Daobin Mu

Fluoroethylene carbonate (FEC) and vinylene carbonate (VC) are common electrolyte additives with complementary interfacial modification for silicon-carbon/graphite (Si@C/Gr) composite anodes. However, their optimal synergistic ratio for practical Si@C/Gr anodes remains empirically determined and poorly understood. High experimental cost, strict test conditions and complex sample preparation make large-scale dataset acquisition for additive ratio optimization and electrochemical characterization extremely difficult, making small-sample data learning an efficient solution for battery material experimental research. Herein, a data-driven machine learning framework based on small-sample experimental data with experimental validation is developed to systematically optimize the dual FEC/VC additive system. A heterogeneous ensemble regression model is constructed using customized electrochemical performance descriptors and a composite evaluation index, which balances reversible capacity and cycling stability. Machine learning screening precisely identifies the optimal electrolyte formulation containing 2.75 wt% FEC and 1.21 wt% VC. Electrochemical measurements demonstrate the optimized electrolyte significantly reduces interfacial resistance, accelerates reaction kinetics, and delivers a high reversible capacity of 432.2 mAh g-1 for Si@C/Gr after 200 cycles at 1 C. Structural and compositional characterizations confirm the optimized dual additives induce an ultrathin, compact, robust hybrid SEI, where FEC-derived LiF-rich inorganic domains guarantee interfacial passivation and VC-generated flexible polymeric organic phases accommodate silicon volume fluctuation. The well-balanced inorganic-organic interphase suppresses continuous electrolyte decomposition and electrode structural deterioration. This work establishes an efficient small-sample machine learning guided electrolyte additive optimization strategy and elucidates the synergistic SEI stabilization mechanism of dual additives, offering a reliable route to high-performance electrolytes for silicon-based high-energy lithium-ion batteries.

Sulfide‐based all‐solid‐state lithium batteries are severely constrained by the intertwined challenges of interfacial instability and sluggish lithium‐ion kinetics at the nickel‐rich layered oxide cathode interface. Herein, we report a design principle centered on electronic‐state continuity across a cathode heterointerphase to simultaneously address these issues. By co‐doping single‐crystal LiNi _0.94 Co _0.04 Mn _0.02 O ₂ with selected period‐5 elements (Y, Zr, Nb, and Mo), a self‐assembled heterointerphase with spatially differentiated functions is achieved. Thermodynamically driven segregation yields a LiNbO ₃ /Li ₂ MoO ₄ outer passivation layer that suppresses side reactions, which remains coherent with a subsurface Y/Zr‐enriched rocksalt interlayer that anchors lattice oxygen. Crucially, the energetically continuous distribution of unoccupied 4 d orbital‐derived electronic states across the heterointerphase establishes an efficient charge redistribution channel and induces a well‐oriented built‐in electric field that screens the space‐charge barrier, thereby driving accelerated interfacial Li ⁺ transport. Consequently, the optimized cathode delivers a high specific capacity of 204.4 mAh g ⁻¹ at 0.1 C and maintains 86.7% capacity retention over 1000 cycles at 0.5 C when paired with a Li ₆ PS ₅ Cl solid‐state electrolyte. This orbital‐level electronic engineering strategy provides a promising design principle for integrating chemical passivity and ionic transport kinetics in high‐capacity all‐solid‐state energy storage systems.

Li-rich Mn-based layered oxides (LRMO) provide high capacity, but operation above 4.5 V is constrained by a transport-stability conflict: carbonate-rich Li+ coordination supports ion conduction while delivering reactive solvent molecules to an oxygen-redox-active cathode and a Li-metal anode. Here, a carbonate electrolyte containing 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (HFE), 1,3,6-hexanetricarbonitrile (HTCN), and trace LiNO3 is used to regulate how Li+-containing species pass through the outer and inner Helmholtz layers. Molecular dynamics, Raman/NMR spectroscopy, in situ Raman tracking, and interfacial electrochemical measurements show that HFE weakens Li+-carbonate coordination and enriches fluorinated species near electrified surfaces. This environment allows HTCN to remain transiently associated with incoming Li+ clusters through the outer Helmholtz plane (OHP) and to become available near LRMO during partial desolvation, where nitrile-derived species participate in cathode electrolyte interphase (CEI) formation. At Li metal, reduced carbonate competition allows trace nitrate to enter the earliest reduction events in the inner Helmholtz plane (IHP). The resulting N/F-rich CEI and Li3N/LiF-rich solid electrolyte interphase (SEI) suppress gas evolution, transition-metal dissolution, and nonuniform Li growth. LRMO cells cycled to 4.8 V deliver 276.9 mAh·g–1 and retain 85.43% after 200 cycles at 0.1 C, demonstrating coordinated dual-interface regulation for high-voltage lithium batteries.

Sodium‐ion batteries (SIBs) have shown significant potential for application in large‐scale energy storage systems due to their abundance of sodium resources, cost‐effectiveness, and environmental compatibility. Polyanionic cathode materials, with their unique crystal structure and high theoretical specific capacity, have become a focus of research in SIBs. In this study, we develop a novel pyrophosphate‐ and sulfate‐containing Na _2+2x Fe _2‐x P ₂ O ₇ SO ₄ (NFPS) polyanionic chemical material featuring a three‐dimensional open‐framework structure for the first time via the sol‐gel method. The diffraction peaks are successfully indexed to the P na2 ₁ orthorhombic system for NFPS. In situ carbon‐coated NFPS cathode materials are prepared successfully with a lower‐cost biomass carbon source. The cathode material delivers an initial specific capacity of up to 101.46 mAh g ⁻¹ at 0.05 C and retains 83.56% of its capacity after 500 cycles at 5 C, demonstrating its feasibility for application in SIBs. This study provides an innovative NFPS polyanionic material and methods for developing high‐performance cathode materials for SIBs, which are expected to promote the application of SIBs in large‐scale energy storage.

Lithium-ion battery management is shifting from scalar state estimation to integrated supervision of health, safety, and fast-charging capability. Existing reviews have addressed battery informatics, probabilistic prognostics, physics-guided learning, or digital-twin concepts as largely separate topics, but the connections among observability, mechanistic state representation, uncertainty quantification, and decision-oriented control remains underdeveloped. This Review reorganizes the field around uncertainty-aware physics-guided digital twins and argues that health loss, safety risk, and fast-charge limitations originate from coupled electrochemical, thermal, mechanical, and interfacial processes rather than from independent objectives. The discussion first identifies the shared physicochemical basis of degradation, with fast charging treated as a stringent validation case for a useful twin. The literature is then structured around four coupled layers: observability and data, physics-based and hybrid models, uncertainty-aware inference, and decision-facing control. On this basis, the Review examines health management beyond scalar state of health, plating-aware safety diagnosis, risk-constrained fast charging, and deployment from cell to pack and fleet levels. Finally, benchmarking, standardization, semantic data governance, and battery-passport requirements are discussed together with future opportunities in multimodal sensing, knowledge-enhanced twins, and autonomous closed-loop optimization. The central conclusion is that a deployable battery digital twin must be physics-grounded, uncertainty-calibrated, and explicitly designed to support decisions.

Hard carbon (HC) derived from coal tar (CT) are intrinsically restricted by the highly oriented and dense stacking of internal aromatic rings, resulting in inherent defects of sluggish sodium storage kinetics and poor cycling stability. Herein, a sucrose assisted in-situ cross linking strategy is developed to achieve a comprehensive microstructural reshaping of CT-derived HC. The study reveals that oxygen rich fragments generated from sucrose decomposition act as molecular anchors to strongly cross link with the polycyclic aromatic hydrocarbon networks, fundamentally blocking the formation of the graphite like mesophase. This cross linking interaction induces the formation of a three dimensional dense carbon skeleton featuring massive nanoscale closed pores and surface defects (CTSU). Benefiting from this unique configuration, the optimized CTSU anode delivers a high reversible capacity of 309.87 mAh g-1, and outstanding rate capability (147.34 mAh g-1 at 6000 mA g-1) while maintaining a high tap density of 1.267 g cm-3. Crucially, the material demonstrates exceptional high rate endurance, retaining 80.59% of its capacity after 20000 cycles under 6000 mA g-1, exhibiting an exceptionally minimal capacity loss of 0.00095% per cycle. This study provides a universal chemical cross linking paradigm to overcome the defects of coal tar based precursors, significantly advancing the practical application of high compaction, fast charging sodium ion batteries.

With the increasing demand for large‐scale power energy storage system applications, pure‐phase Na ₄ Fe _2.91 Mn _x (PO ₄ ) ₂ (P ₂ O ₇ ) cathode materials doped with manganese (Mn) are successfully prepared by the spray drying method combined with a high‐temperature sintering process for sodium ion batteries. The results show that the introduction of Mn effectively regulates the crystal and electronic structure of the material. Mn doping can reduce the lattice band gap, thereby further improving the electronic conductivity. On the other hand, the sodium ion migration channel is moderately widened, thereby increasing the ion diffusion rate. This synergistic optimization of electron conduction and ion diffusion capabilities allows the material to exhibit superior electrochemical performance. The optimal component of the Na ₄ Fe _2.91 Mn _0.015 (PO ₄ ) ₂ (P ₂ O ₇ ) cathode can still maintain a reversible specific capacity of 75 mAhg ⁻¹ at an ultra‐high rate of 30 C, and the capacity retention rate is as high as 81.8% after 1500 cycles at 20 C. This work provides a novel design insight for enhancing the rate performance and cycle stability of cathode materials, thereby facilitating the development of high‐performance sodium‐ion batteries for large‐scale energy storage applications.