Wide Temperature Electrolytes for Lithium Batteries: Solvation Chemistry and Interfacial Reactions.

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.

Synergistically Accelerating Adsorption-Electrocataysis of Sulfur Species via Interfacial Built-In Electric Field of SnS2 -MXene Mott-Schottky Heterojunction in Li-S Batteries.

Developing efficient heterojunction electrocatalysts and uncovering their atomic-level interfacial mechanism in promoting sulfur-species adsorption-electrocatalysis are interesting yet challenging in lithium-sulfur batteries (LSBs). Here, multifunctional SnS2 -MXene Mott-Schottky heterojunctions with interfacial built-in electric field (BIEF) are developed, as a model to decipher their BIEF effect for accelerating synergistic adsorption-electrocatalysis of bidirectional sulfur conversion. Theoretical and experimental analysis confirm that because Ti atoms in MXene easily lost electrons, whereas S atoms in SnS2 easily gain electrons, and under Mott-Schottky influence, SnS2 -MXene heterojunction forms the spontaneous BIEF, leading to the electronic flow from MXene to SnS2 , so SnS2 surface easily bonds with more lithium polysulfides. Moreover, the hetero-interface quickly propels abundant Li+ /electron transfer, so greatly lowering Li2 S nucleation/decomposition barrier, promoting bidirectional sulfur conversion. Therefore, S/SnS2 -MXene cathode displays a high reversible capacity (1,188.5 mAh g-1 at 0.2 C) and a stable long-life span with 500 cycles (≈82.7% retention at 1.0 C). Importantly, the thick sulfur cathode (sulfur loading: 8.0 mg cm-2 ) presents a large areal capacity of 7.35 mAh cm-2 at lean electrolyte of 5.0 µL mgs -1 . This work verifies the substantive mechanism that how BIEF optimizes the catalytic performance of heterojunctions and provides an effective strategy for deigning efficient bidirectional Li-S catalysts in LSBs.

Unraveling the Atomic-Level Manipulation Mechanism of Li2 S Redox Kinetics via Electron-Donor Doping for Designing High-Volumetric-Energy-Density, Lean-Electrolyte Lithium-Sulfur Batteries.

Designing dense thick sulfur cathodes to gain high-volumetric/areal-capacity lithium-sulfur batteries (LSBs) in lean electrolytes is extremely desired. Nevertheless, the severe Li2 S clogging and unclear mechanism seriously hinder its development. Herein, an integrated strategy is developed to manipulate Li2 S redox kinetics of CoP/MXene catalyst via electron-donor Cu doping. Meanwhile a dense S/Cu0.1 Co0.9 P/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/Li2 S on electrocatalyst surface, thereby decreasing the diffusion energy barrier and activation energy of Li2 S nucleation and dissolution, boosting Li2 S redox kinetics, and inhibiting shuttling in the dense thick sulfur cathode. This work deeply understands the atomic-level manipulation mechanism of Li2 S redox kinetics and provides dependable principles for designing high-volumetric-energy-density, lean-electrolyte LSBs through integrating bidirectional electro-catalysts with manipulated Li2 S redox and dense-sulfur engineering.

Green and Scalable Template-Free Strategy to Fabricate Honeycomb-Like Interconnected Porous Micro-Sized Layered Sb for High-Performance Potassium Storage.

The tremendous volume change and severe pulverization of micro-sized Sb anode generate no stable capacity in potassium-ion batteries (PIBs). The honeycomb-like porous structure provides free spaces to accommodate its volume expansion and offers efficient ion transport, yet complex synthesis and low yield limits its large-scale application. Here, a green, scalable template-free method for designing a 3D honeycomb-like interconnected porous micro-sized Sb (porous-Sb) is proposed. Its honeycomb-like porous formation mechanism is also verified. Under hydrothermal conditions, Sb reacts with water and dissolved oxygen in water, undergoing non-homogeneous and continuous corrosion at grain boundaries, and producing soluble H2 Sb2 O6 (H2 O), which regulates the porous structure of Sb by controlling reaction time. Benefiting from its porous structure and micron size, porous-Sb anode displays large gravimetric and volumetric capacities with 655.5 mAh g-1 and 2,001.9 mAh cm-3 at 0.05 A g-1 and superior rate performance of 441.9 mAh g-1 at 2.0 A g-1 in PIBs. Furthermore, ex situ characterization and kinetic analysis uncover the small volume expansion and fast K+ reaction kinetics of porous Sb during potassiation/depotassiation, originating from its large electrolyte contact area and internal expansion mechanism. It verifies a green, scalable template-free strategy to construct honeycomb-like porous metals for energy storage and conversion.

Integrating Dually Encapsulated Si Architecture and Dense Structural Engineering for Ultrahigh Volumetric and Areal Capacity of Lithium Storage.

High-theoretical-capacity silicon anodes hold promise in lithium-ion batteries (LIBs). Nevertheless, their huge volume expansion (∼300%) and poor conductivity show the need for the simultaneous introduction of low-density conductive carbon and nanosized Si to conquer the above issues, yet they result in low volumetric performance. Herein, we develop an integration strategy of a dually encapsulated Si structure and dense structural engineering to fabricate a three-dimensional (3D) highly dense Ti3C2Tx MXene and graphene dual-encapsulated Si monolith architecture (HD-Si@Ti3C2Tx@G). Because of its high density (1.6 g cm-3), high conductivity (151 S m-1), and 3D dense dual-encapsulated Si architecture, the resultant HD-Si@Ti3C2Tx@G monolith anode displays an ultrahigh volumetric capacity of 5206 mAh cm-3 (gravimetric capacity: 2892 mAh g-1) at 0.1 A g-1 and a superior long lifespan of 800 cycles at 1.0 A g-1. Notably, the thick and dense monolithic anode presents a large areal capacity of 17.9 mAh cm-2. In-situ TEM and ex-situ SEM techniques, and systematic kinetics and structural stability analysis during cycling demonstrate that such superior volumetric and areal performances stem from its dual-encapsulated Si architecture by the 3D conductive and elastic networks of MXene and graphene, which can provide fast electron and ion transfer, effective volume buffer, and good electrolyte permeability even with a thick electrode, whereas the dense structure results in a large volumetric performance. This work offers a simple and feasible strategy to greatly improve the volumetric and areal capacity of alloy-based anodes for large-scale applications via integrating a dual-encapsulated strategy and dense-structure engineering.

Honeycomb-like biomass carbon with planted CoNi3 alloys to form hierarchical composites for high-performance supercapacitors.

It is a significant challenge to combine a large pseudocapacitive material with conductive honeycomb-like carbon frameworks for long-term stable supercapacitors. Herein, hierarchical composite materials are manufactured by using biomass carbon, ZIF-67, and a mild pore former (Ni(CH3COO)2) to generate alloy-type CoNi3 nanoparticles planted into conductive honeycomb-like carbon frameworks (C@ZIF-67-T). Meanwhile, the effect of carbonization temperature on the honeycomb-like pore size and the structure of composite materials is systematically investigated. As the honeycomb-like carbon skeleton structure guarantees good ionic and electronic conductivities and a large contact area, whereas the alloy nanoparticles provide a rich redox reaction for Faradaic capacitance. Therefore, the as-obtained C@ZIF-67-600 electrode presents a remarkable specific capacitance of 1044.8 F · g-1 at 1.0 A · g-1 and an ultra-long cycling stability with 30,000 cycles at 5.0 A · g-1 in a three-electrode system. In addition, the assembled C@ZIF-67-600//activated carbon asymmetrical supercapacitor exhibit a high specific capacitance of 274.4F · g-1 at 1.0 A · g-1 and a long-term stable lifespan with a capacitance retention of 87% after 20,000 cycles at 5.0 A · g-1. Besides, the asymmetrical supercapacitor also presents a maximum energy density of 85.13 Wh · kg-1 at a power density of 750 W · kg-1. Such superior electrochemical performance demonstrate that the designed electrode material provides a promising energy storage application.

Ultrahigh-Volumetric-Energy-Density Lithium-Sulfur Batteries with Lean Electrolyte Enabled by Cobalt-Doped MoSe2/Ti3C2Tx MXene Bifunctional Catalyst.

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 MoSe2 that in situ hybridized with conductive Ti3C2Tx MXene, thus obtaining a Co-MoSe2/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-MoSe2/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 mgs-1 at 0.1 C. Experimental and DFT theoretical results uncover that introducing Co element into the MoSe2 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-MoSe2, thereby enhancing its intrinsic electronic conductivity and catalytic activity for fast redox kinetics and uniform Li2S 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.

Green, Template-Less Synthesis of Honeycomb-like Porous Micron-Sized Red Phosphorus for High-Performance Lithium Storage.

Large-volume-expansion-induced material pulverization severely limits the electrochemical performance of high-capacity red phosphorus (RP) in alkali-ion batteries. Honeycomb-like porous materials can effectively solve the issues due to their abundant interconnected pore structures. Nevertheless, it is difficult and greatly challenging to fabricate a honeycomb-like porous RP that has not yet been fabricated via chemical synthesis. Herein, we successfully fabricate a honeycomb-like porous micron-sized red phosphorus (HPRP) with a controlled pore structure via a large-scale green and template-less hydrothermal strategy. It is demonstrated that dissolved oxygen in the solution can accelerate the destruction of P9 cages of RP, thus forming abundant active defects with a faster reaction rate, so the fast corrosion forms the honeycomb-like porous structure. Owing to the free volume, interconnected porous structure, and strong robustness, the optimized HPRP-36 can mitigate drastic volume variation and prevent pulverization during cycling resulting in tiny particle-level outward expansion, demonstrated by in situ TEM and ex situ SEM analysis. Thus, the HPRP-36 anode delivers a large reversible capacity (2587.4 mAh g-1 at 0.05 A g-1) and long-cycling stability with over 500 cycles (∼81.9% capacity retention at 0.5 A g-1) in lithium-ion batteries. This generally scalable, green strategy and deep insights provide a good entry point in designing honeycomb-like porous micron-sized materials for high-performance electrochemical energy storage and conversion.

Non-metallic element modified metal-organic frameworks as high-performance electrodes for all-solid-state asymmetric supercapacitors.

This paper is the first study of the application of non-metallic element modified metal-organic frameworks in supercapacitors. Three-dimensional metal-organic frameworks modified by non-metallic element have a novel flower cluster structure, which effectively improve the structural stability and the electrochemical performance of the supercapacitors. The electrochemical performances of the materials modified by the vulcanizing agent are particularly significant with a high specific capacitance of 1453.5F g-1 at a current density of 1 A g-1 and excellent cycle stability (retention rate of 89.23% after 5000 cycles). In addition, the assembled asymmetric supercapacitor S@Ni-MOF//AC also shows a high energy density of 56.85 Wh kg-1 at power density of 480 W kg-1 and good cycle stability with a capacitance retention of 86.67% after 20,000 cycles at current density 5 A g-1. As a result, metal-organic frameworks materials modified by the non-metallic element make up for the crystal defects, which can be used as promising electrode materials for practical applications.