Voltage Decay of Li-Rich Layered Oxides: Mechanism,Modification Strategies,and Perspectives

Li-rich layered oxides (LLOs) have been considered as the most promising cathode materials for achieving high energy density Li-ion batteries. However, they suffer from continuous voltage decay during cycling, which seriously shortens the lifespan of the battery in practical applications. This review comprehensively elaborates and summarizes the state-of-the-art of the research in this field. It is started from the proposed mechanism of voltage decay that refers to the phase transition, microscopic defects, and oxygen redox or release. Furthermore, several strategies to mitigate the voltage decay of LLOs from different scales, such as surface modification, elemental doping, regulation of components, control of defect, and morphology design are summarized. Finally, a systematic outlook on the real root of voltage decay is provided, and more importantly, a potential solution to voltage recovery from electrochemistry. Based on this progress, some effective strategies with multiple scales will be feasible to create the conditions for their commercialization in the future.     

Enabling On-Demand Conformal Zn-Ion Batteries on Non-Developable Surfaces

Conventional power sources encounter difficulties in achieving structural unitization with complex-shaped electronic devices because of their fixed form factors. Here, it is realized that an on-demand conformal Zn-ion battery (ZIB) on non-developable surfaces uses direct ink writing (DIW)-based nonplanar 3D printing. First, ZIB component (manganese oxide-based cathode, Zn powder-based anode, and UV-curable gel composite electrolyte) inks are designed to regulate their colloidal interactions to fulfill the rheological requirements of nonplanar 3D printing, and establish bi-percolating ion/electron conduction pathways, thereby enabling geometrical synchronization with non-developable surfaces, and ensuring reliable electrochemical performance. The ZIB component inks are conformally printed on arbitrary curvilinear substrates to produce embodied ZIBs that can be seamlessly integrated with complicated 3D objects (including human ears). The conformal ZIB exhibits a high fill factor (i.e., areal coverage of cells on underlying substrates, ≈100%) that ensures high volumetric energy density (50.5 mWh cm_cell⁻³), which exceeds those of previously-reported shape-adaptable power sources.     

Catalytically Induced Robust Inorganic-Rich Cathode Electrolyte Interphase for 4.5 V Li||NCM622 Batteries

Tailoring inorganic components of cathode electrolyte interphase (CEI) and solid electrolyte interphase (SEI) is critical to improving the cycling performance of lithium metal batteries. However, it is challenging due to complicated electrolyte reactions on cathode/anode surfaces. Herein, the species and inorganic component content of the CEI/SEI is enriched with an objectively gradient distribution through employing pentafluorophenyl 4-nitrobenzenesulfonate (PFBNBS) as electrolyte additive guided by engineering bond order with functional groups. In addition, a catalytic effect of LiNi_0.6Mn_0.2Co_0.2O₂ (NCM622) cathode is proposed on the decomposition of PFBNBS. PFBNBS with lower highest occupied molecular orbital can be preferentially oxidized on the NCM622 surface with the help of the catalytic effect to induce an inorganic-rich CEI for superior electrochemical performance at high voltage. Moreover, PFBNBS can be reduced on the Li surface due to its lower lowest unoccupied molecular orbital , increasing inorganic moieties in SEI for inhibiting Li dendrite generation. Thus, 4.5 V Li||NCM622 batteries with such electrolyte can retain 70.4% of initial capacity after 500 cycles at 0.2 C, which is attributed to the protective effect of the excellent CEI on NCM622 and the inhibitory effect of its derived CEI/SEI on continuous electrolyte decomposition.     

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.     

Air-Stable Li2S Cathode for Quasi-Solid-State Anode-Free Batteries with High Volumetric Energy

Anode-free batteries can maximize the energy density but their development is hindered by a lack of Li-rich cathodes for compensating the irreversible Li loss. Li₂S cathode is particularly appealing to this desire due to 2.6–4.7 folds more Li content and 4.2–6.8 times higher capacity than conventional intercalation cathodes. But its practical application is hindered by poor stability against moisture attacking in the air. Herein, a facile expendable polymer sheathing strategy toward air-stable Li₂S cathodes with high capacities for developing high-performance quasi-solid-state anode-free batteries without risk of cell leakage is reported. Tight protection by dense polymer barrier dramatically prolongs the lifetime of Li₂S cathode by 2,000 times at least in the air. Such air-stable Li₂S cathode allows for high compatibility of anode-free battery production with commercial schemes. More attractively, the polymer protective layer can in situ transform to multifunctional gel polymer electrolyte for releasing ionic pathways and enhancing cell performance by inhibiting LiPS loss and smoothing Li plating. With air-stable Li₂S cathode, the quasi-solid-state anode-free cells are assembled in ambient environment to deliver superb volumetric energy density of 1093 Wh L⁻¹. This study may shed new light to push the commercialization of high-energy and reliable anode-free batteries forward.     

Ultra-Thin Single-Particle-Layer Sodium Beta-Alumina-Based Composite Polymer Electrolyte Membrane for Sodium-Metal Batteries

Inorganic/organic composite polymer electrolytes (CPEs) with good flexibility and electrode contact have been pursued for solid−state sodium-metal batteries. However, the application of CPEs for high energy density solid−state sodium-metal batteries is still limited by the low Na⁺ conductivity, large thickness, and low ion transference number. Herein, an ultra-thin single-particle-layer (UTSPL) composite polymer electrolyte membrane with a thickness of ≈20 µm straddled by a sodium beta−alumina ceramic electrolyte (SBACE) is presented. A ceramic Na⁺-ion electrolyte that bridges or percolates across an ultra-thin and flexible polymer membrane provides: 1) the strength and flexibility from the polymer membrane, 2) excellent electrolyte/electrode interfacial contact, and 3) a percolation path for Na⁺-ion transfer. Owing to this novel design, the obtained UTSPL-35SBACE membrane exhibits a high Na⁺-ion conductivity of 0.19 mS cm⁻¹ and a transference number of 0.91 at room temperature, contributing to long−term cycling stability of symmetric sodium cells with a small overpotential. The assembled quasi-solid-state cell with the as−prepared UTSPL-35SBACE membrane displays superior cycling performance with a discharge capacity of 105 mAh g⁻¹ at 0.5 °C rate after 100 cycles and excellent rate performance (82 mAh g⁻¹ at 5 °C rate) at room temperature with the potassium manganese hexacyanoferrate (KMHCF)@CNTs/CNFs cathode, where KMHCF refers to potassium manganese hexacyanoferrate.     

A Stable Polymer-based Solid-State Lithium Metal Battery and its Interfacial Characteristics Revealed by Cryogenic Transmission Electron Microscopy

Solid-state lithium metal batteries (SSLMBs) are a promising candidate for next-generation energy storage systems due to their intrinsic safety and high energy density. However, they still suffer from poor interfacial stability, which can incur high interfacial resistance and insufficient cycle lifespan. Herein, a novel poly(vinylidene fluoride‑hexafuoropropylene)-based polymer electrolyte (PPE) with LiBF₄ and propylene carbonate plasticizer is developed, which has a high room-temperature ionic conductivity up to 1.15 × 10⁻³ S cm⁻¹ and excellent interfacial stability. Benefitting from the stable interphase, the PPE-based symmetric cell can operate for over 1000 h. By virtue of cryogenic transmission electron microscopy (Cryo-TEM) characterization, the high interfacial compatibility between Li metal anode and PPE is revealed. The solid electrolyte interphase is made up of an amorphous outer layer that can keep intimate contact with PPE and an inner Li₂O-dominated layer that can protect Li from continuous side reactions during battery cycling. A LiF-rich transition layer is also discovered in the region of PPE close to Li metal anode. The feasibility of investigating interphases in polymer-based solid-state batteries via Cryo-TEM techniques is demonstrated, which can be widely employed in future to rationalize the correlation between solid-state electrolytes and battery performance from ultrafine interfacial structures.     

Plasma Enhanced Lithium Coupled with Cobalt Fibers Arrays for Advanced Energy Storage

Construction of high efficiency and stable Li metal anodes is extremely vital to the breakthrough of Li metal batteries. In this study, for the first time, groundbreaking in situ plasma interphase engineering is reported to construct high-quality lithium halides-dominated solid electrolyte interphase layer on Li metal to stabilize & protect the anode. Typically, SF₆ plasma-induced sulfured and fluorinated interphase (SFI) is composed of LiF and Li₂S, interwoven with each other to form a consecutive solid electrolyte interphase. Simultaneously, brand-new vertical Co fibers (diameter: ≈5 µm) scaffold is designed via a facile magnetic-field-assisted hydrothermal method to collaborate with plasma-enhanced Li metal anodes (SFI@Li/Co). The Co fibers scaffold accommodates active Li with mechanical integrity and decreases local current density with good lithiophilicity and low geometric tortuosity, supported by DFT calculations and COMSOL Multiphysics simulation. Consequently, the assembled symmetric cells with SFI@Li/Co anodes exhibit superior stability over 525 h with a small voltage hysteresis (125 mV at 5 mA cm⁻²) and improved Coulombic efficiency (99.7%), much better than the counterparts. Enhanced electrochemical performance is also demonstrated in full cells with commercial cathodes and SFI@Li/Co anode. The research offers a new route to develop advanced alkali metal anodes for energy storage.     

An Intrinsically Nonflammable Electrolyte for Prominent-Safety Lithium Metal Batteries with High Energy Density and Cycling Stability

Nex-generation high-energy-density storage battery, assembled with lithium (Li)-metal anode and nickel-rich cathode, puts forward urgent demand for advanced electrolytes that simultaneously possess high security, wide electrochemical window, and good compatibility with electrode materials. Herein an intrinsically nonflammable electrolyte is designed by using 1 M lithium difluoro(oxalato)borate (LiDFOB) in triethyl phosphate (TEP) and N-methyl-N-propyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide [Pyr₁₃][TFSI] ionic liquid (IL) solvents. The introduction of IL can bring plentiful organic cations and anions, which provides a cation shielding effect and regulates the Li⁺ solvation structure with plentiful Li⁺-DFOB⁻ and Li⁺-TFSI⁻ complexes. The unique Li⁺ solvation structure can induce stable anion-derived electrolyte/electrode interphases, which effectively inhibit Li dendrite growth and suppress side reactions between TEP and electrodes. Therefore, the LiNi_0.9Co_0.05Mn_0.05O₂ (NCM90)/Li coin cell with this electrolyte can deliver stable cycling even under 4.5 V and 60 °C. Moreover, a Li-metal battery with thick NCM90 cathode (≈ 15 mg cm⁻²) and thin Li-metal anode (≈ 50 µm) (N/P ≈ 3), also reveals stable cycling performance under 4.4 V. And a 2.2 Ah NCM90/Li pouch cell can simultaneously possess prominent safety with stably passing the nail penetration test, and high gravimetric energy density of 470 Wh kg⁻¹ at 4.4 V.     

Comprehensively Strengthened Metal-Oxygen Bonds for Reversible Anionic Redox Reaction

Introducing anionic redox in layered oxides is an effective approach to breaking the capacity limit of conventional cationic redox. However, the anionic redox reaction generally suffers from excessive oxidation of lattice oxygen to O₂ and O₂ release, resulting in local structural deterioration and rapid capacity/voltage decay. Here, a Na_0.71Li_0.22Al_0.05Mn_0.73O₂ (NLAM) cathode material is developed by introducing Al³⁺ into the transition metal (TM) sites. Thanks to the strong Al–O bonding strength and small Al³⁺ radius, the TMO₂ skeleton and the holistic TM–O bonds in NLAM are comprehensively strengthened, which inhibits the excessive lattice oxygen oxidation. The obtained NLAM exhibits a high reversible capacity of 194.4 mAh g^-1 at 20 mA g^-1 and decent cyclability with 98.6% capacity retention over 200 cycles at 200 mA g⁻¹. In situ characterizations reveal that the NLAM experiences phase transitions with an intermediate OP4 phase during the charge–discharge. Theoretical calculations further confirm that the Al substitution strategy is beneficial for improving the overlap between Mn 3d and O 2p orbitals. This finding sheds light on the design of layered oxide cathodes with highly reversible anionic redox for sodium storage.