The dendrite-free Zn anode is crucial for the commercialization of aqueous Zn-metal batteries (ZMBs), but dendrite growth and thermodynamic instability are two major obstacles. Regulating the specific crystal plane growth of Zn can effectively address these issues. Here, we propose an in situ construction of a selective self-assembled monolayer (S-SAM) strategy to induce the growth of the (002) crystal plane (85%) and improve the interface properties. Specifically, 2,2'-dithiobis(ethylamine) generated unsaturated -S groups through the cleavage of S-S bonds, which selectively self-assemble on the (100) and (101) planes to shield the nucleation process of these planes, leading to the single growth of (002) plane finally. Therefore, compared to the blank electrolyte, the S-SAM anode with preferential exposure of the (002) crystal plane significantly improved cycling lifetime under conditions of high current density and large plating capacity, with a cumulative plating capacity exceeding 2.875 Ah cm(-2). Furthermore, a Zn//V2O5 full battery with an areal capacity of over 11 mAh cm(-2) achieved more than 128 stable cycles at 0.4 A g(-1). This study enhances the understanding of SAM in crystal plane regulation and has universal value for constructing metal batteries with ultra-high areal capacities.

Lithium-rich manganese-based cathode materials (LR) offer ultra-high capacity and energy density due to their cation/anion co-redox mechanism. However, the layered structure irreversibly changes to spinel/rock-salt phase during cycling, resulting in serious voltage and capacity attenuation. Traditional strategies to block phase transitions often sacrifices capacity, this study proposes a diversion strategy: implanting highly dispersed micro-spinel dots into layered phases via hydrothermal sulfidation followed by lithium calcination. This actively constructs a sulfur-doped layered-spinel heterostructure lithium-rich manganese-based cathode material (LRS). S anions incorporate into oxygen sites, expanding lattice spacing and reducing Li+/Ni2+ mixing without altering transition metal valence. More importantly, the spinel phase template preferentially formed by Mn/Co ions during hydrothermal process evolved into uniformly dispersed micro-spinel dots after lithiation. The three-dimensional ion channel of spinel phase alleviates the anisotropic lattice strain, and its thermodynamic stability inhibits the spread of harmful phase transition. Consequently, the optimized LRS delivers a high capacity retention of 89.7% after 500 cycles at 1C and significantly mitigates voltage decay with 94.2% voltage retention after 200 cycles. This study achieved the implantation of micro-spinel dots with high bulk dispersion through sulfur doping, effectively suppressing structural distortion and opening a new pathway for developing high-energy-density cathode materials.

Direct metal anodes are plating/stripping processes without a supporting framework and bulk ion conductivity; they are the electrodes susceptible to collapse and limiting the electrochemical reaction to the two-dimensional surface. The focus of this era is mostly on building a solid electrolyte interface (SEI). However, simply building protective layers cannot address essential issues; a thorough transformation of the metal electrode bulk is critical. We propose a reconstructed sodium metal anode (RSMA) by implanting an activatable ion-conductive network to the bulk. NaPF6 will be activated with an electrolyte to conduct ions and form an anion-derived SEI. Conductive polymers become the supporting skeleton; thus, the RSMA has a metal-bulk storage matrix and an expanded three-dimensional plating/stripping mechanism and permits the homogeneous deposition/dissolution of Na+ in high dimensions. Last, RSMA symmetric cells were stably cycled for 2700 hours and achieved a 100% depth of discharge. RSMA||PB cells can achieve 10-coulomb cycling and a proof-of-concept pouch cell energy density of 367 watt-hours per kilogram.

Rechargeable aluminum-ion batteries with graphite as cathode material are highly attractive for energy storage due to their low cost, high abundance, and high capacity. Although some techniques have been employed to investigate intercalation/deintercalation behavior of AlCl4 - in graphite materials, the microscopic mechanism remains ambiguous and controversial, leading to a question that needs to be answered. Therefore, direct and in-situ characterization of nanoscale variations in the z direction is a reliable avenue to finding the answer to the intercalation stage mechanism. In this work, in-situ AFM was used to directly monitor the intercalation/deintercalation process of AlCl4 - in highly oriented pyrolytic graphite, pyrolytic graphite and natural graphite electrode materials. We demonstrate that during the initial stage of intercalation, AlCl4 - ions tend to intercalate intensively into the same graphite layer, and that as potential increases the intercalation of AlCl4 - ions displays a mixed-staged process. Moreover, during the intercalation of AlCl4 - into the pyrolytic graphite electrode, noticeable exfoliation of the graphite layers was observed. This phenomenon accounts for the energy loss that occurs in the initial cycles of the graphite/Al battery system. Finally, we propose an optimization strategy to prevent exfoliation.

Constructing an enhanced SEI based on the mortise and tenon joints using chemical and electrochemical reactions.

Lithium metal has been considered the most ideal choice for the anode in rechargeable high energy density batteries. Direct metal anode is a plating/stripping process without any self‐supporting framework, thus making the metal electrodes susceptible to collapse and difficult for the repeating processes. Herein, we construct a stretchable molecular chain as a flexible skeleton to achieve the lithium repeated plating/stripping. The Cu x S‐In 2 S 3 can in situ be converted into lithiophilic LixIny and Li 2 S composites during the lithium deposition process in which an “expandable molecule chains” is formed through the S connections. Once formed, the lithiophilic chains remain existing stable but just their upright state changes thus serving as a functionalized flexible matrix (FFM) for the lithium dissolution and deposition process. Benefiting from these features, the anode‐free full cells FFM||LFP display superior cycling stability and long lifespan, with a high‐capacity retention of 86.7 % at 0.2 C‐rate after 100 cycles. These explorations provide new strategies for developing high‐performance ‘Anode‐free’ lithium metal battary (AFLMB).

The practical application of lithium–sulfur batteries is hindered by the polysulfide shuttle effect and sluggish kinetics inherent in solid–liquid–solid conversion mechanism, particularly under lean electrolyte conditions (<5 µL mg⁻¹). Weakly solvating electrolytes and localized high‐concentration electrolytes can suppress polysulfide dissolution and enable a quasi‐solid‐phase mechanism but suffer from severely limited reaction kinetics. Herein, a clustered‐polysulfide‐mediated sulfur conversion mechanism enabled by a novel electrolyte composed of 1,2‐dimethylbenzene (DTL) and 1,2‐dimethoxyethane (DME) is proposed. The encapsulation effect of DTL and the coordination of TFSI⁻ with polysulfides drives the aggregation of polysulfides so that the clustered polysulfides with virtual shell boundaries can be the new basic reactive that bridges the gap between the traditional dissolution‐dominated mechanism and quasi‐solid‐state mechanism. The clustered polysulfide electrolyte (CPE) not only suppresses the shuttle effect and stabilizes the lithium anode by mitigating parasitic reactions but also enables alternative reaction kinetics and promotes 3D Li₂S deposition, minimizing electrode passivation. Ultimately, lithium–sulfur batteries can achieve excellent electrochemical performance and can stably operate under lean electrolyte (<4.0 µL mg⁻¹) with an area capacity of >4 mAh cm −2 . This work elucidates the relationship between polysulfide dissolution behavior and redox kinetics, providing a new insight into the understanding of complex sulfur conversion mechanisms.

Lithium-oxygen (Li-O2) batteries, renowned for their high theoretical energy density, have garnered significant interest as prime candidates for future electric device development. However, their actual capacity is often unsatisfactory due to the passivation of active sites by solid-phase discharge products. Optimizing the growth and storage of these products is a crucial step in advancing Li-O2 batteries. Here, a fluorine-doped bimetallic cobalt-nickel oxide (CoNiO2- xFx/CC) with an interlaced catalytic surface (ICS) and a corncob-like structure is proposed as an oxygen electrode. Unlike conventional oxide electrodes with a "single adsorption catalytic mechanism," the ICS of CoNiO2- xFx/CC offers a "competitive adsorption catalytic mechanism," where oxygen sites facilitate oxygen conversion while fluorine sites contribute to the growth of Li2O2. This results in a change in Li2O2 morphology from a surface film to toroidal particles, effectively preventing the burial of active sites. Additionally, the unique open architecture aids in the capture and release of oxygen and the formation of well-contacted Li2O2/electrode interfaces, which benefits the complete decomposition of Li2O2 products. Consequently, the Li-O2 battery with a CoNiO2- xFx/CC cathode demonstrates a high specific capacity of up to 30923 mAh g-1 and a lifespan exceeding 580 cycles, surpassing most reported metal oxide-based cathodes.

Rechargeable lithium batteries using 5 V positive electrode materials can deliver considerably higher energy density as compared to state-of-the-art lithium-ion batteries. However, their development remains plagued by the lack of electrolytes with concurrent anodic stability and Li metal compatibility. Here we report a new electrolyte based on dimethyl 2,5-dioxahexanedioate solvent for 5 V-class batteries. Benefiting from the particular chemical structure, weak interaction with lithium cation and resultant peculiar solvation structure, the resulting electrolyte not only enables stable, dendrite-free lithium plating-stripping, but also displays anodic stability up to 5.2 V (vs. Li/Li + ), in additive or co-solvent-free formulation, and at low salt concentration of 1 M. Consequently, the Li | |LiNi 0.5 Mn 1.5 O 4 cells using the 1 M LiPF 6 in 2,5-dioxahexanedioate based electrolyte retain >97% of the initial capacity after 250 cycles, outperforming the conventional carbonate-based electrolyte formulations, making this, and potentially other dicarbonate solvents promising for future Lithium-based battery practical explorations.

For the lithium (Li) metal anode, constructing a strong and durable protective layer with lithium-ion permeability is crucial, especially in high donor number (DN) solvent system. High DN solvent-based electrolytes can support both higher capacity and lower charge overpotential in the rechargeable lithium-oxygen batteries (LOBs). However, Li anodes in high DN solvent system suffer from severe corrosion and uncontrolled dendrite growth due to the unstable solid-electrolyte interphase (SEI). Typically, this interface is formed in situ through electrochemical processes with complicated component and spatial distribution. Here, a functional molecule is introduced to construct an ion-wall (IW) on Li surface by prechemical sequential reactions (p-CSRs), through which the crystalline nanoparticles as bricks and amorphous hybrid compounds as the mortar can be produced to build such a "wall." Different from the conventional SEI, this wall is not only compact and uniform, but also possess high strength, excellent passivation properties and high ionic conductivity. With these properties, the IW could suppress Li dendrites and inhabit the side reaction, supporting highly reversible Li plating/stripping behavior in high DN solvent system. As a result, the cycle stability of LOBs based on the IW protected Li anode is significantly improved.

Thick electrodes represent an effective approach for augmenting energy density of batteries. However, their increased thickness invariably leads to longer electron and ion transport distance, limiting the utilization of active material and hindering practical application. Herein, an electron‐conducting‐enhanced and ion‐conducting‐enhanced strategy is presented for fabricating ultrahigh loading electrodes via constructing an interlaced 3D network. Carbon nanotubes (CNTs) serve as extended electron pathways. Different from the polyvinylidene fluoride binder which needs to be dissolved into molecules for preparing electrode, polytetrafluoroethylene (PTFE), however, exists as a separate phase inside the electrode, thus can become the extended pathways for electrolyte elongating due to its strong affinity to organic electrolyte. Note that based on the synergistic effect between CNT and PTFE, the latter can exhibit a form of long‐distance extension fibers rather than agglomeration. Finally, a LiFePO4 electrode with a record‐high loading of 141 mg cm−2 is successfully prepared. This electrode exhibits outstanding area capacity (20.7 mAh cm−2 at 0.2 C) and cycling stability with impressive energy density of 224 Wh kg−1 and 517 Wh L−1 in a full cell (graphite anode). The findings present a novel strategy for achieving high energy density in lithium‐ion batteries using existing material systems.

Constructing powerful anode/cathode interphases by modulate ion solvation structure is the principle of electrolyte design. However, the methodological and theoretical design principles of electrolyte/solvation structure and their effect on electrochemical performance are still vague. Here, we propose a cationic weakly coordinating-intervention strategy for modulating the Na+ solvation sheathes and constructing robust anode/cathode interphases in sodium-metal batteries. Unlike the local highly concentrated electrolytes, 1,2-difluorobenzene can weakly coordinate with Na+ thus transforming the solvation structure into Na+-anion-incorporated structures and strengthening anode/cathode interphases formation by combining with salt decomposition. Furthermore, the correlations between the electrode interface properties and solvation structure are revealed, which can be tuned by the weakly coordination. Ultimately, the modulated electrolyte achieves 97.5% Coulombic efficiency for 600 cycles in Na & Vert;Cu cells at 1 mA cm(-2) and a beneficial lifetime (2500 h) in Na & Vert;Na cells. Meanwhile, Na & Vert;PB cells have achieved long-term operation at 4.8 V, along with operation at wide temperatures.

Wide operation temperature is the crucial objective for an energy storage system that can be applied under harsh environmental conditions. For lithium-sulfur batteries, the "shuttle effect" of polysulfide intermediates will aggravate with the temperature increasing, while the reaction kinetics decreases sharply as the temperature decreasing. In particular, sulfur reaction mechanism at low temperatures seems to be quite different from that at room temperature. Here, through in situ Raman and electrochemical impedance spectroscopy studies, the newly emerged platform at cryogenic temperature corresponds to the reduction process of Li2S8 to Li2S4, which will be another rate-determining step of sulfur conversion reaction, in addition to the solid-phase conversion process of Li2S4 to Li2S2/Li2S at low temperatures. Porous bismuth vanadate (BiVO4) spheres are designed as sulfur host material, which achieve the rapid snap-transfer-catalytic process by shortening lithium-ion transport pathway and accelerating the targeted rate-determining steps. Such promoting effect greatly inhibits severe "shuttle effect" at high temperatures and simultaneously improves sulfur conversion efficiency in the cryogenic environment. The cell with the porous BiVO4 spheres as the host exhibits excellent rate capability and cycle performance under wide working temperatures.

The emergence of solid-state battery technology presents a potential solution to the dissolution challenges of high-capacity small molecule quinone redox systems. Nonetheless, the successful integration of argyrodite-type Li6PS5Cl, the most promising solid-state electrolyte system, and quinone redox systems remains elusive due to their inherent reactivity. Here, a library of quinone derivatives is selected as model electrode materials to ascertain the critical descriptors governing the (electro)chemical compatibility and subsequently the performances of Li6PS5Cl-based solid-state organic lithium metal batteries (LMBs). Compatibility is attained if the lowest unoccupied molecular orbital level of the quinone derivative is sufficiently higher than the highest occupied molecular orbital level of Li6PS5Cl. The energy difference is demonstrated to be critical in ensuring chemical compatibility during composite electrode preparation and enable high-efficiency operation of solid-state organic LMBs. Considering these findings, a general principle is proposed for the selection of quinone derivatives to be integrated with Li6PS5Cl, and two solid-state organic LMBs, based on 2,5-diamino-1,4-benzoquinone and 2,3,5,6-tetraamino-1,4-benzoquinone, are successfully developed and tested for the first time. Validating critical factors for the design of organic battery electrode materials is expected to pave the way for advancing the development of high-efficiency and long cycle life solid-state organic batteries based on sulfides electrolytes.

The mixed solvent strategy was applied to construct optimized highly concentrated electrolytes (HCEs). Hybrid HCEs based on FEC and AN were investigated systematically. The accelerated ion transport and enhanced anions-derived SEI were achieved.

The high-voltage battery has now become a goal in order to meet the demands for high energy density. However, the severe side reactions between Li metal and carbonate-based electrolytes in this system result in unstable interphase, leading to non-uniform Li-ion flux and thus aggravating the dendrite growth of Li. The protect interphase, traditional solid electrolyte interface (SEI), is a loose solid layer consisted of many components, which generally does not possess the function of preventing the lithium budding. Herein, based on polysulfide solubility in ester, we proposed a strategy to eliminate the dendrite by constructing a unique SEI in which the dynamic polysulfides were in situ formed and encapsuled. For this purpose, a 2-fluorophenylsulfur pentafluoride (2-FSPF) was employed as an additive in carbonate-based electrolyte that can be decomposed electrochemically during battery operation to form such a polysulfide-rich interphase. These polysulfides with certain fluidity can adhere to dynamically the budding tip of Li metal, as a so-called tip-inhibitor, when the local current density of the tip rising, thus to hinder Li+ diffusion toward the tip, resulting in inhibiting the further growth of Li dendrites and leveling the Li deposition. At the current density of 1 mA cm(-2), the average Coulombic efficiency of Li//Cu cells is as high as 98.39% during 600 cycles, and the stable cycling of Li//Li symmetric cell reaches 3500 h. Furthermore, due to the high anodic stability, the Li//high-voltage LiCoO2 (LCO) full cells and Li-O-2 battery achieve excellent cycle performance with lean electrolyte.

基于有机离子盐(离子液体或离子塑性晶体)的离子型局部高浓电解液(iLHCEs)可用于高性能锂金属二次电池,但Li+传导能力、与锂金属负极和高电压正极的兼容性等需优化.使用有机离子塑性晶体N-乙基-N-甲基吡咯烷鎓双(三氟甲基磺酰)亚胺盐(Pyr12TFSI)构筑iLHCEs,形成的[Li+][FSI-][TFSI-][Pyr12+]紧密离子簇可衍生稳定的固体电解质相界面(SEI),抑制副反应发生与锂枝晶生成,使锂沉积/剥离的库仑效率高达99.03％.使用基于Pyr12TFSI的iLHCEs的高电压Li|LiCoO2(4.5 V)及Li|LiNi0.5Mn1.5O4(5.0 V)电池,具有较高的首次库仑效率、长循环稳定性及理想的倍率性能.

Lithium-rich materials exhibit high capacity and high voltage properties due to the charge compensation mechanism, but the disadvantages such as material voltage decay and poor cycling stability limit their practical application. The fixation and stabilizations of surface lattice oxygen is considered the most challenging problem the materials. We have successfully prepared a lithium-rich cathode material with a triad of oxygen vacancies, surface spinel and polyanionic SO 4 2− doping by a mild surface pre-activation treatment, and systematically investigated the stabilization mechanism of surface oxygen vacancies in the materials. The VS-LR 0.25 material with multiple stabilizations of oxygen vacancies exhibited excellent cycling stability and rate performance, with an initial Coulomb efficiency of 82.7%, and capacity retention of 95.1% after 200 cycles at 1 C.

Solid-state lithium metal batteries are hindered from practical applications by insufficient room-temperature ionic conductivity and poor electrode/electrolyte interfaces. Herein, we designed and synthesized a high ionic conductivity metal-organic-framework-based composite solid electrolyte (MCSE) with the synergy of high DN value ligands from Uio66-NH2 and succinonitrile (SN). XPS and FTIR reveal that the amino group (-NH2) of Uio66-NH2 and the cyano group (-C≡N) of SN have a stronger solvated coordination with Li+, which can promote the dissociation of crystalline LiTFSI, achieving an ionic conductivity of 9.23 × 10-5 S cm-1 at RT. Afterward, a flexible polymer electrolyte membrane (FPEM) with admirable ionic conductivity (1.56 × 10-4 S cm-1 at RT) and excellent electrode/electrolyte interfaces (86.2 Ω for the Li|20% FPEM|Li cell and 303.1 Ω for the LiFePO4|20% FPEM|Li cell) was successfully obtained after compounding the MCSE with polyethylene oxide (PEO). Moreover, a stable solid electrolyte layer (SEI) was formed in situ on the surface of the lithium metal, which enables the Li|20% FPEM|Li cell to exhibit remarkable cycling stability (1000 h at a current density of 0.05 mA cm-2). At the same time, the assembled LiFePO4|20% FPEM|Li cell offers a discharge-specific capacity of 155 mAh g-1 at 0.1 C and a columbic efficiency of 99.5% after 200 cycles. This flexible polymer electrolyte provides a possibility for operating long lifespan solid-state electrochemical energy storage systems at RT.