critical issue of Li dendrite growth and even infiltration throughout garnets limits their practical applications. Herein, a hybrid interlayer consisting of Li₃Bi alloy embedded in antiperovskite-type Li₃OCl matrix is in situ constructed at Li/Li_6.75La₃Zr_1.75Ta_0.25O₁₂ interface by taking the conversion reaction of BiOCl with Li metal. The lithiophilic nature of such interlayer enables an intimate contact of garnet against Li metal, guaranteeing a dramatically reduced interfacial resistance of 27 Ω cm². In addition, the inside electron-conducting Li₃Bi nanoparticles homogenize the interfacial potential distribution, while the outside ion-conducting Li₃OCl matrix with a bandgap of 5.06 eV blocks electron tunneling from Li bulk. Profiting from such synergistic effect, the resultant Li symmetric cell displays a high critical current density of 1.1 mA cm⁻², along with an ultralong cycling life of 1000 h at 0.5 mA cm⁻². Furthermore, the corresponding solid LiNi_0.6Co_0.2Mn_0.2O₂/Li cell delivers a high cycling stability for 150 times accompanied by a capacity retention of 82%. This study puts forward a potential solution for construction of functional layers at Li/garnet interfaces by making use of in situ conversion reaction.     

Incombustible Polymer Electrolyte Boosting Safety of Solid-State Lithium Batteries: A Review

Lithium-ion batteries with their portability, high energy density, and reusability are frequently used in today's world. Under extreme conditions, lithium-ion batteries leak, burn, and even explode. Therefore, improving the safety of lithium-ion batteries has become a focus of attention. Researchers believe using a solid electrolyte instead of a liquid one can solve the lithium battery safety issue. Due to the low price, good processability and high safety of the solid polymer electrolytes, increasing attention have been paid to them. However, polymer electrolytes can also decompose and burn under extreme conditions. Moreover, lithium dendrites are formed continuously due to the uneven charge distribution on the surface of the lithium metal anode. A short circuit caused by a lithium dendrite can cause the battery to thermal runaway. As a result, the safety of polymer solid-state batteries remains a challenge. In this review, the thermal runaway mechanism of the batteries is summarized, and the batteries abuse test standard is introduced. In addition, the recent works on the high-safety polymer electrolytes and the solution strategies of lithium anode problems in polymer batteries are reviewed. Finally, the development direction of safe polymer solid lithium batteries is prospected.     

水雷锂离子电池组充电控制策略研究

为解决某型水雷大容量锂离子电池组充电过程中存在的安全问题,缩短充电时间,提高单体电池一致性,设计了水雷锂离子电池组充电管理系统。采用恒流串充-恒压串充-并联均衡充电的充电控制策略,兼顾了锂离子电池安全性和充电效率,延长了锂离子电池组的使用寿命,从而提高了水雷的维护和保障能力。     

高冲击高温下电引信关键元器件可靠性测试

为了保证电引信的可靠性和安全性,在设计或生产前有必要对电引信关键元器件进行可靠性测试,文中在分析了电引信关键元器件及其失效模式的基础上选择电引信部分关键元器件:起爆电路用闸流管、抗干扰电路用独石电容和点火电路用固体钽电容,设计测试电路,提出了在高机械冲击和高温条件下对电引信的性能参数进行动态可靠性测试的方案,并进行了试验,试验结果对电引信关键元器件的选型、筛选及后续测试具有一定的参考价值。     

科学改造无功补偿装置减少电费支出

分析了功率因数偏低的原因,主要原因有原有低压无功补偿装置设计不合理,器件出现故障,不能提供系统所需的无功补偿功率。通过实例给出了无功补偿装置改造的具体做法,如加装电抗器,选用耐压等级合适的电容器,采用无功补偿装置专用交流接触器,并合理规划了无功补偿柜内散热通道。最后对改造前后的经济效益进行了分析。