Lithium-ion thermoelectrochemical cell(LTEC), featuring simultaneous energy conversion and storage, has emerged as promising candidate for low-grade heat harvesting. However, relatively poor thermosensitivity and heat...Lithium-ion thermoelectrochemical cell(LTEC), featuring simultaneous energy conversion and storage, has emerged as promising candidate for low-grade heat harvesting. However, relatively poor thermosensitivity and heat-to-current behavior limit the application of LTECs using LiPF_6 electrolyte. Introducing additives into bulk electrolyte is a reasonable strategy to solve such problem by modifying the solvation structure of electrolyte ions. In this work, we develop a dual-salt electrolyte with fluorosurfactant(FS) additive to achieve high thermopower and durability of LTECs during the conversion of low-grade heat into electricity. The addition of FS induces a unique Li~+ solvation with the aggregated double anions through a crowded electrolyte environment,resulting in an enhanced mobility kinetics of Li~+ as well as boosted thermoelectrochemical performances. By coupling optimized electrolyte with graphite electrode, a high thermopower of 13.8 mV K^(-1) and a normalized output power density of 3.99 mW m^(–2) K^(–2) as well as an outstanding output energy density of 607.96 J m^(-2) can be obtained.These results demonstrate that the optimization of electrolyte by regulating solvation structure will inject new vitality into the construction of thermoelectrochemical devices with attractive properties.展开更多
Aqueous Zn-ion batteries(AZIBs)have attracted increasing attention in next-generation energy storage systems due to their high safety and economic.Unfortunately,the side reactions,dendrites and hydrogen evolution effe...Aqueous Zn-ion batteries(AZIBs)have attracted increasing attention in next-generation energy storage systems due to their high safety and economic.Unfortunately,the side reactions,dendrites and hydrogen evolution effects at the zinc anode interface in aqueous electrolytes seriously hinder the application of aqueous zinc-ion batteries.Here,we report a critical solvation strategy to achieve reversible zinc electrochemistry by introducing a small polar molecule acetonitrile to form a“catcher”to arrest active molecules(bound water molecules).The stable solvation structure of[Zn(H_(2)O)_(6)]^(2+)is capable of maintaining and completely inhibiting free water molecules.When[Zn(H_(2)O)_(6)]^(2+)is partially desolvated in the Helmholtz outer layer,the separated active molecules will be arrested by the“catcher”formed by the strong hydrogen bond N-H bond,ensuring the stable desolvation of Zn^(2+).The Zn||Zn symmetric battery can stably cycle for 2250 h at 1 mAh cm^(-2),Zn||V_(6)O_(13) full battery achieved a capacity retention rate of 99.2%after 10,000 cycles at 10 A g^(-1).This paper proposes a novel critical solvation strategy that paves the route for the construction of high-performance AZIBs.展开更多
Aqueous zinc-ion batteries(AZIBs),known for their high safety,low cost,and environmental friendliness,have a wide range of potential applications in large-scale energy storage systems.However,the notorious dendrite gr...Aqueous zinc-ion batteries(AZIBs),known for their high safety,low cost,and environmental friendliness,have a wide range of potential applications in large-scale energy storage systems.However,the notorious dendrite growth and severe side reactions on the anode have significantly hindered their further practical development.Recent studies have shown that the solvation chemistry in the electrolyte is not only closely related to the barriers to the commercialization of AZIBs,but have also sparked a number of valuable ideas to address the challenges of AZIBs.Therefore,we systematically summarize and discuss the regulatory mechanisms of solvation chemistry in various types of electrolytes and the influence of the solvation environment on battery performance.The challenges and future directions for solvation strategies based on the electrolyte environment are proposed to improve their performance and expand their application in AZIBs.展开更多
The solvation structure of Li^(+) in chemical prelithiation reagent plays a key role in improving the low initial Coulombic efficiency(ICE) and poor cycle performance of silicon-based materials. Never theless, the che...The solvation structure of Li^(+) in chemical prelithiation reagent plays a key role in improving the low initial Coulombic efficiency(ICE) and poor cycle performance of silicon-based materials. Never theless, the chemical prelithiation agent is difficult to dope active Li^(+) in silicon-based anodes because of their low working voltage and sluggish Li^(+) diffusion rate. By selecting the lithium–arene complex reagent with 4-methylbiphenyl as an anion ligand and 2-methyltetrahydrofuran as a solvent, the as-prepared micro-sized Si O/C anode can achieve an ICE of nearly 100%. Interestingly, the best prelithium efficiency does not correspond to the lowest redox half-potential(E_(1/2)), and the prelithiation efficiency is determined by the specific influencing factors(E_(1/2), Li^(+) concentration, desolvation energy, and ion diffusion path). In addition, molecular dynamics simulations demonstrate that the ideal prelithiation efficiency can be achieved by choosing appropriate anion ligand and solvent to regulate the solvation structure of Li^(+). Furthermore, the positive effect of prelithiation on cycle performance has been verified by using an in-situ electrochemical dilatometry and solid electrolyte interphase film characterizations.展开更多
A high-performance all-inorganic magnesium-lithium chloride complex(MLCC)electrolyte is synthesized by a simple room-temperature reaction of LiCl with MgCl_(2) in tetrahydrofuran(THF)solvent.Molecular dynamics simulat...A high-performance all-inorganic magnesium-lithium chloride complex(MLCC)electrolyte is synthesized by a simple room-temperature reaction of LiCl with MgCl_(2) in tetrahydrofuran(THF)solvent.Molecular dynamics simulation,density functional theory calculation,Raman spectroscopy,and nuclear magnetic resonance spectroscopy reveal that the formation of[Mg_(x)Li_(y)Cl_(2x+y)·nTHF]complex solvation structure significantly lowers the coordination number of THF in the first solvation sheath of Mg^(2+),which significantly enhances its de-solvation kinetics.The MLCC electrolyte presents a stable electrochemical window up to 3.1 V(vs Mg/Mg^(2+))and enables reversible cycling of Mg metal deposition/stripping with an outstanding Coulombic efficiency up to 99%at current densities as high as 10 mA cm^(-2).Utilizing the MLCC electrolyte,a Mg/Mo_(6)S_(8) full cell can be cycled for over 10000 cycles with a superior capacity retention of 85 mA h g^(-1) under an ultrahigh rate of 50 C(1 C=128.8 mA g^(-1)).The facile synthesis of highperformance MLCC electrolyte provides a promising solution for future practical magnesium batteries.展开更多
The rapid development and widespread application of lithium-ion batteries(LIBs) have increased demand for high-safety and high-performance LIBs. Accordingly, various additives have been used in commercial liquid elect...The rapid development and widespread application of lithium-ion batteries(LIBs) have increased demand for high-safety and high-performance LIBs. Accordingly, various additives have been used in commercial liquid electrolytes to severally adjust the solvation structure of lithium ions, control the components of solid electrolyte interphase, or reduce flammability. While it is highly desirable to develop low-cost multifunctional electrolyte additives integrally that address both safety and performance on LIBs, significant challenges remain. Herein, a novel phosphorus-containing organic small molecule, bis(2-methoxyethyl) methylphosphonate(BMOP), was rationally designed to serve as a fluorine-free and multifunctional additive in commercial electrolytes. This novel electrolyte additive is low-toxicity,high-efficiency, low-cost, and electrode-compatible, which shows the significant improvement to both electrochemical performance and fire safety for LIBs through regulating the electrolyte solvation structure, constructing the stable electrode-electrolyte interphase, and suppressing the electrolyte combustion. This work provides a new avenue for developing safer and high-performance LIBs.展开更多
Commercial carbonate-based electrolytes feature highly reactive activities with alkali metals,yielding low Coulombic efficiencies and poor cycle life in lithium metal batteries,which possess much higher chemical activ...Commercial carbonate-based electrolytes feature highly reactive activities with alkali metals,yielding low Coulombic efficiencies and poor cycle life in lithium metal batteries,which possess much higher chemical activity in the rising star sodium metal batteries.To be motivated,we have proposed that decreasing the solvent solvation ability in carbonate-based electrolytes stepwise could enable longterm stable cycling of high-voltage sodium metal batteries.As the solvation capacity reduces,more anions are enticed into the solvation sheath of Na^(+),resulting in the formation of the more desirable interphase layers on the surface of the anode and the cathode.The inorganic-dominated interphases allow highly efficient Na^(+)deposition/stripping processes with a lower rate of dead sodium generation,as well as maintain a stable structure of the high-voltage cathode material.Specifically,the assembled Na||Na_(3)V_(2)(PO_(4))_(2)F_(3)battery exhibits an accelerated ion diffusion kinetics and achieves a higher capacity retention of 85.9%with during the consecutive 200 cycles under the high voltage of 4.5 V.It is anticipated that the tactics we have proposed could be applicable in other secondary metal battery systems as well.展开更多
Aluminum-ion batteries(AIBs)have been highlighted as a potential alternative to lithium-ion batteries for large-scale energy storage due to the abundant reserve,light weight,low cost,and good safety of Al.However,the ...Aluminum-ion batteries(AIBs)have been highlighted as a potential alternative to lithium-ion batteries for large-scale energy storage due to the abundant reserve,light weight,low cost,and good safety of Al.However,the development of AIBs faces challenges due to the usage of AlCl_(3)-based ionic liquid electrolytes,which are expensive,corrosive,and sensitive to humidity.Here,we develop a low-cost,non-corrosive,and air-stable hydrated eutectic electrolyte composed of aluminum perchlorate nonahydrate and methylurea(MU)ligand.Through optimizing the molar ratio to achieve the unique solvation structure,the formed Al(ClO_4)_(3)·9H_(2)O/MU hydrated deep eutectic electrolyte(AMHEE)with an average coordination number of 2.4 can facilely realize stable and reversible deposition/stripping of Al.When combining with vanadium oxide nanorods positive electrode,the Al-ion full battery delivers a high discharge capacity of 320 mAh g^(-1)with good capacity retention.The unique solvation structure with a low desolvation energy of the AMHEE enables Al^(3+)insertion/extraction during charge/discharge processes,which is evidenced by in situ synchrotron radiation X-ray diffraction.This work opens a new pathway of developing low-cost,safe,environmentally friendly and high-performance electrolytes for practical and sustainable AIBs.展开更多
With the booming development of lithium-ion batteries,safety has become one of the most primary focuses of current researches.Although there are various approaches to enhance the safety of lithiumion batteries,phospha...With the booming development of lithium-ion batteries,safety has become one of the most primary focuses of current researches.Although there are various approaches to enhance the safety of lithiumion batteries,phosphate-based electrolyte holds the greatest potential for practical application due to their non-flammability.Nonetheless,its compatibility issue with the graphite anode remains a significant obstacle to its widespread use.Herein,an effective method is proposed to improve the compatibility of electrolyte with graphite(Gr)anode by rationally adjusting the proportion of lithium salt and solvent components to optimize the Li^(+)solvation structure.By slightly increasing the Li^(+)/triethyl phosphate(TEP)ratio,TEP alone cannot fully occupy the inner solvation sheath and therefore less polar ethylene carbonate(EC)has to be recruited,and the solvation structure gradually changes from Li^(+)–[TEP]_(4)to Li^(+)–[TEP]_(3)[EC]with the coexistence of EC and TEP.Simultaneously,EC molecules in the Li^(+)–[TEP]_(3)[EC]could be preferentially reduced on graphite compared to the TEP molecules,resulting in the formation of a uniform and durable solid-electrolyte interphase(SEI)layer.Benefiting from the optimized phosphate-based electrolyte,the Gr|Li battery exhibits a capacity retention rate of 96.8%after stable cycling at 0.5 C for 470 cycles which shows a longer cycle life than the battery with carbonate electrolyte(cycling at 0.5 C for 450 cycles).Therefore,this work provides the guidance for designing a non-flammable phosphate-based electrolyte for high-safety and long cycling-life lithium-ion batteries.展开更多
Severe lithium(Li)dendrite growth caused by the uneven overpotential deposition is a formidable challenge for high energy density Li metal batteries(LMBs).Herein,we investigate a synergetic interfacial kinetic to regu...Severe lithium(Li)dendrite growth caused by the uneven overpotential deposition is a formidable challenge for high energy density Li metal batteries(LMBs).Herein,we investigate a synergetic interfacial kinetic to regulate Li deposition behavior and stabilize Li metal anode.Through constructing Li alloying matrix with a bi-functional silver(Ag)-Li_(3)N blended interface,fast Li^(+)conductivity and high Li affinity can be achieved simultaneously,resulting in both decreased Li nucleation and mass transfercontrolled overpotentials.Beyond these properties,a more important feature is demonstrated herein;that is,the inward diffusion depth of the Li adatoms inside of the Ag site can be restricted by the Li^(+)solvation structure in a highly coordinating environment.The latter feature can ensure the durability of the operational Ag sites,thereby elongating the Li protection ability of the Ag-Li_(3)N interface greatly.This work provides a deep insight into the synergetic effect of functional alloying structure and Li^(+)solvation mediated interfacial kinetic on Li metal protection.展开更多
Zinc(Zn)metal anodes have enticed substantial curiosity for large-scale energy storage owing to inherent safety,high specific and volumetric energy capacities of Zn metal anodes.However,the aqueous electrolyte traditi...Zinc(Zn)metal anodes have enticed substantial curiosity for large-scale energy storage owing to inherent safety,high specific and volumetric energy capacities of Zn metal anodes.However,the aqueous electrolyte traditionally employed in Zn batteries suffers severe decomposition due to the narrow voltage stability window.Herein,we introduce N-methylformamide(NMF)as an organic solvent and modulate the solvation structure to obtain a stable organic/aqueous hybrid electrolyte for high-voltage Zn batteries.NMF is not only extremely stable against Zn metal anodes but also reduces the free water molecule availability by creating numerous hydrogen bonds,thereby accommodating high-voltage Zn‖LiMn_(2)O_(4)batteries.The introduction of NMF prevented hydrogen evolution reaction and promoted the creation of an Frich solid electrolyte interphase,which in turn hampered dendrite growth on Zn anodes.The Zn‖LiMn_(2)O_(4)full cells delivered a high average Coulombic efficiency of 99.7%over 400 cycles.展开更多
The host structure of polymers significantly influences ion transport and interfacial stability of electrolytes,dictating battery cycle life and safety for solid-state lithium metal batteries.Despite promising propert...The host structure of polymers significantly influences ion transport and interfacial stability of electrolytes,dictating battery cycle life and safety for solid-state lithium metal batteries.Despite promising properties of ethylene oxide-based electrolytes,their typical clamp-like coordination geometry leads to crowd solvation sheath and overly strong interactions between Li^(+)and electrolytes,rendering difficult dissociation of Li+and unfavorable solid electrolyte interface(SEI).Herein,we explore weakly solvating characteristics of polyacetal electrolytes owing to their alternately changing intervals between–O–coordinating sites in the main chain.Such structural asymmetry leads to unique distorted helical solvation sheath,and can effectively reduce Li^(+)-electrolyte binding and tune Li^(+)desolvation kinetics in the insitu formed polymer electrolytes,yielding anion-derived SEI and dendrite-free Li electrodeposition.Combining with photoinitiated cationic ring-opening polymerization,polyacetal electrolytes can be instantly formed within 5 min at the surface of electrode,with high segmental chain motion and well adapted interfaces.Such in-situ polyacetal electrolytes enabled more than 1300-h of stable lithium electrodeposition and prolonged cyclability over 200 cycles in solid-state batteries at ambient temperatures,demonstrating the vital role of molecular structure in changing solvating behavior and Li deposition stability for high-performance electrolytes.展开更多
Lithium-sulfur(Li-S)batteries possess overwhelming energy density of 2654 Wh kg-1,and are considered as the next-generation battery technology for energy demanding applications.Flooded electrolytes are ubiquitously em...Lithium-sulfur(Li-S)batteries possess overwhelming energy density of 2654 Wh kg-1,and are considered as the next-generation battery technology for energy demanding applications.Flooded electrolytes are ubiquitously employed in cells to ensure sufficient redox kinetics and preclude the interference of the electrolyte depletion due to side reactions with the lithium metal anode.This strategy is capable of enabling long-lasting,high-capacity and excellent-rate battery performances,but it mask the requirements of practical Li-S batteries,where high-sulfur-loading/content and lean electrolyte are prerequisite to realize the energy-dense Li-S batteries.Sparingly and highly solvating electrolytes have emerged as effective yet simple approaches to decrease the electrolyte/sulfur ratio through altering sulfur species and exerting new reaction pathways.Sparingly solvating electrolytes are characterized by few free solvents to solvate lithium polysulfides,rendering a quasi-solid sulfur conversion and decoupling the reaction mechanisms from electrolyte quantity used in cells;while highly solvating electrolytes adopt highdonicity or high-permittivity solvents and take their advantages of strong solvation ability toward polysulfide intermediates,thereby favoring the polysulfide formation and stabilizing unique radicals,which subsequently accelerate redox kinetics.Both solvation chemistry approaches have their respective features to allow the operation of cells under electrolyte-starved conditions.This Review discusses their unique features and basic physicochemical properties in the working Li-S batteries,presents remaining technical and scientific issues and provides future directions for the electrolyte chemistry to attain highenergy Li-S batteries.展开更多
The dispersion of a solid particle in a liquid may lead to the formation of solvation film on the particle surface, which can strongly increase the repulsive force between particles and thus strongly affect the stabil...The dispersion of a solid particle in a liquid may lead to the formation of solvation film on the particle surface, which can strongly increase the repulsive force between particles and thus strongly affect the stability of dispersions. The solvation film thickness, which varies with the variation of the property of suspension particles and solutions, is one of the most important parameters of the solvation film, and is also one of the most difficult parameters that can be measured accurately. In this paper, a method, based on the Einstein viscosity equation of dispersions, for determining the solvation film thickness of particles is developed. This method was tested on two kinds of silica spherical powders (namely M1 and M2) dispersed in ethyl alcohol, in water, and in a water-ethyl alcohol mixture (1:1 by volume) through measuring the relative viscosity of dispersions of the particles as a function of the volume fraction of the dry particles in the dispersion, and of the specific surface area and the density of the particles. The calculated solvation film thicknesses on M1 are 7.48, 18.65 and 23.74 nm in alcohol, water and the water-ethyl alcohol mixture, 12.41, 12.71 and 13.13 nm on M2 in alcohol, water and the water-ethyl alcohol mixture, respectively.展开更多
Over the full range of compositions, in the ternary-pseudo-binary mixtures of x[(1-y)C6H5CH=CH2+ yCH3COOC2H5(or C6H6)]+(1-x)[(1-y)NMP+yCH3COOC2Hs(or C6H6)], the apparent molar volumes of each pseudo-pure ...Over the full range of compositions, in the ternary-pseudo-binary mixtures of x[(1-y)C6H5CH=CH2+ yCH3COOC2H5(or C6H6)]+(1-x)[(1-y)NMP+yCH3COOC2Hs(or C6H6)], the apparent molar volumes of each pseudo-pure component at different y values were calculated from the density data at 298.15 K and atmospheric pressure. The results show that the four parameters cubic polynomial can correlate the apparent molar volume with the molar fraction well over the full molar fraction range. The limiting partial molar volumes and the molar volumes of each pseudo-pure component were evaluated with different methods. Based on the limiting partial molar volume and molar volume at a certain y value, a new universal coefficient termed as solvation coefficient γ was defined to describe quantitatively the solvation degree of pseudo-pure solute and the interactions of solute-solvent molecules from the macroscopical thermodynamics viewpoint. The results demonstrate the solvation coefficients decrease with the amount of the third component increasing for each pseudo-pure solute, irrespective of the pseudo-pure solvent. Then the solvation degrees of each pseudo-pure component, the specific interactions between the solute molecule and the solvent one were discussed in terms of the solvation coefficient.展开更多
It is important for the electrolytes to maintain and enhance the lithium ion battery electrochemical performance,and solvation of Li^+is a key parameter for the property of the electrolytes.The comparative study on Li...It is important for the electrolytes to maintain and enhance the lithium ion battery electrochemical performance,and solvation of Li^+is a key parameter for the property of the electrolytes.The comparative study on Li^+ solvation structures,energy,enthalpy,Gibbs free energy,infrared and Raman spectra in common organic electrolyte solvents is completed by density functional theory(DFT)method.The solvation reaction energy results suggest that the Li^+solvation priority order is propylene carbonate(PC)>ethylene carbonate(EC)>ethyl methyl carbonate(EMC)>diethyl carbonate(DEC)>tetrahydrofuran(THF)>dimethyl carbonate(DMC)>1,3-dioxolane(DOL)>dimethoxyethane(DME)to form 5sol Li^+.It is also indicated that the most innermost solvation shell compounds formations by stepwise spontaneous solvation reaction are four cyclic solvent molecules and three linear solvent molecules combining one Li^+ forming 4sol-Li^+ and 3sol-Li^+,respectively,at room temperature.Besides,the vibration peaks for C=O and C-O bonds in carbonate ester solvents-Li^+ compounds shift to lower frequency and higher frequency,respectively,when the Li^+ concentration increases in the solvation compounds.All Li-O stretching vibration peaks shift to higher frequency until forming 2solvent-Li^+ complexes,and C-H stretching also shifts to higher frequency except for nDME-Li^+ solvation compounds.The Raman spectrum is more agile to characterize C-H vibrations and IR is agile to C=O,C-O,and Li-O vibrations for Li^+solvation compounds.展开更多
Rechargeable lithium-based battery is hailed as next-generation high-energy-density battery systems.However, growth of lithium dendrites, shuttle effect of lithium polysulfides intermediates and unstable interphase of...Rechargeable lithium-based battery is hailed as next-generation high-energy-density battery systems.However, growth of lithium dendrites, shuttle effect of lithium polysulfides intermediates and unstable interphase of high-voltage intercalation-type cathodes largely prevent their practical deployment.Herein, to fully conquer the three challenges via one strategy, a novel electrolyte with highlycoordinated solvation structure-in-nonsolvent is designed. On account of the particular electrolyte structure, the shuttle effect is completely suppressed by quasi-solid conversion of S species in Li-S batteries,with a stable cycle performance even at lean electrolyte(5μL mg^(-1)). Simultaneously, in-situ-formed highly-fluorinated interphases can not only lower Li+diffusion barrier to ensure uniform nucleation of Li but also improve stability of NCM cathodes, which enable excellent capacity retention of Lik LiNi(0.5)Co(0.2)Mn(0.3)O2 batteries under conditions toward practical applications(high loading of 2.7 m Ah cm^(-2) and lean electrolyte of 5 m L Ah^(-1)). Besides, the electrolyte is also nonflammable. This electrolyte structure offers useful guidelines for the design of novel organic electrolytes for practical lithium-based batteries.展开更多
Through tailoring interfacial chemistry,electrolyte engineering is a facile yet effective strategy for highperformance lithium(Li)metal batteries,where the solvation structure is critical for interfacial chemistry.Her...Through tailoring interfacial chemistry,electrolyte engineering is a facile yet effective strategy for highperformance lithium(Li)metal batteries,where the solvation structure is critical for interfacial chemistry.Herein,the effect of electrostatic interaction on regulating an anion-rich solvation is firstly proposed.The moderate electrostatic interaction between anion and solvent promotes anion to enter the solvation sheath,inducing stable solid electrolyte interphase with fast Li+transport kinetics on the anode.This asdesigned electrolyte exhibits excellent compatibility with Li metal anode(a Li deposition/stripping Coulombic efficiency of 99.3%)and high-voltage LiCoO_(2) cathode.Consequently,the 50μm-thin Li||high-loading LiCoO_(2) cells achieve significantly improved cycling performance under stringent conditions of high voltage over 4.5 V,lean electrolyte,and wide temperature range(-20 to 60℃).This work inspires a groundbreaking strategy to manipulate the solvation structure through regulating the interactions of solvent and anion for highperformance Li metal batteries.展开更多
Magnesium metal anode holds great potentials toward future high energy and safe rechargeable magnesium battery technology due to its divalent redox and dendrite-free nature. Electrolytes based on Lewis acid chemistry ...Magnesium metal anode holds great potentials toward future high energy and safe rechargeable magnesium battery technology due to its divalent redox and dendrite-free nature. Electrolytes based on Lewis acid chemistry enable the reversible Mg plating/stripping,while they fail to match most cathode materials toward highvoltage magnesium batteries. Herein,reversible Mg plating/stripping is achieved in conventional carbonate electrolytes enabled by the cooperative solvation/surface engineering. Strongly electronegative Cl from the MgCl_(2) additive of electrolyte impairs the Mg…O = C interaction to reduce the Mg^(2+) desolvation barrier for accelerated redox kinetics,while the Mg^(2+)-conducting polymer coating on the Mg surface ensures the facile Mg^(2+) migration and the e ective isolation of electrolytes. As a result,reversible plating and stripping of Mg is demonstrated with a low overpotential of 0.7 V up to 2000 cycles. Moreover,benefitting from the wide electrochemical window of carbonate electrolytes,high-voltage(> 2.0 V) rechargeable magnesium batteries are achieved through assembling the electrode couple of Mg metal anode and Prussian blue-based cathodes. The present work provides a cooperative engineering strategy to promote the application of magnesium anode in carbonate electrolytes toward high energy rechargeable batteries.展开更多
Exploring low-cost and effective approaches to extend the potentials of aqueous electrolytes is highly desired.Herein,it is found that the activity of H_(2)O in aqueous electrolytes could be intensively manipulated by...Exploring low-cost and effective approaches to extend the potentials of aqueous electrolytes is highly desired.Herein,it is found that the activity of H_(2)O in aqueous electrolytes could be intensively manipulated by introducing small urea and long-chain polyethylene glycol(PEG)molecules into Li TFSI-H_(2)O electrolyte systems without super salt concentration.The urea and PEG molecules could exclude partial coordinated H_(2)O out of the inner solvation shell of Li_(4) and reconstruct hydrogen-bonding network between H_(2)O and PEG molecules outside the solvation sheaths with restricted H_(2)O activity and extended electrochemical window.The bonding competitions in aqueous electrolytes and their correlation to the electrochemical performance of full cells are studied.When the occurrence probability of H_(2)O around Li_(4)is lower than 40%,stable cycling of 3.1 V LiMn_(2)O_(4)-Li_(4)Ti_(5)O_(12) full cell is achieved,showing 73%capacity retention after 200 cycles at 1 C rate in optimal electrolytes.This work provides new avenues to understand the role of H_(2)O and explore low-cost and effective approaches for the development of nextgeneration aqueous lithium-ion batteries.展开更多
基金supported by the Leading Edge Technology of Jiangsu Province (BK20220009, BK20202008)Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)。
文摘Lithium-ion thermoelectrochemical cell(LTEC), featuring simultaneous energy conversion and storage, has emerged as promising candidate for low-grade heat harvesting. However, relatively poor thermosensitivity and heat-to-current behavior limit the application of LTECs using LiPF_6 electrolyte. Introducing additives into bulk electrolyte is a reasonable strategy to solve such problem by modifying the solvation structure of electrolyte ions. In this work, we develop a dual-salt electrolyte with fluorosurfactant(FS) additive to achieve high thermopower and durability of LTECs during the conversion of low-grade heat into electricity. The addition of FS induces a unique Li~+ solvation with the aggregated double anions through a crowded electrolyte environment,resulting in an enhanced mobility kinetics of Li~+ as well as boosted thermoelectrochemical performances. By coupling optimized electrolyte with graphite electrode, a high thermopower of 13.8 mV K^(-1) and a normalized output power density of 3.99 mW m^(–2) K^(–2) as well as an outstanding output energy density of 607.96 J m^(-2) can be obtained.These results demonstrate that the optimization of electrolyte by regulating solvation structure will inject new vitality into the construction of thermoelectrochemical devices with attractive properties.
基金supported by the National Natural Science Foundation of China(No.52272198 and 52002122)the Project funded by China Postdoctoral Science Foundation(No.2021M690947).
文摘Aqueous Zn-ion batteries(AZIBs)have attracted increasing attention in next-generation energy storage systems due to their high safety and economic.Unfortunately,the side reactions,dendrites and hydrogen evolution effects at the zinc anode interface in aqueous electrolytes seriously hinder the application of aqueous zinc-ion batteries.Here,we report a critical solvation strategy to achieve reversible zinc electrochemistry by introducing a small polar molecule acetonitrile to form a“catcher”to arrest active molecules(bound water molecules).The stable solvation structure of[Zn(H_(2)O)_(6)]^(2+)is capable of maintaining and completely inhibiting free water molecules.When[Zn(H_(2)O)_(6)]^(2+)is partially desolvated in the Helmholtz outer layer,the separated active molecules will be arrested by the“catcher”formed by the strong hydrogen bond N-H bond,ensuring the stable desolvation of Zn^(2+).The Zn||Zn symmetric battery can stably cycle for 2250 h at 1 mAh cm^(-2),Zn||V_(6)O_(13) full battery achieved a capacity retention rate of 99.2%after 10,000 cycles at 10 A g^(-1).This paper proposes a novel critical solvation strategy that paves the route for the construction of high-performance AZIBs.
基金supported by grants from the Major Basic Research Projects of Shandong Natural Science Foundation(ZR2020ZD07)the Key Scientific and Technological Innovation Project of Shandong(2020CXGC010401).
文摘Aqueous zinc-ion batteries(AZIBs),known for their high safety,low cost,and environmental friendliness,have a wide range of potential applications in large-scale energy storage systems.However,the notorious dendrite growth and severe side reactions on the anode have significantly hindered their further practical development.Recent studies have shown that the solvation chemistry in the electrolyte is not only closely related to the barriers to the commercialization of AZIBs,but have also sparked a number of valuable ideas to address the challenges of AZIBs.Therefore,we systematically summarize and discuss the regulatory mechanisms of solvation chemistry in various types of electrolytes and the influence of the solvation environment on battery performance.The challenges and future directions for solvation strategies based on the electrolyte environment are proposed to improve their performance and expand their application in AZIBs.
基金supported by the National Natural Science Foundation of China (21875107, U1802256, and 22209204)Leading Edge Technology of Jiangsu Province (BK20220009), the Natural Science Foundation of Jiangsu Province (BK20221140)+2 种基金the China Postdoctoral Science Foundation (2022M713364)Jiangsu Specially Appointed Professors ProgramPriority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)。
文摘The solvation structure of Li^(+) in chemical prelithiation reagent plays a key role in improving the low initial Coulombic efficiency(ICE) and poor cycle performance of silicon-based materials. Never theless, the chemical prelithiation agent is difficult to dope active Li^(+) in silicon-based anodes because of their low working voltage and sluggish Li^(+) diffusion rate. By selecting the lithium–arene complex reagent with 4-methylbiphenyl as an anion ligand and 2-methyltetrahydrofuran as a solvent, the as-prepared micro-sized Si O/C anode can achieve an ICE of nearly 100%. Interestingly, the best prelithium efficiency does not correspond to the lowest redox half-potential(E_(1/2)), and the prelithiation efficiency is determined by the specific influencing factors(E_(1/2), Li^(+) concentration, desolvation energy, and ion diffusion path). In addition, molecular dynamics simulations demonstrate that the ideal prelithiation efficiency can be achieved by choosing appropriate anion ligand and solvent to regulate the solvation structure of Li^(+). Furthermore, the positive effect of prelithiation on cycle performance has been verified by using an in-situ electrochemical dilatometry and solid electrolyte interphase film characterizations.
基金supported by the National Natural Science Foundation of China(NSFCU1832218)the Beijing Advanced Innovation Center for Future Chip(ICFC).
文摘A high-performance all-inorganic magnesium-lithium chloride complex(MLCC)electrolyte is synthesized by a simple room-temperature reaction of LiCl with MgCl_(2) in tetrahydrofuran(THF)solvent.Molecular dynamics simulation,density functional theory calculation,Raman spectroscopy,and nuclear magnetic resonance spectroscopy reveal that the formation of[Mg_(x)Li_(y)Cl_(2x+y)·nTHF]complex solvation structure significantly lowers the coordination number of THF in the first solvation sheath of Mg^(2+),which significantly enhances its de-solvation kinetics.The MLCC electrolyte presents a stable electrochemical window up to 3.1 V(vs Mg/Mg^(2+))and enables reversible cycling of Mg metal deposition/stripping with an outstanding Coulombic efficiency up to 99%at current densities as high as 10 mA cm^(-2).Utilizing the MLCC electrolyte,a Mg/Mo_(6)S_(8) full cell can be cycled for over 10000 cycles with a superior capacity retention of 85 mA h g^(-1) under an ultrahigh rate of 50 C(1 C=128.8 mA g^(-1)).The facile synthesis of highperformance MLCC electrolyte provides a promising solution for future practical magnesium batteries.
基金supported by the National Natural Science Foundation of China (51773134)the Sichuan Science and Technology Program (2019YFH0112)+2 种基金the Fundamental Research Funds for the Central UniversitiesInstitutional Research Fund from Sichuan University (2021SCUNL201)the 111 Project (B20001)。
文摘The rapid development and widespread application of lithium-ion batteries(LIBs) have increased demand for high-safety and high-performance LIBs. Accordingly, various additives have been used in commercial liquid electrolytes to severally adjust the solvation structure of lithium ions, control the components of solid electrolyte interphase, or reduce flammability. While it is highly desirable to develop low-cost multifunctional electrolyte additives integrally that address both safety and performance on LIBs, significant challenges remain. Herein, a novel phosphorus-containing organic small molecule, bis(2-methoxyethyl) methylphosphonate(BMOP), was rationally designed to serve as a fluorine-free and multifunctional additive in commercial electrolytes. This novel electrolyte additive is low-toxicity,high-efficiency, low-cost, and electrode-compatible, which shows the significant improvement to both electrochemical performance and fire safety for LIBs through regulating the electrolyte solvation structure, constructing the stable electrode-electrolyte interphase, and suppressing the electrolyte combustion. This work provides a new avenue for developing safer and high-performance LIBs.
基金financial support from the National Natural Science Foundation of China(Grant No.22005172)the Natural Science Foundation of Sichuan Province(Grant No.2023NSFSC1124)+3 种基金the Fundamental Research Funds for the Central Universities(Grant No.YJ2021141)the Science and Technology Cooperation Special Fund of Sichuan University and Zigong City(Grant No.2022CDZG-9)the Natural Science Foundation of Shangdong Province(Grant No.ZR202211280350)the Technological Innovation Project of Tai’an City(Grant No.2022GX064)。
文摘Commercial carbonate-based electrolytes feature highly reactive activities with alkali metals,yielding low Coulombic efficiencies and poor cycle life in lithium metal batteries,which possess much higher chemical activity in the rising star sodium metal batteries.To be motivated,we have proposed that decreasing the solvent solvation ability in carbonate-based electrolytes stepwise could enable longterm stable cycling of high-voltage sodium metal batteries.As the solvation capacity reduces,more anions are enticed into the solvation sheath of Na^(+),resulting in the formation of the more desirable interphase layers on the surface of the anode and the cathode.The inorganic-dominated interphases allow highly efficient Na^(+)deposition/stripping processes with a lower rate of dead sodium generation,as well as maintain a stable structure of the high-voltage cathode material.Specifically,the assembled Na||Na_(3)V_(2)(PO_(4))_(2)F_(3)battery exhibits an accelerated ion diffusion kinetics and achieves a higher capacity retention of 85.9%with during the consecutive 200 cycles under the high voltage of 4.5 V.It is anticipated that the tactics we have proposed could be applicable in other secondary metal battery systems as well.
基金supported by the National Natural Science Foundation of China(52274302)。
文摘Aluminum-ion batteries(AIBs)have been highlighted as a potential alternative to lithium-ion batteries for large-scale energy storage due to the abundant reserve,light weight,low cost,and good safety of Al.However,the development of AIBs faces challenges due to the usage of AlCl_(3)-based ionic liquid electrolytes,which are expensive,corrosive,and sensitive to humidity.Here,we develop a low-cost,non-corrosive,and air-stable hydrated eutectic electrolyte composed of aluminum perchlorate nonahydrate and methylurea(MU)ligand.Through optimizing the molar ratio to achieve the unique solvation structure,the formed Al(ClO_4)_(3)·9H_(2)O/MU hydrated deep eutectic electrolyte(AMHEE)with an average coordination number of 2.4 can facilely realize stable and reversible deposition/stripping of Al.When combining with vanadium oxide nanorods positive electrode,the Al-ion full battery delivers a high discharge capacity of 320 mAh g^(-1)with good capacity retention.The unique solvation structure with a low desolvation energy of the AMHEE enables Al^(3+)insertion/extraction during charge/discharge processes,which is evidenced by in situ synchrotron radiation X-ray diffraction.This work opens a new pathway of developing low-cost,safe,environmentally friendly and high-performance electrolytes for practical and sustainable AIBs.
基金the National Natural Science Foundation of China(52034011 and 52101278)the Central South University Research Programme of Advanced Interdisciplinary Studies(2023QYJC005)the Fundamental Research Funds for Central Universities of the Central South University(2022ZZTS0405)。
文摘With the booming development of lithium-ion batteries,safety has become one of the most primary focuses of current researches.Although there are various approaches to enhance the safety of lithiumion batteries,phosphate-based electrolyte holds the greatest potential for practical application due to their non-flammability.Nonetheless,its compatibility issue with the graphite anode remains a significant obstacle to its widespread use.Herein,an effective method is proposed to improve the compatibility of electrolyte with graphite(Gr)anode by rationally adjusting the proportion of lithium salt and solvent components to optimize the Li^(+)solvation structure.By slightly increasing the Li^(+)/triethyl phosphate(TEP)ratio,TEP alone cannot fully occupy the inner solvation sheath and therefore less polar ethylene carbonate(EC)has to be recruited,and the solvation structure gradually changes from Li^(+)–[TEP]_(4)to Li^(+)–[TEP]_(3)[EC]with the coexistence of EC and TEP.Simultaneously,EC molecules in the Li^(+)–[TEP]_(3)[EC]could be preferentially reduced on graphite compared to the TEP molecules,resulting in the formation of a uniform and durable solid-electrolyte interphase(SEI)layer.Benefiting from the optimized phosphate-based electrolyte,the Gr|Li battery exhibits a capacity retention rate of 96.8%after stable cycling at 0.5 C for 470 cycles which shows a longer cycle life than the battery with carbonate electrolyte(cycling at 0.5 C for 450 cycles).Therefore,this work provides the guidance for designing a non-flammable phosphate-based electrolyte for high-safety and long cycling-life lithium-ion batteries.
基金supported by the 21C Innovation Laboratory,Contemporary Amperex Technology Ltd by project No.21C-OP-202004,the Ningbo S&T Innovation 2025 Major Special Program(Grant No.2018B10061,2018B10087,2019B10044,and 2020Z101)the National Key R&D Program of China(Grant No.2018YFB0905400).
文摘Severe lithium(Li)dendrite growth caused by the uneven overpotential deposition is a formidable challenge for high energy density Li metal batteries(LMBs).Herein,we investigate a synergetic interfacial kinetic to regulate Li deposition behavior and stabilize Li metal anode.Through constructing Li alloying matrix with a bi-functional silver(Ag)-Li_(3)N blended interface,fast Li^(+)conductivity and high Li affinity can be achieved simultaneously,resulting in both decreased Li nucleation and mass transfercontrolled overpotentials.Beyond these properties,a more important feature is demonstrated herein;that is,the inward diffusion depth of the Li adatoms inside of the Ag site can be restricted by the Li^(+)solvation structure in a highly coordinating environment.The latter feature can ensure the durability of the operational Ag sites,thereby elongating the Li protection ability of the Ag-Li_(3)N interface greatly.This work provides a deep insight into the synergetic effect of functional alloying structure and Li^(+)solvation mediated interfacial kinetic on Li metal protection.
基金financial support from the Australian Research Council(ARC)through the ARC Discovery projects(DP200101249,DP210101389,DP230101579)ARC Future Fel owship(FT220100561)+1 种基金ARC Linkage project(LP200200926)ARC Industry Transformation Research Hub(IH180100020)
文摘Zinc(Zn)metal anodes have enticed substantial curiosity for large-scale energy storage owing to inherent safety,high specific and volumetric energy capacities of Zn metal anodes.However,the aqueous electrolyte traditionally employed in Zn batteries suffers severe decomposition due to the narrow voltage stability window.Herein,we introduce N-methylformamide(NMF)as an organic solvent and modulate the solvation structure to obtain a stable organic/aqueous hybrid electrolyte for high-voltage Zn batteries.NMF is not only extremely stable against Zn metal anodes but also reduces the free water molecule availability by creating numerous hydrogen bonds,thereby accommodating high-voltage Zn‖LiMn_(2)O_(4)batteries.The introduction of NMF prevented hydrogen evolution reaction and promoted the creation of an Frich solid electrolyte interphase,which in turn hampered dendrite growth on Zn anodes.The Zn‖LiMn_(2)O_(4)full cells delivered a high average Coulombic efficiency of 99.7%over 400 cycles.
基金financially supported by National Natural Science Foundation of China(52003231,22065037)Yunnan Fundamental Research Projects(202201AW070015)。
文摘The host structure of polymers significantly influences ion transport and interfacial stability of electrolytes,dictating battery cycle life and safety for solid-state lithium metal batteries.Despite promising properties of ethylene oxide-based electrolytes,their typical clamp-like coordination geometry leads to crowd solvation sheath and overly strong interactions between Li^(+)and electrolytes,rendering difficult dissociation of Li+and unfavorable solid electrolyte interface(SEI).Herein,we explore weakly solvating characteristics of polyacetal electrolytes owing to their alternately changing intervals between–O–coordinating sites in the main chain.Such structural asymmetry leads to unique distorted helical solvation sheath,and can effectively reduce Li^(+)-electrolyte binding and tune Li^(+)desolvation kinetics in the insitu formed polymer electrolytes,yielding anion-derived SEI and dendrite-free Li electrodeposition.Combining with photoinitiated cationic ring-opening polymerization,polyacetal electrolytes can be instantly formed within 5 min at the surface of electrode,with high segmental chain motion and well adapted interfaces.Such in-situ polyacetal electrolytes enabled more than 1300-h of stable lithium electrodeposition and prolonged cyclability over 200 cycles in solid-state batteries at ambient temperatures,demonstrating the vital role of molecular structure in changing solvating behavior and Li deposition stability for high-performance electrolytes.
基金supported by the National Natural Science Foundation of China(21805162 and 21671096)National Key Research and Development Program(2018YFB0104300)+3 种基金Key Program of the Natural Science Foundation of China(51732005)Guangdong Provincial Key Laboratory of Energy Materials for Electric Power(2018B030322001)Shenzhen Key Laboratory of Solid State Batteries(No.ZDSYS201802081843465)Research Support for Postdoctoral Scholars coming to Shenzhen(K19407556)。
文摘Lithium-sulfur(Li-S)batteries possess overwhelming energy density of 2654 Wh kg-1,and are considered as the next-generation battery technology for energy demanding applications.Flooded electrolytes are ubiquitously employed in cells to ensure sufficient redox kinetics and preclude the interference of the electrolyte depletion due to side reactions with the lithium metal anode.This strategy is capable of enabling long-lasting,high-capacity and excellent-rate battery performances,but it mask the requirements of practical Li-S batteries,where high-sulfur-loading/content and lean electrolyte are prerequisite to realize the energy-dense Li-S batteries.Sparingly and highly solvating electrolytes have emerged as effective yet simple approaches to decrease the electrolyte/sulfur ratio through altering sulfur species and exerting new reaction pathways.Sparingly solvating electrolytes are characterized by few free solvents to solvate lithium polysulfides,rendering a quasi-solid sulfur conversion and decoupling the reaction mechanisms from electrolyte quantity used in cells;while highly solvating electrolytes adopt highdonicity or high-permittivity solvents and take their advantages of strong solvation ability toward polysulfide intermediates,thereby favoring the polysulfide formation and stabilizing unique radicals,which subsequently accelerate redox kinetics.Both solvation chemistry approaches have their respective features to allow the operation of cells under electrolyte-starved conditions.This Review discusses their unique features and basic physicochemical properties in the working Li-S batteries,presents remaining technical and scientific issues and provides future directions for the electrolyte chemistry to attain highenergy Li-S batteries.
基金This work is financially supported by the Consejo Nacional de Ciencia y Tecnología (CONACyT) of Mexico under the grant #485100-5-38214-U.
文摘The dispersion of a solid particle in a liquid may lead to the formation of solvation film on the particle surface, which can strongly increase the repulsive force between particles and thus strongly affect the stability of dispersions. The solvation film thickness, which varies with the variation of the property of suspension particles and solutions, is one of the most important parameters of the solvation film, and is also one of the most difficult parameters that can be measured accurately. In this paper, a method, based on the Einstein viscosity equation of dispersions, for determining the solvation film thickness of particles is developed. This method was tested on two kinds of silica spherical powders (namely M1 and M2) dispersed in ethyl alcohol, in water, and in a water-ethyl alcohol mixture (1:1 by volume) through measuring the relative viscosity of dispersions of the particles as a function of the volume fraction of the dry particles in the dispersion, and of the specific surface area and the density of the particles. The calculated solvation film thicknesses on M1 are 7.48, 18.65 and 23.74 nm in alcohol, water and the water-ethyl alcohol mixture, 12.41, 12.71 and 13.13 nm on M2 in alcohol, water and the water-ethyl alcohol mixture, respectively.
基金Supported by the National Natural Science Foundation of China(No.20673080)the Scientific Research Fund of Xi’an Polytechnic University of China(No.BS0704)
文摘Over the full range of compositions, in the ternary-pseudo-binary mixtures of x[(1-y)C6H5CH=CH2+ yCH3COOC2H5(or C6H6)]+(1-x)[(1-y)NMP+yCH3COOC2Hs(or C6H6)], the apparent molar volumes of each pseudo-pure component at different y values were calculated from the density data at 298.15 K and atmospheric pressure. The results show that the four parameters cubic polynomial can correlate the apparent molar volume with the molar fraction well over the full molar fraction range. The limiting partial molar volumes and the molar volumes of each pseudo-pure component were evaluated with different methods. Based on the limiting partial molar volume and molar volume at a certain y value, a new universal coefficient termed as solvation coefficient γ was defined to describe quantitatively the solvation degree of pseudo-pure solute and the interactions of solute-solvent molecules from the macroscopical thermodynamics viewpoint. The results demonstrate the solvation coefficients decrease with the amount of the third component increasing for each pseudo-pure solute, irrespective of the pseudo-pure solvent. Then the solvation degrees of each pseudo-pure component, the specific interactions between the solute molecule and the solvent one were discussed in terms of the solvation coefficient.
基金Project supported by International Science&Technology Cooperation of China(Grant No.2019YFE0100200)the National Natural Science Foundation of China(Grant No.51902024)+3 种基金the National Postdoctoral Program for Innovative Talents of China(Grant No.BX20180038)China Postdoctoral Science Foundation(Grant No.2019M650014)NASF,China(Grant No.U1930113)Beijing Natural Science Foundation,China(Grant No.L182022)。
文摘It is important for the electrolytes to maintain and enhance the lithium ion battery electrochemical performance,and solvation of Li^+is a key parameter for the property of the electrolytes.The comparative study on Li^+ solvation structures,energy,enthalpy,Gibbs free energy,infrared and Raman spectra in common organic electrolyte solvents is completed by density functional theory(DFT)method.The solvation reaction energy results suggest that the Li^+solvation priority order is propylene carbonate(PC)>ethylene carbonate(EC)>ethyl methyl carbonate(EMC)>diethyl carbonate(DEC)>tetrahydrofuran(THF)>dimethyl carbonate(DMC)>1,3-dioxolane(DOL)>dimethoxyethane(DME)to form 5sol Li^+.It is also indicated that the most innermost solvation shell compounds formations by stepwise spontaneous solvation reaction are four cyclic solvent molecules and three linear solvent molecules combining one Li^+ forming 4sol-Li^+ and 3sol-Li^+,respectively,at room temperature.Besides,the vibration peaks for C=O and C-O bonds in carbonate ester solvents-Li^+ compounds shift to lower frequency and higher frequency,respectively,when the Li^+ concentration increases in the solvation compounds.All Li-O stretching vibration peaks shift to higher frequency until forming 2solvent-Li^+ complexes,and C-H stretching also shifts to higher frequency except for nDME-Li^+ solvation compounds.The Raman spectrum is more agile to characterize C-H vibrations and IR is agile to C=O,C-O,and Li-O vibrations for Li^+solvation compounds.
基金financial support from the National Key Research and Development Program of China (2018YFB0104200)。
文摘Rechargeable lithium-based battery is hailed as next-generation high-energy-density battery systems.However, growth of lithium dendrites, shuttle effect of lithium polysulfides intermediates and unstable interphase of high-voltage intercalation-type cathodes largely prevent their practical deployment.Herein, to fully conquer the three challenges via one strategy, a novel electrolyte with highlycoordinated solvation structure-in-nonsolvent is designed. On account of the particular electrolyte structure, the shuttle effect is completely suppressed by quasi-solid conversion of S species in Li-S batteries,with a stable cycle performance even at lean electrolyte(5μL mg^(-1)). Simultaneously, in-situ-formed highly-fluorinated interphases can not only lower Li+diffusion barrier to ensure uniform nucleation of Li but also improve stability of NCM cathodes, which enable excellent capacity retention of Lik LiNi(0.5)Co(0.2)Mn(0.3)O2 batteries under conditions toward practical applications(high loading of 2.7 m Ah cm^(-2) and lean electrolyte of 5 m L Ah^(-1)). Besides, the electrolyte is also nonflammable. This electrolyte structure offers useful guidelines for the design of novel organic electrolytes for practical lithium-based batteries.
基金supported by National Nature Science Foundation of China(No.51872157 and No.52072208)National Key R&D Program of China 2021YFA1202802Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program(2017BT01N111)。
文摘Through tailoring interfacial chemistry,electrolyte engineering is a facile yet effective strategy for highperformance lithium(Li)metal batteries,where the solvation structure is critical for interfacial chemistry.Herein,the effect of electrostatic interaction on regulating an anion-rich solvation is firstly proposed.The moderate electrostatic interaction between anion and solvent promotes anion to enter the solvation sheath,inducing stable solid electrolyte interphase with fast Li+transport kinetics on the anode.This asdesigned electrolyte exhibits excellent compatibility with Li metal anode(a Li deposition/stripping Coulombic efficiency of 99.3%)and high-voltage LiCoO_(2) cathode.Consequently,the 50μm-thin Li||high-loading LiCoO_(2) cells achieve significantly improved cycling performance under stringent conditions of high voltage over 4.5 V,lean electrolyte,and wide temperature range(-20 to 60℃).This work inspires a groundbreaking strategy to manipulate the solvation structure through regulating the interactions of solvent and anion for highperformance Li metal batteries.
基金supported by National Key Research and Development Program (2019YFE0111200)the National Natural Science Foundation of China (51722105)+1 种基金Zhejiang Provincial Natural Science Foundation of China (LR18B030001)the Fundamental Research Funds for the Central Universities and the Fundamental Research Funds for the Central Universities。
文摘Magnesium metal anode holds great potentials toward future high energy and safe rechargeable magnesium battery technology due to its divalent redox and dendrite-free nature. Electrolytes based on Lewis acid chemistry enable the reversible Mg plating/stripping,while they fail to match most cathode materials toward highvoltage magnesium batteries. Herein,reversible Mg plating/stripping is achieved in conventional carbonate electrolytes enabled by the cooperative solvation/surface engineering. Strongly electronegative Cl from the MgCl_(2) additive of electrolyte impairs the Mg…O = C interaction to reduce the Mg^(2+) desolvation barrier for accelerated redox kinetics,while the Mg^(2+)-conducting polymer coating on the Mg surface ensures the facile Mg^(2+) migration and the e ective isolation of electrolytes. As a result,reversible plating and stripping of Mg is demonstrated with a low overpotential of 0.7 V up to 2000 cycles. Moreover,benefitting from the wide electrochemical window of carbonate electrolytes,high-voltage(> 2.0 V) rechargeable magnesium batteries are achieved through assembling the electrode couple of Mg metal anode and Prussian blue-based cathodes. The present work provides a cooperative engineering strategy to promote the application of magnesium anode in carbonate electrolytes toward high energy rechargeable batteries.
基金supported by the Startup Foundation for Hundred-Talent Program of Zhejiang University。
文摘Exploring low-cost and effective approaches to extend the potentials of aqueous electrolytes is highly desired.Herein,it is found that the activity of H_(2)O in aqueous electrolytes could be intensively manipulated by introducing small urea and long-chain polyethylene glycol(PEG)molecules into Li TFSI-H_(2)O electrolyte systems without super salt concentration.The urea and PEG molecules could exclude partial coordinated H_(2)O out of the inner solvation shell of Li_(4) and reconstruct hydrogen-bonding network between H_(2)O and PEG molecules outside the solvation sheaths with restricted H_(2)O activity and extended electrochemical window.The bonding competitions in aqueous electrolytes and their correlation to the electrochemical performance of full cells are studied.When the occurrence probability of H_(2)O around Li_(4)is lower than 40%,stable cycling of 3.1 V LiMn_(2)O_(4)-Li_(4)Ti_(5)O_(12) full cell is achieved,showing 73%capacity retention after 200 cycles at 1 C rate in optimal electrolytes.This work provides new avenues to understand the role of H_(2)O and explore low-cost and effective approaches for the development of nextgeneration aqueous lithium-ion batteries.