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Improving the wide‐temperature operation of rechargeable batteries is crucial for boosting the adoption of electric vehicles and further advancing their application scope in harsh environments like deep ocean and space probes. Herein, recent advances in electrolyte solvation chemistry are critically summarized, aiming to address the long‐standing challenge of notable energy diminution at sub‐zero temperatures and rapid capacity degradation at elevated temperatures (>45°C). This review provides an in‐depth analysis of the fundamental mechanisms governing the Li‐ion transport process, illustrating how these insights have been effectively harnessed to synergize with high‐capacity, high‐rate electrodes. Another critical part highlights the interplay between solvation chemistry and interfacial reactions, as well as the stability of the resultant interphases, particularly in batteries employing ultrahigh‐nickel layered oxides as cathodes and high‐capacity Li/Si materials as anodes. The detailed examination reveals how these factors are pivotal in mitigating the rapid capacity fade, thereby ensuring a long cycle life, superior rate capability, and consistent high‐/low‐temperature performance. In the latter part, a comprehensive summary of in situ/operational analysis is presented. This holistic approach, encompassing innovative electrolyte design, interphase regulation, and advanced characterization, offers a comprehensive roadmap for advancing battery technology in extreme environmental conditions. [ABSTRACT FROM AUTHOR]

Fabricating metal boride heterostructures and deciphering their interface interaction mechanism on accelerating polysulfide conversion at atomic levels are meaningful yet challenging in lithium–sulfur batteries (LSBs). Herein, novel highly‐conductive and binary sulfiphilic NbB2‐MXene heterostructures are elaborately designed with spontaneous built‐in electric field (BIEF) via a simple one‐step borothermal reduction strategy. Experimental and theoretical results reveal that Nb and B atoms can chemically bond with polysulfides, thereby enriching chemical anchor and catalytic active sites. Meanwhile, the spontaneous BIEF induces interfacial charge redistribution to make more electrons transferred to surface NbB2 sites, thereby weakening its strong adsorption property yet accelerating polysulfide transfer and electron diffusion on hetero‐interface, so providing moderate polysulfide adsorb‐ability yet decreasing sulfur‐species conversion energy barriers, further boosting the intrinsically catalytic activity of NbB2‐MXene for accelerated bidirectional sulfur conversion. Thus, S/NbB2‐MXene cathode presents high initial capacity of 1310.1 mAh g−1 at 0.1 C, stable long‐term lifespan with 500 cycles (0.076% capacity decay per cycle) at 1 C, and large areal capacity of 6.5 mAh cm−2 (sulfur loading: 7.0 mg cm−2 in lean electrolyte of 5 µL mgs−1) at 0.1 C. This work clearly unveils the mechanism of interfacial BIEF and binary sulfiphilic effect on accelerating stepwise sulfur conversion at atomic levels. [ABSTRACT FROM AUTHOR]

Large volume expansion and sluggish reaction kinetics of low‐conductivity red phosphorus (RP) anodes hinder its practical application in potassium‐ion batteries (PIBs). Here, a self‐limited growth strategy to fabricate Bi (Sb) nanoparticles is demonstrated, as electrochemically active and conductive coating, in situ embedded into honeycomb‐like porous red phosphorus (HPRP) to form HPRP@Bi (HPRP@Sb) composites, greatly improving the potassium‐storage kinetics, stability and volumetric performance of HPRP. Here, Bi nanoparticles are converted into amorphous Bi during cycling, which are uniformly coated on the porous HPRP skeleton to form 3D conductive Bi networks. Theoretical calculations verify that introducing amorphous Bi significantly decreases K+ diffusion barrier in composites, and greatly enhancing their electrical conductivity and interfacial ion transport between HPRP and Bi, thereby accelerating their potassium storage kinetics and stability. Whereas the robust porous structure and inward expansion mechanism of HPRP effectively buffer their volume expansion of RP and Bi. Therefore, HPRP@Bi anode delivers high gravimetric and volumetric capacity (465.6 mAh g−1, 745 mAh cm−3) and stable long lifespan with 200 cycles at 0.05 A g−1 in PIBs. This work demonstrates a new approach to promote ion storage kinetics and stability of RP via integrating the synergy of high‐conductivity active metal and high‐capacity porous RP. [ABSTRACT FROM AUTHOR]

Designing dense thick sulfur cathodes to gain high‐volumetric/areal‐capacity lithium–sulfur batteries (LSBs) in lean electrolytes is extremely desired. Nevertheless, the severe Li2S clogging and unclear mechanism seriously hinder its development. Herein, an integrated strategy is developed to manipulate Li2S redox kinetics of CoP/MXene catalyst via electron‐donor Cu doping. Meanwhile a dense S/Cu0.1Co0.9P/MXene cathode (density = 1.95 g cm−3) is constructed, which presents a large volumetric capacity of 1664 Ah L−1 (routine electrolyte) and a high areal capacity of ≈8.3 mAh cm−2 (lean electrolyte of 5.0 µL mgs−1) at 0.1 C. Systematical thermodynamics, kinetics, and theoretical simulation confirm that electron‐donor Cu doping induces the charge accumulation of Co atoms to form more chemical bonding with polysulfides, whereas weakens CoS bonding energy and generates abundant lattice vacancies and active sites to facilitate the diffusion and catalysis of polysulfides/Li2S on electrocatalyst surface, thereby decreasing the diffusion energy barrier and activation energy of Li2S nucleation and dissolution, boosting Li2S redox kinetics, and inhibiting shuttling in the dense thick sulfur cathode. This work deeply understands the atomic‐level manipulation mechanism of Li2S redox kinetics and provides dependable principles for designing high‐volumetric‐energy‐density, lean‐electrolyte LSBs through integrating bidirectional electro‐catalysts with manipulated Li2S redox and dense‐sulfur engineering. [ABSTRACT FROM AUTHOR]

Transition metal sulfides derived from metal‐organic frameworks (MOFs) have received increasing attention as a potential energy storage electrode material. Here, a series of NiS2/CoS2/NC‐T (T=temperature) have been successfully constructed by carbonizing and sulfuring the precursor of Ni/Co‐MOF. It is worth emphasizing that N‐doped carbon materials improve the conductivity of the electrode material. Moreover, NiS2/CoS2/NC‐500 maintains the rod‐like structure of the precursor and exhibits a high specific capacitance of 1325 F g−1 at a current density of 1 A g−1. Apart from high capacitance, the NiS2/CoS2/NC‐500 also demonstrated excellent cycling stability with retention rate of 75 % after 5000 cycles at a current density of 5 A g−1. The good performance could be attributed to the unique rod‐like structure and pore‐size distribution of NiS2/CoS2/NC‐500. Moreover, an assembled asymmetric supercapacitor NiS2/CoS2/NC‐500//AC displays a high energy density of 53.93 Wh kg−1 at a power density of 800 W kg−1 and good cycle stability with capacitance retention of 85.71 % after 20,000 cycles at 5 A g−1. In particular, a red LED can be illuminated by the assembled ASC, indicating that as‐synthesized NiS2/CoS2/NC‐500 hold great potential for practical applications. [ABSTRACT FROM AUTHOR]

Transition‐metal compound based heterostructures hold promise but challenge in expediting stepwise sulfur redox because of their inferior adsorption‐catalysis activity and unclear mechanism in Li–S batteries (LSBs). Herein, the p‐band centers and interfacial charge rearrangement of Mo‐doped VS2/MXene heterostructure are tuned through Mo doping and built‐in electric field (BIEF) effect to boost dual‐directional sulfur redox. Experimental and theoretical calculations demonstrate that Mo doping tunes the p‐band center of active S in VS2, shifting it positively toward the Fermi level to enhance the polysulfide adsorption ability and electrocatalytic activity. Whereas BIEF between Mo‐VS2 and MXene accelerates electrons transfer from MXene to Mo‐VS2 surface, generating more electrons accumulation at the surface‐S sites. Their synergy accelerates sulfur‐species conversion by reducing the energy barrier of polysulfide reduction and Li2S oxidation. Ultimately, S/Mo‐VS2/MXene cathode exhibits large initial capacity of 1387 mAh g−1at 0.2 C and stable 500‐cycle long‐term lifespan at 0.5 C. Impressively, the thick S/Mo‐VS2/MXene cathode (S loading: 5.4 mg cm−2, lean electrolyte: 4.5 µL mgsulfur−1) achieves a high areal capacity of 6.44 mAh cm−2 with 91.5% retention for 61 cycles. This work highlights the synergistic strategy of doping engineering and BIEF to tune the p‐band centers and interfacial charge rearrangement for designing high‐performance LSBs. [ABSTRACT FROM AUTHOR]

It is a significant challenge to design a dense high-sulfur-loaded cathode and meanwhile to acquire fast sulfur redox kinetics and suppress the heavy shuttling in the lean electrolyte, thus to acquire a high volumetric energy density without sacrificing gravimetric performance for realistic Li-S batteries (LSBs). Herein, we develop a cation-doping strategy to tailor the electronic structure and catalytic activity of MoSe 2 that in situ hybridized with conductive Ti 3 C 2 T x MXene, thus obtaining a Co-MoSe 2 /MXene bifunctional catalyst as a high-efficient sulfur host. Combining a smart design of the dense sulfur structure, the as-fabricated highly dense S/Co-MoSe 2 /MXene monolith cathode (density: 1.88 g cm -3 , conductivity: 230 S m -1 ) achieves a high reversible specific capacity of 1454 mAh g -1 and an ultrahigh volumetric energy density of 3659 Wh L -1 at a routine electrolyte and a high areal capacity of ∼8.0 mAh cm -2 under an extremely lean electrolyte of 3.5 μL mg s -1 at 0.1 C. Experimental and DFT theoretical results uncover that introducing Co element into the MoSe 2 plane can form a shorter Co-Se bond, impel the Mo 3d band to approach the Fermi level, and provide strong interactions between polysulfides and Co-MoSe 2 , thereby enhancing its intrinsic electronic conductivity and catalytic activity for fast redox kinetics and uniform Li 2 S nucleation in a dense high-sulfur-loaded cathode. This deep work provides a good strategy for constructing high-volumetric-energy-density, high-areal-capacity LSBs with lean electrolytes.