Recent progress on confinement of polysulfides through physical andchemical methods

With high theoretical energy density and the natural abundance of S, lithium-sulfur （Li-S） batteries areconsidered to be the promising next generation high-energy rechargeable energy storage devices. How-ever, issues including electronical insulation of S, the lithium polysulfides （LiPSs） dissolution and the shortcycle lifespan have prevented Li-S batteries from being practical applied. Feasible settlements of confiningLiPSs to reduce the loss of active substances and improve the cycle stability include wrapping sulfur withcompact layers, designing matrix with porous or hollow structures, adding adsorbents owning stronginteraction with sulfur and inserting polysulfide barriers between cathodes and separators. This reviewcategorizes them into physical and chemical confinements according to the influencing mechanism. Withfurther discussion of their merits and flaws, synergy of the physical and chemical confinement is believedto be the feasible avenue that can guide Li-S batteries to the practical application.

Insights into the nitride-regulated processes at the electrolyte/electrode interface in quasi-solid-state lithium metal batteries

Gel polymer electrolytes(GPEs)are one of the promising candidates for high-energy-density quasi-solid-state lithium metal batteries(QSSLMBs),for their high ionic conductivity and excellent interfacial compatibility.The comprehension of dynamic evolution and structure-reactivity correlation at the GPE/Li interface becomes significant.Here,in situ electrochemical atomic force microscopy(EC-AFM)provides insights into the LiNO_(3)-regulated micromechanism of the Li plating/stripping processes upon cycles in GPE-based LMBs at nanoscale.The additive LiNO_(3)induces the formation of amorphous nitride SEI film and facilitates Li^(+) ion diffusion.It stabilizes a compatible interface and regulates the Li nucleation/growth at steady kinetics.The deposited Li is in the shape of chunks and tightly compact.The Li dissolution shows favorable reversibility,which guarantees the cycling performance of LMBs.In situ AFM monitoring provides a deep understanding into the dynamic evolution of Li deposition/dissolution and the interphasial properties of tunable SEI film,regulating the rational design of electrolyte and optimizing interfacial establishment for GPE-based QSSLMBs.

Electrode materials for aqueous multivalent metal-ion batteries: Current status and future prospect

In recent years,the pursuit of high-efficiency electrochemical storage technology,the multivalent metalion batteries (MIBs) based on aqueous electrolytes have been widely explored by researchers because of their safety,environmental friendliness,abundant reserves and low price,and especially the merits in energy and power densities.This review firstly expounds on the problems existing in the electrode materials of aqueous multivalent MIBs (Zn^(2+),Mg^(2+),Al^(3+),Ca^(2+)),from the classical inorganic materials to the emerging organic compounds,and then summarizes the design strategies in bulk and interface structure of electrodes with favorable kinetics and stable cycling performance,especially laying the emphasis on the charge storage mechanism of cathode materials and dendrite-free Zinc anode from the aspect of electrolyte optimization strategies,which can be extended to other aqueous multivalent MIBs.Ultimately,the possible development directions of the aqueous multivalent MIBs in the future are provided,anticipating to provide a meaningful guideline for researchers in this area.

Stable Li storage in micron-sized SiO_(x) particles with rigid-flexible coating

Micrometre-sized electrode materials have distinct advantages for battery applications in terms of energy density,processability,safety and cost.For the silicon monoxide anode that undergoes electrochemical alloying reaction with Li,the Li(de)intercalation by micron-sized active particles usually accompanies with a large volume variation,which pulverizes the particle structure and leads to rapidly faded storage performance.In this work,we proposed to stabilize the electrochemistry vs.Li of the micron-SiO_(x) anode by forming a rigid-flexible bi-layer coati ng on the particle surface.The coati ng consists of pyrolysis carbon as the inner layer and polydopamine as the outer layer.While the inner layer guarantees high structural rigidity at particle surface and provides efficient pathway for electron conduction,the outer layer shows high flexibility for maintaining the integrity of micrometre-sized particles against drastic volume variation,and together they facilitate formation of stable solid electrolyte interface on the SiO_(x) particles.A composite an ode prepared by mixing the coated micron-SiOx with graphite delivered improved Li storage performance,and promised a high-capacity,long-life LiFePO_(4)/SiO_(x)-graphite pouch cell.Our strategy provides a general and feasible solution for building high-energy rechargeable batteries from micrometre-sized electrode materials with significant volume variation.

Roadmap for rechargeable batteries:present and beyond

Rechargeable batteries currently hold the largest share of the electrochemical energy storage market,and they play a major role in the sustainable energy transition and industrial decarbonization to respond to global climate change.Due to the increased popularity of consumer electronics and electric vehicles,lithium-ion batteries have quickly become the most successful rechargeable batteries in the past three decades,yet growing demands in diversified application scenarios call for new types of rechargeable batteries.Tremendous efforts are made to developing the next-generation post-Li-ion rechargeable batteries,which include,but are not limited to solid-state batteries,lithium–sulfur batteries,sodium-/potassium-ion batteries,organic batteries,magnesium-/zinc-ion batteries,aqueous batteries and flow batteries.Despite the great achievements,challenges persist in precise understandings about the electrochemical reaction and charge transfer process,and optimal design of key materials and interfaces in a battery.This roadmap tends to provide an overview about the current research progress,key challenges and future prospects of various types of rechargeable batteries.New computational methods for materials development,and characterization techniques will also be discussed as they play an important role in battery research.

Solid-state lithium-ion batteries for grid energy storage:opportunities and challenges

The energy crisis and environmental pollution drive more attention to the development and utilization of renewable energy.Considering the capricious nature of renewable energy resource,it has difficulty supplying electricity directly to consumers stably and efficiently,which calls for energy storage systems to collect energy and release electricity at peak periods.Due to their flexible power and energy,quick response,and high energy conversion efficiency,lithium-ion batteries stand out among multiple energy storage technologies and are rapidly deployed in the grid.Pursuing superior performance and ensuring the safety of energy storage systems,intrinsically safe solid-state electrolytes are expected as an ideal alternative to liquid electrolytes.In this review,we systematically evaluate the priorities and issues of traditional lithium-ion batteries in grid energy storage.Beyond lithium-ion batteries containing liquid electrolytes,solid-state lithium-ion batteries have the potential to play a more significant role in grid energy storage.The challenges of developing solid-state lithium-ion batteries,such as low ionic conductivity of the electrolyte,unstable electrode/electrolyte interface,and complicated fabrication process,are discussed in detail.Additionally,the safety of solid-state lithium-ion batteries is re-examined.Following the obtained insights,inspiring prospects for solid-state lithium-ion batteries in grid energy storage are depicted.

Preface:special topic on rechargeable battery technology

Rechargeable batteries play a major role in the transition from fossil energy to renewable energy and are considered the key-enabling decarbonization technology for several industries,including electronics,transportation,and future-oriented artificial intelligence and aerospace,in response to global climate change.

Structural Restoration of Degraded LiFePO_(4)Cathode with Enhanced Kinetics Using Residual Lithium in Spent Graphite Anodes

Enormous LiFePO_(4)(LFP)/graphite batteries retired from the market need urgent rational disposal and reutilization based on the degradation analysis of the evolutional mechanism for electrodes.Typically,Li inventory loss is one of the main reasons for the degradation of LFP-based batteries.The reduced portion of lithium in a cathode is inevitably consumed to form solid electrolyte interphase or trapped in the anode.Herein,we propose a comprehensive strategy for battery recycling and conduct the work by simply regenerating the degraded LFP materials directly with the extracted lithium compounds from spent anodes.Moreover,inter-particle three-dimensional(3D)conductive networks are built via an in situ carbonization to reinforce the electronic conductivity of regenerated cathodes.An improved electrochemical performance was achieved in the regenerated LFP materials even compared with the pristine LFP.This integrated recycling strategy not only brings more added value to the recycled materials by leveraging the recycling process but also aims to apply the concept of“treating waste with waste”and spur innovations in battery recycling technologies in the future.

Hydrogen isotope effects: A new path to high-energy aqueous rechargeable Li/Na-ion batteries

Aqueous rechargeable Li/Na-ion batteries have shown promise for sustainable large-scale energy storage due to their safety,low cost,and environmental benignity.However,practical applications of aqueous batteries are plagued by water's intrinsically narrow electrochemical stability window,which results in low energy density.In this perspective article,we review several strategies to broaden the electrochemical window of aqueous electrolytes and realize high-energy aqueous batteries.Specifically,we highlight our recent findings on stabilizing aqueous Li storage electrochemistry using a deuterium dioxide-based aqueous electrolyte,which shows significant hydrogen isotope effects that trigger a wider electrochemical window and inhibit detrimental parasitic processes.

An ion-percolating electrolyte membrane for ultrahigh efficient and dendrite-free lithium metal batteries

The development of lithium(Li)metal batteries has been severely limited by the formation of lithium dendrites and the associated catastrophic failure and inferior Coulombic efficiency which caused by non-uniform or insufficient Li^(+)supply across the electrode-electrolyte interface.Therefore,a rational strategy is to construct a robust electrolyte that can allow efficient and uniform Li^(+)transport to ensure sufficient Li^(+)supply and homogenize the Li plating/stripping.Herein,we report an ion-percolating electrolyte membrane that acts as a stable Li^(+)reservoir to ensure a near-single Li^(+)transference number(0.78)and homogenizes Li^(+)migration to eradicate dendrite growth,endowing Li//LFP cell with an ultrahigh average Coulombic efficiency(ca.99.97%)after cycling for nearly half of a year and superior cycling stability when pairing with LiCoO_(2) with limited Li amount and LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2).These estimable attributes demonstrate significant potential of utility value for the ion-percolating electrolyte.

Designing solid-state interfaces on lithium-metal anodes: a review

Li-metal anodes are one of the most promising energy storage systems that can considerably exceed the current technology to meet the ever-increasing demand of power applications. The apparent cycling performances and dendrite challenges of Li-metal anodes are highly influenced by the interface layer on the Li-metal anode because the intrinsic high reactivity of metallic Li results in an inevitable solid-state interface layer between the Li-metal and electrolytes. In this review, we summarize the recent progress on the interfacial chemistry regarding the interactions between electrolytes and ion migration through dynamic interfaces. The critical factors that affect the interface formation for constructing a stable interface with a low resistance are reviewed. Moreover, we review emerging strategies for rationally designing multiple-structured solid-state electrolytes and their interfaces, including the interfacial properties within hybrid electrolytes and the solid electrolyte/electrode interface. Finally, we present scientific issues and perspectives associated with Li-metal anode interfaces toward a practical Li-metal battery.

Sodium iron hexacyanoferrate with high Na content as a Na-rich cathode material for Na-ion batteries

Owing to the worldwide abundance and low-cost of Na, room-temperature Na-ion batteries are emerging as attractive energy storage systems for large- scale grids. Increasing the Na content in cathode materials is one of the effective ways to achieve high energy density. Prussian blue and its analogues （PBAs） are promising Na-rich cathode materials since they can theoretically store two Na＋ ions per formula unit. However, increasing the Na content in PBAs cathode materials remains a major challenge. Here we show that sodium iron hexacyanoferrate with high Na content can be obtained by simply controlling the reducing agent and reaction atmosphere during synthesis. The Na content can reach as high as 1.63 per formula, which is the highest value for sodium iron hexacyanoferrate. This Na-rich sodium iron hexacyanoferrate demonstrates a high specific capacity of 150 mAh·g^-1 and remarkable cycling performance with 90% capacity retention after 200 cycles. Furthermore, the Na intercalation/ de-intercalation mechanism has been systematically studied by in situ Raman spectroscopy, X-ray diffraction and X-ray absorption spectroscopy analysis for the first time. The Na-rich sodium iron hexacyanoferrate can function as a plenteous Na reservoir and has great potential as a cathode material for practical Na-ion batteries.

Air-stability of sodium-based layered-oxide cathode materials

Sodium-ion batteries have the potential to be an alternative to lithium-ion batteries especially for applications such as large-scale grid energy storage. The development of suitable cathode materials is crucial to the commercialization of sodium-ion batteries.Sodium-based layered-type transition metal oxides are promising candidates as cathode materials as they offer decent energy density and are easy to be synthesized. Unfortunately, most layered oxides suffer from poor air-stability, which greatly increases the cost of manufacturing and handling. The air-sensitivity severely limits the development and commercial application of sodium-ion batteries. A review that summarizes the latest understanding and solutions of air-sensitivity is desired. In this review,the background and fundamentals of sodium-based layered-type cathode materials are presented, followed by a discussion on the latest research on air-sensitivity of these materials. The mechanism is complex and involves multiple chemical and physical reactions. Various strategies are shown to alleviate some of the corresponding problems and promote the feasible application of sodium-ion batteries, followed by an outlook on current and future research directions of air-stable cathode materials. It is believed that this review will provide insights for researchers to develop practically relevant materials for sodium-ion batteries.

Advances of polymer binders for silicon-based anodes in high energy density lithium-ion batteries

Conventional lithium-ion batteries(LIBs)with graphite anodes are approaching their theoretical limitations in energy density.Replacing the conventional graphite anodes with high-capacity Si-based anodes represents one of the most promising strategies to greatly boost the energy density of LIBs.However,the inherent huge volume expansion of Si-based materials after lithiation and the resulting series of intractable problems,such as unstable solid electrolyte interphase layer,cracking of electrode,and especially the rapid capacity degradation of cells,severely restrict the practical application of Sibased anodes.Over the past decade,numerous reports have demonstrated that polymer binders play a critical role in alleviating the volume expansion and maintaining the integrity and stable cycling of Si-based anodes.In this review,the state-of-the-art designing of polymer binders for Si-based anodes have been systematically summarized based on their structures,including the linear,branched,crosslinked,and conjugated conductive polymer binders.Especially,the comprehensive designing of multifunctional polymer binders,by a combination of multiple structures,interactions,crosslinking chemistries,ionic or electronic conductivities,soft and hard segments,and so forth,would be promising to promote the practical application of Si-based anodes.Finally,a perspective on the rational design of practical polymer binders for the large-scale application of Si-based anodes is presented.

Improving the stability of LiNi_(0.80)Co_(0.15)Al_(0.05)O_2 by AlPO_4 nanocoating for lithium-ion batteries

Nickel-rich layered materials,such as LiNi_(0.8)0Co_(0.15)Al_(0.05)O_2(NCA),have been considered as one alternative cathode materials for lithium-ion batteries(LIBs) due to their high capacity and low cost.However,their poor cycle life and low thermal stability,caused by the electrode/electrolyte side reaction,prohibit their prosperity in practical application.Herein,AlPO4 has been homogeneously coated on the surface of NCA via wet chemical method towards the target of protecting NCA from the attack of electrolyte.Compared with the bare NCA,NCA@AlPO_4 electrode delivers high capacity without sacrificing the discharge capacity and excellent cycling stability.After 150 cycles at 0.5 C between 3.0-4.3 V,the capacity retention of the coated material is 86.9%,much higher than that of bare NCA(66.8%).Furthermore,the thermal stability of cathode is much improved due to the protection of the uniform coating layer on the surface of NCA.These results suggest that AlPO4 coated NCA materials could act as one promising candidate for next-generation LIBs with high energy density in the near future.

In situ fluorinated solid electrolyte interphase towards long-life lithium metal anodes

The urgent demands for high-energy-density rechargeable batteries promote a flourishing development of Li metal anode.However,the uncontrollable dendrites growth and serious side reactions severely lirmit its commercial application.Herein,an artificial LiF-rich solid electrolyte interphase(SEl)is constructed at molecular-level using one-step photopolymerization of hexafluorobutyl acrylate based solution,where the LiF is in situ generated during photopolymerization process(denoted as PHALF).The LiF-rich layercomprised flexible polymer matrix and inorganic LiF filler not only ensures intimate contact with Li anode and adapts volume fluctuations during cycling but also regulates Li deposition behavior,enabling it to suppress the dendrite growth and block side reactions between the electrolyte and Li metal.Accordingly,the PHALF-Li anode presents superior stable cycling performance over 500 h at 1 mA·cm^-2 for 1 mA·h·cm^-2 without dendrites growth in carbonate electrolyte.The work provides a novel approach to design and build in situ artificial SEl layer for high-safety and stable Li metal anodes.

Chalcogen cathode and its conversion electrochemistry in rechargeable Li/Na batteries

Chalcogen elements,such as sulfur(S),selenium(Se),tellurium(Te)and the interchalcogen compounds,have been studied extensively as cathode materials for the next-generation rechargeable lithium/sodium(Li/Na)batteries.The high energy output of the Li/Na-chalcogen battery originates from the two-electron conversion reaction between chalcogen cathode and alkali metal anode,through which both electrodes are able to deliver high theoretical capacities.The reaction also leads to parasitic reactions that deteriorate the chemical environment in the battery,and different cathode-anode combinations show their own features.In this article,we intend to discuss the fundamental conversion electrochemistry between chalcogen elements and alkali metals and its potential influence,either positive or negative,on the performance of batteries.The strategies to improve the conversion electrochemistry of chalcogen cathode are also reviewed to offer insights into the reasonable design of rechargeable Li/Nachalcogen batteries.

Raising the capacity of lithium vanadium phosphate via anion and cation co-substitution

The pursuit for batteries with high specific energy provokes the research of high-voltage/capacity cathode materials with superior stability and safety as the alternative for lithium iron phosphate.Herein,using the sol-gel method,a lithium vanadium phosphate with higher average discharge voltage(3.8 V,vs.Li+/Li) was obtained from a single source for Mg2+ and Cl-co-substitution and uniform carbon coating,and a nearly theoretical capacity(130.1 mA h g^-1) and outstanding rate performance(25 C) are acquired together with splendid capacity retention(80%) after 650 cycles.This work reveals that the well-sized anion and cation substitution and uniform carbon coating are of both importance to accelerate kinetic performance in the context of nearly undisturbed crystal structure for other analogue materials.It is anticipated that the electrochemistry comprehension will shed light on preparing cathode materials with high energy density in the future.

Large-Scale Synthesis of the Stable Co-Free Layered Oxide Cathode by the Synergetic Contribution of Multielement Chemical Substitution for Practical Sodium-Ion Battery

The O3-type layered oxide cathodes for sodium-ion batteries(SIBs)are considered as one of the most promising systems to fully meet the requirement for future practical application.However,fatal issues in several respects such as poor air stability,irreversible complex multiphase evolution,inferior cycling lifespan,and poor industrial feasibility are restricting their commercialization development.Here,a stable Co-free O3-type NaNi_(0.4)Cu_(0.05)Mg_(0.05)Mn_(0.4)Ti_(0.1O2) cathode material with large-scale production could solve these problems for practical SIBs.Owing to the synergetic contribution of the multielement chemical substitution strategy,this novel cathode not only shows excellent air stability and thermal stability as well as a simple phase-transition process but also delivers outstanding battery performance in half-cell and full-cell systems.Meanwhile,various advanced characterization techniques are utilized to accurately decipher the crystalline formation process,atomic arrangement,structural evolution,and inherent effect mechanisms.Surprisingly,apart from restraining the unfavorable multiphase transformation and enhancing air stability,the accurate multielement chemical substitution engineering also shows a pinning effect to alleviate the lattice strains for the high structural reversibility and enlarges the interlayer spacing reasonably to enhance Na^(+)diffusion,resulting in excellent comprehensive performance.Overall,this study explores the fundamental scientific understandings of multielement chemical substitution strategy and opens up a new field for increasing the practicality to commercialization.

Structurally modulated Li-rich cathode materials through cooperative cation doping and anion hybridization

High capacity Li-rich materials are mighty contenders for building rechargeable batteries that coincide with the demand in energy density. Fully realizing the extraordinary capacity involves oxygen evolution and related cation migration, resulting in phase transitions and deteriorations that would hinder their practical application. In an attempt to enhance the anodic redox participation and stabilize the structure at the same time, we proposed a structural modulation strategy with modification on anion hybridization intensifying and cation doping. Spectator ions with large ionic radius were introduced into the lattice during calcination with stannous chloride and the d-p hybridization between transition metal 3 d and oxygen 2 p orbitals was subsequently intensified along with expelling weakly bonded chloride species in the reheating process. Both of the reversible capacity and stability upon cycling were remarkably improved through the cooperation of bond alteration and dopant. This strategy might provide new insight into the modulation of the structure to truly fulfill the potential of Li-rich materials.