Designing Advanced Liquid Electrolytes for Alkali Metal Batteries:Principles,Progress,and Perspectives

The ever-growing pursuit of high energy density batteries has triggered extensive efforts toward developing alkali metal(Li,Na,and K)battery(AMB)technologies owing to high theoretical capacities and low redox potentials of metallic anodes.Typically,for new battery systems,the electrolyte design is critical for realizing the battery electrochemistry of AMBs.Conventional electrolytes in alkali ion batteries are generally unsuitable for sustaining the stability owing to the hyper-reactivity and dendritic growth of alkali metals.In this review,we begin with the fundamentals of AMB electrolytes.Recent advancements in concentrated and fluorinated electrolytes,as well as functional electrolyte additives for boosting the stability of Li metal batteries,are summarized and discussed with a special focus on structure-composition-performance relationships.We then delve into the electrolyte formulations for Na-and K metal batteries,including those in which Na/K do not adhere to the Li-inherited paradigms.Finally,the challenges and the future research needs in advanced electrolytes for AMB are highlighted.This comprehensive review sheds light on the principles for the rational design of promising electrolytes and offers new inspirations for developing stable AMBs with high performance.

Gallium-based anodes for alkali metal ion batteries

Alkali metal ion batteries(AMIBs)are playing an irreplaceable part in the energy revolution,due to their intrinsic advantages of large capacity/power density and abundance of alkali metal ions in the earth’s crust.Despite their great promise,the inborn deficiencies of commercial graphite and other anodes being researched so far call for the quest of better alternatives that exhibit all-round performance with the balance of energy/power density and cycling stability.Gallium-based materials,with impressive capacity utilization and self-healing ability,provide an anticipated solution to this conundrum.In this review,an overview on the recent progress of gallium-based anodes and their storage mechanism is presented.The current strategies used as engineering solutions to meet the scientific challenges ahead are discussed,in addition to the insightful outlook for possible future study.

First-principles study on β-GeS monolayer as high performance electrode material for alkali metal ion batteries

Based on the density functional theory calculations,we have investigated the feasibility of two-dimensionalβ-GeS monolayer as high-performance anodes for alkali metal ion batteries.The results show that the electrical conductivity of β-GeS monolayer can be enhanced after adsorbing the alkali metal atoms owing to the semiconductor-to-metal transition.The low diffusion barriers of alkali metal atoms on the β-GeS surface indicate a rapid charge/discharge rate without metal clustering.Moreover,the low average open-circuit voltage(0.211 V)and a high theoretical capacity(1024 mAh·g^(-1))for Na suggest that theβ-GeS monolayer is a promising anode material for Na-ion batteries with high performance.

Revealing the structure design of alloyed based electrodes for alkali metal ion batteries with in situ TEM

Alloyed based anode materials with high theoretical specific capacity and low reaction potential are considered to be highly potential high-energy density anode materials for alkali metal ion batteries(AMIBs).Thus,the design of alloyed based materials with high electrochemical performance has attracted great attention.Among the numerous characterization methods for guiding electrode materials design,in situ transmission electron microscopy(TEM)gradually plays an irreplaceable role due to its high temporal and spatial resolution in directly observing the change of morphology,crystal structure and element evolutions.Herein,we reviewed the two current research hotspots and mainly focused on the structure design of alloyed based electrode material under the guidance of in situ TEM.Specifically,various nanostructure designs of alloyed based electrode materials with guidance of in situ TEM were employed to solve the key scientific issues of the violent volume change during alloying/dealloying processes for enhanced electrochemical performances.Mainly through introducing buffer space in the electrode material to reduce volume change to improve structural stability,including porous structure(0 D),nanotube structure(1 D),simple hollow structure,yolk-shell structure and some hybrid hollow structures(3 D).Furthermore,the direct guidance of in situ TEM is expected for creating new opportunities to nextgeneration electrode material design for AMIBs.

Rational construction of hollow nanoboxes for long cycle life alkali metal ion batteries

Hollow nanostructures are extremely attractive in energy storage and show broad application prospects.But the preparation method is accompanied by a complicated process.In this article,the CoZn-based hol-low nanoboxes with electrochemical synergy are prepared in a simple way.This structure can effectively shorten the transmission distance of ions and electrons,and alleviate the volume expansion during the cycle.In particular,bimetallic oxides are rich in oxygen vacancies,providing more active sites for electro-chemical reactions.In addition,the stepwise oxidation-reduction reaction can also improve the volume change of the electrode material.According to the kinetic analysis and density functional theory(DFT)calculation,it is confirmed that the synergistic effect of the bimetallic oxide can accelerate the reaction kinetics.Based on these characteristics,the electrode exhibits stable cycle performance and long cycle life in alkali metal ion batteries,and can provide reversible capacities of 302.1(LIBs,2000 cycles),172.5(SIBs,10000 cycles)and 109.6(PIBs,5000 cycles)mA h g^(-1)at a current density of 1.0 A g^(-1),respectively.In ad-dition,by assembling(LiCoO_(2)//CoZn-O_(2))and(Na_(3)V_(2)(PO_(4))_(3)//CoZn-O_(2))full-cells,the practical application value is demonstrated.The sharing of this work introduces a simple way to synthesize hollow nanoboxes,and shows excellent electrochemical performance,which can also be expanded in other areas.

Anodes for low-temperature rechargeable batteries

Rechargeable alkali metal ion(Li^(+),Na^(+),K^(+))batteries have shown great success in room-temperature energy storage.However,their low-temperature(subzero temperature)applications are still severely restricted,and the poor electrochemical performance of the anode materials at low temperature serves as a critical obstacle.Therefore,it is urgent to obtain a comprehensive understanding towards the key effects of low temperatures on the performance of the anodes and overview the related improving strategies.In this work,the effects that temperature would impose on electrode performance are firstly discussed.Next,the progress in low-temperature anodes of alkali metal ion batteries is reviewed,by the classification of the reaction types of the anode materials,including intercalation-type anodes,conversion-type anodes,alloy anodes and alkali metal anodes,and corresponding strategies to improve the performance of the anodes are summarized as well.At last,some promising research directions in this field are proposed.This work is intended to shed some light on future exploitation of high-performance low-temperature anode materials.

Sb nanoparticles encapsulated in N-doped carbon nanotubes as freestanding anodes for high-performance lithium and potassium ion batteries

Sb-based materials with high specific capacity have targeted as an alternative anode material for alkali metal ion batteries.Herein,Sb nanoparticles embedded in hollow porous N-doped carbon nanotubes(Sb@N-C nanotubes)are used as freestanding anode for Li-ion batteries(LIBs)and K-ion batteries(PIBs).The Sb@N-C nanotubes demonstrate exceptional reversible capacity of643 mAh·g^(-1)at 0.1 A·g^(-1)with long cycle stability,as well as outstanding rate performance(219.6 mAh·g^(-1)at10 A·g^(-1))in LIBs.As the anode material of PIBs,they reveal impressive capacity of 325.4 mAh·g^(-1)at 0.1 A·g^(-1).The superior electrochemical properties mainly originate from the novel structure.To be specific,the obtained 3D connected network allows for quick ion and electron migration,and prevents the aggregation of Sb nanoparticles.The hollow porous nanotubes can not only accommodate the volume expansion of Sb nanoparticles during cycling,but also facilitate the infiltration of the electrolyte and reduce the ion diffusion length.This work provides a new insight for designing advanced Sb-based anodes for alkali metal ion batteries.

Revealing interfacial space charge storage of Li^(+)/Na^(+)/K^(+)by operando magnetometry

Interfacial space charge storage between ionic and electronic conductor is a promising scheme to further improve energy and power density of alkali metal ion batteries(AMIBs).However,the general behavior of space charge storage in AMIBs has been less investigated experimentally,mostly due to the complicated electrochemical behavior and lack of proper characterization techniques.Here,we use operando magnetometry to verify that in FeSe_(2)AMIBs,abundant Li^(+)/Na^(+)/K^(+)(M^(+))can be stored at M_(2)Se phase while electrons accumulate at Fe nanoparticles,forming interfacial space charge layers.Magnetic and dynamics tests further demonstrate that with increasing ionic radius from Li^(+),Na^(+)to K^(+),the reaction kinetics can be hindered,resulting in limited Fe formation and reduced space charge storage capacity.This work lays solid foundation for studying the complex interfacial effect in electrochemical processes and designing advanced energy storage devices with substantial capacity and considerable power density.