Aqueous zinc-ion batteries encounter impediments on their trajectory towards commercialization,primarily due to challenges such as dendritic growth,hydrogen evolution reaction.Throughout recent decades of investigatio...Aqueous zinc-ion batteries encounter impediments on their trajectory towards commercialization,primarily due to challenges such as dendritic growth,hydrogen evolution reaction.Throughout recent decades of investigation,electrolyte modulation by using function additives is widely considered as a facile and efficient way to prolong the Zn anode lifespan.Herein,N-(2-hydroxypropyl)ethylenediamine is employed as an additive to attach onto the Zn surface with a substantial adsorption energy with(002)facet.The as-formed in-situ solid-electrolyte interphase layer effectively mitigates hydrogen evolution reaction by constructing a lean-water internal Helmholtz layer.Additionally,N-(2-hydroxypropyl)ethylenediamine establishes a coordination complex with Zn^(2+),thereby modulating the solvation structure and enhancing the mobility of Zn^(2+).As expected,the Zn-symmetrical cell with N-(2-hydroxypropyl)ethylenediamine additive demonstrated successful cycling exceeding 1500 h under 1 mA cm^(-2) for0.5 mAh cm^(-2).Furthermore,the Zn//δ-MnO_(2) battery maintains a capacity of approximately 130 mAh g^(-1) after 800 cycles at 1 A g^(-1),with a Coulombic efficiency surpassing 98%.This work presents a streamlined approach for realizing aqueous zinc-ion batteries with extended service life.展开更多
Designing anion-dominated weak solvation structures is often achieved by elevating the concentration of Li salts.However,this is accompanied by the increase in the cost.Herein,a medium concentration electrolyte (1 M) ...Designing anion-dominated weak solvation structures is often achieved by elevating the concentration of Li salts.However,this is accompanied by the increase in the cost.Herein,a medium concentration electrolyte (1 M) with weak solvation structures is established by the multi-anion strategy.Multiple anions in the electrolyte strengthen the anion-solvent interactions through stronger ion–dipole interactions.This reduces the quantity of free solvent and improves the reduction resistance of solvents.In addition,the Li ion–solvent interaction is weakened,facilitating the anions to enter the solvation sheaths of Li ions.This multi-anion-dominated weak solvation structures boost Li ion diffusion in the electrolyte,accelerate the desolvation process of Li ions,and induce inorganic-rich solid electrolyte interphase and uniform Li deposition.An average Coulombic efficiency of 99.1%for repeated Li plating/stripping can be achieved.Li||LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) cells with a high cathode loading of 3.0 m A h cm^(-2) can maintain a capacity retention as high as 95% after 150 cycles.This finding provides novel standpoints to modulate the interaction of solvation structures and extend the lifespan of high-energy–density Li metal batteries.展开更多
Monovalent anions,with relatively low charge density,exhibit weak bond energy with Zn^(2+)ions,which facilitates the solubility of Zn salts and the regulation of solvation structures.In this study,zinc bis(aminosulfat...Monovalent anions,with relatively low charge density,exhibit weak bond energy with Zn^(2+)ions,which facilitates the solubility of Zn salts and the regulation of solvation structures.In this study,zinc bis(aminosulfate)(Zn(NH_(2)SO_(3))_(2))with a monovalent anion,NH_(2)SO_(3)^(-),was synthesized and dissolved in different ratios of dimethyl sulfoxide(DMSO)and H_(2)O as electrolytes for Zn-ion batteries(ZIBs).From the perspective of game theory,the influences of DMSO and H_(2)O on the solvation structure and electrochemical performance of the Zn(NH_(2)SO_(3))_(2)based electrolytes has been meticulously discussed.Computations and spectra analysis indicate that DMSO molecules are reluctant to penetrate the primary solvation structure of Zn^(2+)ions.Indeed,increasing DMSO in electrolytes can induce a transition from solvent-separated ion pairs(SSIP)to contact ion pairs(CIP),resulting in an enrichment of anions in the primary solvation structure.This alteration can significantly suppress parasitic reactions,enhance nucleation density,and refine the deposition morphology during the Zn plating process,leading to superior cyclic stability and high coulombic efficiency(CE)of Zn//Cu and Zn//Zn cells.However,the enrichment of anions in the primary solvation structure also inhibits the activity of Zn^(2+)ions,amplifies the polarization effect,and engenders a sluggish ionization dynamics,resulting in the low energy conversion efficiency of the battery.These findings underscore the influence of the anion ratio within the primary solvation structure on electrochemical properties of electrolytes for ZIBs,which may be a pivotal determinant in the Zn deposition process.展开更多
Quasi-solid polymer electrolytes(QSPEs)have been attracted significant attentions due to their benefits for simultaneously improved safety and energy density of batteries.Developing electrolytes capable of forming a s...Quasi-solid polymer electrolytes(QSPEs)have been attracted significant attentions due to their benefits for simultaneously improved safety and energy density of batteries.Developing electrolytes capable of forming a stable solid electrolyte interphase(SEI)layer is a great challenge for QSPE-based lithium(Li)metal batteries(LMBs).Herein,unlike previously reports that the reconstruction of Li^(+)solvation structures in QSPE requires time-consuming bottom-up polymer synthesis,in current study,a facile approach has been developed to reconstruct the Li^(+)solvation structures in QSPE by adjustment of the salt concentrations.The high proportion of Li^(+)-anion complexes can effectively accelerate interfacial Li^(+)diffusion,mitigate the decompositions of organic solvents and induce the formation of a LiF-rich SEI layer,contributing to suppressed Li-dendrite growth.As a result,the Li/QSPE-3/LiFePO_(4)(LFP)cell performs an ultralong lifespan with capacity retention of 77.4%over 3000 cycles at 1 C.With a high-voltage LiCoO_(2)cathode,the cell can stably cycle over 200 cycles at 25℃(capacity retention of∼83.8%).With accelerated ion transport dynamics due to the reconstructed Li^(+)solvation structure,the QSPE-3(the salt concentration is 3 M)is applicable in a wide temperature range.The Li/QSPE-3/LFP full cell exhibits 58.1%and 102.6%of discharge capacity at−15 and 90℃,respectively,compared to those operated at 25℃This study demonstrates a facile yet effective approach on enhancing electrode/electrolyte interfacial stability,enabling the LMBs with simultaneously enhanced safety and high energy density.展开更多
The high safety of aqueous magnesium ion batteries(AMIBs)contrasts with their limited electrochemical performance.To overcome electrolyte-induced parasitic reactions,it is essential to understand the dynamic evolution...The high safety of aqueous magnesium ion batteries(AMIBs)contrasts with their limited electrochemical performance.To overcome electrolyte-induced parasitic reactions,it is essential to understand the dynamic evolution of concentration-dependent metal ion solvation structures(MISSs).This study systematically reveals the solvation structure evolution of MgCl_(2) aqueous solutions across a full concentration range(0-30 M)and its impact on electrochemical properties using molecular dynamics simulations and density functional theory calculations.Results indicate that six characteristic solvation configurations exist,exhibiting a dynamic,concentration-dependent inter-evolution defined as the solvation structure evolutionary processes(SSEP).The four-phase glass transition mechanism in solvation structure evolution is revealed by analyzing the percentage of each type of solvation structure in different concentrations.The study shows that conductivity is directly related to the dynamic transitions of dominant solvation structures,with a shift in the Mg^(2+) coordination mode—from octahedral through pentahedral intermediates to tetrahedral—revealing a concentration-dependent ion transport mechanism.At low concentrations,free-state stochastic diffusion predominates,reaching a maximum conductivity before transitioning to relay transport within a restricted network at high concentrations.Key contributions include:a general strategy for electrolyte design based on the solvation structure evolution process,which quantitatively correlates structural occupancy with migration properties,and the“Concentration Window”regulation model that balances high conductivity with reduced side reactions.These findings clarify the structural origins of anomalous conductivity in highly concentrated electrolytes and establish a mapping between microstructural evolution and macroscopic performance,providing a theoretical basis for engineering high-security electrolytes of AMIBs.展开更多
Sodium-ion hybrid capacitors(SICs),which combine the high energy density of batteries with the high power density and long cycle life of capacitors,are considered promising next-generation energy storage devices.Ensur...Sodium-ion hybrid capacitors(SICs),which combine the high energy density of batteries with the high power density and long cycle life of capacitors,are considered promising next-generation energy storage devices.Ensuring the performance of SICs in low-temperature environments is crucial for applications in high-altitude cold regions,where the desolvation process of Na+and the transport process in the solid electrolyte interphase(SEI)are determinant.In this paper,we proposed a multi-ether modulation strategy to construct a solvation sheath with multi-ether participation by modulating the coordination of Na+and solvents.This unique solvation sheath not only reduces the desolvation energy barrier of Na+,but more importantly forms a Na_(2)O-rich inorganic SEI and enhances the ionic dynamics of Na+.Benefiting from the excellent solvation structure design,SICs prepared with this electrolyte can achieve energy density of up to 178 Wh·kg^(-1) and ultra-high power density of 42390 W·kg^(-1) at room temperature.Notably,this SIC delivers record-high energy densities of 149 Wh·kg^(-1) and 119 Wh·kg^(-1) as well as power densities of up to 25200 W·kg^(-1) and 24591 W·kg^(-1) at−20℃ and−40℃,respectively.This work provides new ideas for the development of high-performance SICs for low-temperature operating environments.展开更多
Aqueous aluminum-ion batteries(AIBs)are promising candidates for large-scale energy storage due to the abundant resource reserve,high theoretical capacity,intrinsic safety,and low cost of Al.However,the development of...Aqueous aluminum-ion batteries(AIBs)are promising candidates for large-scale energy storage due to the abundant resource reserve,high theoretical capacity,intrinsic safety,and low cost of Al.However,the development of aqueous AIBs is constrained by the inefficient Al plating,inevitable parasitic side reactions,and the collapse of the cathode materials.Herein,we propose a novel Al^(3+)/Mn^(2+)hybrid electrolyte in a water-acetonitrile co-solvent system with a regulated solvation structure to realize cathode-free AIBs.The inclusion of acetonitrile as a co-solvent plays a crucial role in reducing the desolvation energy and suppressing side reactions.The introduction of Mn^(2+)can enable the reversible plating/stripping of Al-Mn alloy with reduced overpotentials on the anode and deposition/stripping of Al_(x)MnO_(2) on the cathodic current collector to realize cathode-free AIBs.The architected AIB delivers a high discharge capacity of 397.9 mAh g^(-1),coupled with superior rate capability and stable cycling performance.Moreover,the cathode-free AIB shows superior low-temperature performance and can operate at-20℃ for over 120 cycles.This work provides new ideas for developing high-performance and low-cost aqueous AIBs.展开更多
Aqueous zinc-ion batteries are regarded as the promising candidates for large-scale energy storage systems owing to low cost and high safety;however,their applications are restricted by their poor low-temperature perf...Aqueous zinc-ion batteries are regarded as the promising candidates for large-scale energy storage systems owing to low cost and high safety;however,their applications are restricted by their poor low-temperature performance.Herein,a low-temperature electrolyte for low-temperature aqueous zinc-ion batteries is designed by introducing low-polarity diglyme into an aqueous solution of Zn(ClO_(4))_(2).The diglyme disrupts the hydrogenbonding network of water and lowers the freezing point of the electrolyte to-105℃.The designed electrolyte achieves ionic conductivity up to16.18 mS cm^(-1)at-45℃.The diglyme and ClO_(4)^(-)reconfigure the solvated structure of Zn^(2+),which is more favorable for the desolvation of Zn^(2+)at low temperatures.In addition,the diglyme effectively suppresses the dendrites,hydrogen evolution reaction,and by-products of the zinc anode,improving the cycle stability of the battery.At-20℃,a Zn‖Zn symmetrical cell is cycled for 5200 h at 1 mA cm^(-2)and 1 mA h cm^(-2),and a Zn‖polyaniline battery achieves an ultra-long cycle life of 10000 times.This study sheds light on the future design of electrolytes with high ionic conductivity and easy desolvation at low temperatures for rechargeable batteries.展开更多
The battery energy density can be improved by raising the operating voltage,however,which may lead to rapid capacity decay due to the continuous electrolyte decomposition and the thickening of electrode electrolyte in...The battery energy density can be improved by raising the operating voltage,however,which may lead to rapid capacity decay due to the continuous electrolyte decomposition and the thickening of electrode electrolyte interphases.To address these challenges,we proposed tripropyl phosphate(TPP)as an additive-regulating Li~+solvation structure to construct a stable Li F–rich electrode carbonate-based electrolyte interphases for sustaining 4.6 V Li||LiCoO_(2)batteries.This optimized interphases could help reduce the resistance and achieve better rate performance and cycling stability.As expected,the Li||LiCoO_(2)battery retained 79.4%capacity after 100 cycles at 0.5 C,while the Li||Li symmetric cell also kept a stable plating/stripping process over 450 h at the current density of 1.0 mA/cm^(2)with a deposited amount of0.5 mAh/cm^(2).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
Tris(trimethylsilyl)borate(TMSB) has been intensively studied to improve the performances of lithiumion batteries. However, it is still an interesting issue needed to be resolved for the research on the Li^(+) solvati...Tris(trimethylsilyl)borate(TMSB) has been intensively studied to improve the performances of lithiumion batteries. However, it is still an interesting issue needed to be resolved for the research on the Li^(+) solvation structure affected by TMSB additive. Herein, the electrochemical tests, quantum chemistry calculations, potential-resolved in-situ electrochemical impedance spectroscopy measurements and surface analyses were used to explore the effects of Li^(+) solvation structure with TMSB additive on the formation of the cathode electrolyte interface(CEI) film in LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)/Li half cells. The results reveal that the TMSB additive is easy to complex with Li^(+) ion, thus weaken the intermolecular force between Li^(+) ions and ethylene carbonate solvent, which is benefit for the cycle performance. Besides, the changed Li^(+) solvation structure results in a thin and dense CEI film containing compounds with Si–O and B–O bonds which is favorable to the transfer of Li^(+) ions. As a result, the performances of the LNCM811/Li half cells are effectively improved. This research provides a new idea to construct a high-performance CEI film by adjusting the Li^(+) solvation structures.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
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
Lithium metal batteries(LMBs)are considered to be one of the most promising high-energy-density battery systems.However,their practical application in carbonate electrolytes is hampered by lithium dendrite growth,resu...Lithium metal batteries(LMBs)are considered to be one of the most promising high-energy-density battery systems.However,their practical application in carbonate electrolytes is hampered by lithium dendrite growth,resulting in short cycle life.Herein,an electrolyte regulation strategy is developed to improve the cyclability of LMBs in carbonate electrolytes by introducing LiNO3 using trimethyl phosphate with a slightly higher donor number compared to NO_(3)^(-)as a solubilizer.This not only allows the formaion of Li^(+)-coordinated NO3 but also achieves the regulation of electrolyte solvation structures,leading to the formation of robust and ion-conductive solid-electrolyte interphase films with inorganic-rich inner and organic-rich outer layers on the Li metal anodes.As a result,high Coulombic efficiency of 99.1%and stable plating/stripping cycling of Li metal anode in LilCu cells were realized.Furthermore,excellent performance was also demonstrated in Li||LiNi_(0.83)Co_(0.11)Mn_(0.06)O_(2)(NCM83)full cells and Cul/NCM83 anodefree cells using high mass-loading cathodes.This work provides a simple interphase engineering strategy through regulating the electrolyte solvation structures for high-energy-density LMBs.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
Sodium metal batteries(SMBs)are expected to become an alternative solution for energy storage and power systems in the future due to their abundant resources,substantial energy–density,and all-climate performance.How...Sodium metal batteries(SMBs)are expected to become an alternative solution for energy storage and power systems in the future due to their abundant resources,substantial energy–density,and all-climate performance.However,uneven Na deposition and slow charge transfer kinetics still significantly impair their low temperature and rate performance.Herein,we report a non-solvating trifluoromethoxy benzene(PhOCF_(3))that modulates dipole–dipole interactions in the solvation structure.This modulation effectively reduces the affinity between Na+and solvents,promoting an anion-rich solvation sheath formation and significantly enhancing room temperature electrochemical performance in SMBs.Furthermore,temperature-dependent spectroscopic characterizations and molecular dynamics simulations reveal that these dipole–dipole interactions thermodynamically exclude solvent molecules from inner Na^(+)solvation sphere at low temperatures,which endows the electrolyte with exceptional temperature adaptability,leading to remarkable improvement in low temperature SMB performance.Consequently,Na||Vanadium phosphate sodium(NVP)cells with the optimized electrolyte achieve 10,000 cycles at 10 C with capacity retention of 90.2%at 25℃and over 650 cycles at 0.5 C with a capacity of 92.1 mA h g^(−1)at−40℃.This work probed the temperature-responsive property of Na+solvation structure and designed the temperature-adaptive electrolyte by regulating solvation structure via dipole–dipole interactions,offering a valuable guidance for low temperature electrolytes design for SMBs.展开更多
Optimizing electrolytes is non-trivial and yet promising strategies to simultaneously address dendrite growth and parasitic reactions for aqueous zinc-ion batteries.Herein,we present a low-cost zwitterionic additive,1...Optimizing electrolytes is non-trivial and yet promising strategies to simultaneously address dendrite growth and parasitic reactions for aqueous zinc-ion batteries.Herein,we present a low-cost zwitterionic additive,1-butylsulfonic-3-methylimidazolium(BSM),to enhance conventional ZnSO_(4)electrolytes.Combining experimental characterization and theoretical calculations,the results reveal that the zincophilic sulfonate groups in BSM partially substitute coordinated H_(2)O molecules in the Zn^(2+)hydration shell,thereby optimizing solvation dynamics.Meanwhile,the imidazole groups are preferentially adsorbed onto the zinc anode surface,forming an adaptive layer that guides uniform Zn^(2+)deposition along the(002)crystal orientation,suppresses parasitic reaction,and mitigates dendrite growth.Consequently,the Zn||Zn symmetric cells with BSM electrolyte achieve an exceptional plating/stripping lifespan of 4000 h at 1 mA cm^(-2)(1 mA h cm^(-2))and over 1600 h under elevated current density(5 mA cm^(-2),5 mA h cm^(-2)).Moreover,the Zn||Cu asymmetric cell demonstrates a long cycle life exceeding 1100 cycles while it maintains an average Coulombic efficiency(CE)of above 99.5%.Impressively,the assembled Zn||NH_(4)V_(4)O_(10)(NVO)full cell with BSM modified ZnSO_(4)electrolyte retains 77.6%capacity retention after 1000 cycles at 5 A g^(-1).Thus,this work establishes a dual-regulatory mechanism through zwitterionic additives to enable dendrite-free anodes and ultra-stable aqueous metal batteries.展开更多
Although MXene has attracted great interest in diverse fields,it is susceptible to oxidation in water(H_(2)O)with transition metal ions such as Co^(2+),Fe^(2+),and Cu^(2+),which is pronounced at high temperatures.This...Although MXene has attracted great interest in diverse fields,it is susceptible to oxidation in water(H_(2)O)with transition metal ions such as Co^(2+),Fe^(2+),and Cu^(2+),which is pronounced at high temperatures.This impedes the preparation of MXene-based composites and their functional applications.Here,this study revealed that Co^(2+)increases the maximum and average atomic charge of H in H_(2)O to improve the reactivity of H_(2)O,which leads to the fact that Co^(2+)catalyzes the oxidation of Ti_(3)C_(2)T_(x)MXene.Furthermore,the addition of N,Ndimethyl formamide(DMF)reduces theH_(2)Oactivity and improves the oxidation stability of Ti_(3)C_(2)T_(x)in the presence of Co^(2+)via preferentially forming coordination bonds with Co^(2+).This strategy is also effective in enhancing the oxidation tolerance of Ti_(3)C_(2)T_(x)to Fe^(2+)in H_(2)O.Moreover,it is feasible to enhance the oxidation stability of Ti2CTx MXene in H_(2)O with the existence of Co^(2+).By virtue of these,the CoO/Ti_(3)C_(2)T_(x)composite was successfully prepared without obvious Ti_(3)C_(2)T_(x)oxidation,which is desirable to harness the advantages of Ti_(3)C_(2)T_(x)as the complementary component for lithium-ion batteries.This work provides a straightforward paradigm to enhance the oxidation resistance of MXene in H_(2)O in the presence of transition metal ions and at high temperatures,which opens a new vista to use MXene for target applications.展开更多
基金supported by the National Natural Science Foundation of China(52272258 and 52411530056)the Beijing Nova Program(20220484214)+1 种基金Key R&D and Transformation Projects in Qinghai Province(2023-HZ-801)the financial support from the China Scholarship Council(No.202006210070)。
文摘Aqueous zinc-ion batteries encounter impediments on their trajectory towards commercialization,primarily due to challenges such as dendritic growth,hydrogen evolution reaction.Throughout recent decades of investigation,electrolyte modulation by using function additives is widely considered as a facile and efficient way to prolong the Zn anode lifespan.Herein,N-(2-hydroxypropyl)ethylenediamine is employed as an additive to attach onto the Zn surface with a substantial adsorption energy with(002)facet.The as-formed in-situ solid-electrolyte interphase layer effectively mitigates hydrogen evolution reaction by constructing a lean-water internal Helmholtz layer.Additionally,N-(2-hydroxypropyl)ethylenediamine establishes a coordination complex with Zn^(2+),thereby modulating the solvation structure and enhancing the mobility of Zn^(2+).As expected,the Zn-symmetrical cell with N-(2-hydroxypropyl)ethylenediamine additive demonstrated successful cycling exceeding 1500 h under 1 mA cm^(-2) for0.5 mAh cm^(-2).Furthermore,the Zn//δ-MnO_(2) battery maintains a capacity of approximately 130 mAh g^(-1) after 800 cycles at 1 A g^(-1),with a Coulombic efficiency surpassing 98%.This work presents a streamlined approach for realizing aqueous zinc-ion batteries with extended service life.
基金funded by National Natural Science Foundation of China (22379072, 92372111, 22179070)the Startup Foundation for Introducing Talent of NUIST (2022r038)+1 种基金the Jiangsu Specially Appointed Professor Program, the Natural Science Foundation of Jiangsu Province (BK20220073)the Fundamental Research Funds for the Central Universities (RF1028623157)。
文摘Designing anion-dominated weak solvation structures is often achieved by elevating the concentration of Li salts.However,this is accompanied by the increase in the cost.Herein,a medium concentration electrolyte (1 M) with weak solvation structures is established by the multi-anion strategy.Multiple anions in the electrolyte strengthen the anion-solvent interactions through stronger ion–dipole interactions.This reduces the quantity of free solvent and improves the reduction resistance of solvents.In addition,the Li ion–solvent interaction is weakened,facilitating the anions to enter the solvation sheaths of Li ions.This multi-anion-dominated weak solvation structures boost Li ion diffusion in the electrolyte,accelerate the desolvation process of Li ions,and induce inorganic-rich solid electrolyte interphase and uniform Li deposition.An average Coulombic efficiency of 99.1%for repeated Li plating/stripping can be achieved.Li||LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) cells with a high cathode loading of 3.0 m A h cm^(-2) can maintain a capacity retention as high as 95% after 150 cycles.This finding provides novel standpoints to modulate the interaction of solvation structures and extend the lifespan of high-energy–density Li metal batteries.
基金supported by the National Natural Science Foundation of China(51972187 and 22279068)the Natural Science Foundation of Shandong Province(ZR2023ME182)the Fundation of Key Laboratory of Green Fabrication and Surface Technology of Advanced Metal Materials(Anhui University of Technology)(GFST2024KF03)。
文摘Monovalent anions,with relatively low charge density,exhibit weak bond energy with Zn^(2+)ions,which facilitates the solubility of Zn salts and the regulation of solvation structures.In this study,zinc bis(aminosulfate)(Zn(NH_(2)SO_(3))_(2))with a monovalent anion,NH_(2)SO_(3)^(-),was synthesized and dissolved in different ratios of dimethyl sulfoxide(DMSO)and H_(2)O as electrolytes for Zn-ion batteries(ZIBs).From the perspective of game theory,the influences of DMSO and H_(2)O on the solvation structure and electrochemical performance of the Zn(NH_(2)SO_(3))_(2)based electrolytes has been meticulously discussed.Computations and spectra analysis indicate that DMSO molecules are reluctant to penetrate the primary solvation structure of Zn^(2+)ions.Indeed,increasing DMSO in electrolytes can induce a transition from solvent-separated ion pairs(SSIP)to contact ion pairs(CIP),resulting in an enrichment of anions in the primary solvation structure.This alteration can significantly suppress parasitic reactions,enhance nucleation density,and refine the deposition morphology during the Zn plating process,leading to superior cyclic stability and high coulombic efficiency(CE)of Zn//Cu and Zn//Zn cells.However,the enrichment of anions in the primary solvation structure also inhibits the activity of Zn^(2+)ions,amplifies the polarization effect,and engenders a sluggish ionization dynamics,resulting in the low energy conversion efficiency of the battery.These findings underscore the influence of the anion ratio within the primary solvation structure on electrochemical properties of electrolytes for ZIBs,which may be a pivotal determinant in the Zn deposition process.
基金supported by the Natural Science Foundation of China(22379073,52373275)the Natural Science Foundation of Tianjin,China(18JCZDJC31400)the Ministry of Education Innovation Team(IRT13022).
文摘Quasi-solid polymer electrolytes(QSPEs)have been attracted significant attentions due to their benefits for simultaneously improved safety and energy density of batteries.Developing electrolytes capable of forming a stable solid electrolyte interphase(SEI)layer is a great challenge for QSPE-based lithium(Li)metal batteries(LMBs).Herein,unlike previously reports that the reconstruction of Li^(+)solvation structures in QSPE requires time-consuming bottom-up polymer synthesis,in current study,a facile approach has been developed to reconstruct the Li^(+)solvation structures in QSPE by adjustment of the salt concentrations.The high proportion of Li^(+)-anion complexes can effectively accelerate interfacial Li^(+)diffusion,mitigate the decompositions of organic solvents and induce the formation of a LiF-rich SEI layer,contributing to suppressed Li-dendrite growth.As a result,the Li/QSPE-3/LiFePO_(4)(LFP)cell performs an ultralong lifespan with capacity retention of 77.4%over 3000 cycles at 1 C.With a high-voltage LiCoO_(2)cathode,the cell can stably cycle over 200 cycles at 25℃(capacity retention of∼83.8%).With accelerated ion transport dynamics due to the reconstructed Li^(+)solvation structure,the QSPE-3(the salt concentration is 3 M)is applicable in a wide temperature range.The Li/QSPE-3/LFP full cell exhibits 58.1%and 102.6%of discharge capacity at−15 and 90℃,respectively,compared to those operated at 25℃This study demonstrates a facile yet effective approach on enhancing electrode/electrolyte interfacial stability,enabling the LMBs with simultaneously enhanced safety and high energy density.
基金supported by the National Natural Science Foundation of China(No.11047164)the National Key Laboratory of Infrared Detection Technologies(No.IRDT-23-S01)the Shanghai Explorer Program(No.24TS1403400)。
文摘The high safety of aqueous magnesium ion batteries(AMIBs)contrasts with their limited electrochemical performance.To overcome electrolyte-induced parasitic reactions,it is essential to understand the dynamic evolution of concentration-dependent metal ion solvation structures(MISSs).This study systematically reveals the solvation structure evolution of MgCl_(2) aqueous solutions across a full concentration range(0-30 M)and its impact on electrochemical properties using molecular dynamics simulations and density functional theory calculations.Results indicate that six characteristic solvation configurations exist,exhibiting a dynamic,concentration-dependent inter-evolution defined as the solvation structure evolutionary processes(SSEP).The four-phase glass transition mechanism in solvation structure evolution is revealed by analyzing the percentage of each type of solvation structure in different concentrations.The study shows that conductivity is directly related to the dynamic transitions of dominant solvation structures,with a shift in the Mg^(2+) coordination mode—from octahedral through pentahedral intermediates to tetrahedral—revealing a concentration-dependent ion transport mechanism.At low concentrations,free-state stochastic diffusion predominates,reaching a maximum conductivity before transitioning to relay transport within a restricted network at high concentrations.Key contributions include:a general strategy for electrolyte design based on the solvation structure evolution process,which quantitatively correlates structural occupancy with migration properties,and the“Concentration Window”regulation model that balances high conductivity with reduced side reactions.These findings clarify the structural origins of anomalous conductivity in highly concentrated electrolytes and establish a mapping between microstructural evolution and macroscopic performance,providing a theoretical basis for engineering high-security electrolytes of AMIBs.
基金support from National Outstanding Youth Science Fund(52222314)Near Space Technology and Industry Guidance Fund Project(LKJJ-2023010-01)+3 种基金CNPC Innovation Found(2021DQ02-1001)Dalian Outstanding Youth Science and Technology Talent Project(2023RJ006)Dalian Science and Technology Innovation Project(2022JJ12GX022)Xinghai Talent Cultivation Plan(X20200303).
文摘Sodium-ion hybrid capacitors(SICs),which combine the high energy density of batteries with the high power density and long cycle life of capacitors,are considered promising next-generation energy storage devices.Ensuring the performance of SICs in low-temperature environments is crucial for applications in high-altitude cold regions,where the desolvation process of Na+and the transport process in the solid electrolyte interphase(SEI)are determinant.In this paper,we proposed a multi-ether modulation strategy to construct a solvation sheath with multi-ether participation by modulating the coordination of Na+and solvents.This unique solvation sheath not only reduces the desolvation energy barrier of Na+,but more importantly forms a Na_(2)O-rich inorganic SEI and enhances the ionic dynamics of Na+.Benefiting from the excellent solvation structure design,SICs prepared with this electrolyte can achieve energy density of up to 178 Wh·kg^(-1) and ultra-high power density of 42390 W·kg^(-1) at room temperature.Notably,this SIC delivers record-high energy densities of 149 Wh·kg^(-1) and 119 Wh·kg^(-1) as well as power densities of up to 25200 W·kg^(-1) and 24591 W·kg^(-1) at−20℃ and−40℃,respectively.This work provides new ideas for the development of high-performance SICs for low-temperature operating environments.
基金financially supported by the National Natural Science Foundation of China(No.52274302)。
文摘Aqueous aluminum-ion batteries(AIBs)are promising candidates for large-scale energy storage due to the abundant resource reserve,high theoretical capacity,intrinsic safety,and low cost of Al.However,the development of aqueous AIBs is constrained by the inefficient Al plating,inevitable parasitic side reactions,and the collapse of the cathode materials.Herein,we propose a novel Al^(3+)/Mn^(2+)hybrid electrolyte in a water-acetonitrile co-solvent system with a regulated solvation structure to realize cathode-free AIBs.The inclusion of acetonitrile as a co-solvent plays a crucial role in reducing the desolvation energy and suppressing side reactions.The introduction of Mn^(2+)can enable the reversible plating/stripping of Al-Mn alloy with reduced overpotentials on the anode and deposition/stripping of Al_(x)MnO_(2) on the cathodic current collector to realize cathode-free AIBs.The architected AIB delivers a high discharge capacity of 397.9 mAh g^(-1),coupled with superior rate capability and stable cycling performance.Moreover,the cathode-free AIB shows superior low-temperature performance and can operate at-20℃ for over 120 cycles.This work provides new ideas for developing high-performance and low-cost aqueous AIBs.
文摘Aqueous zinc-ion batteries are regarded as the promising candidates for large-scale energy storage systems owing to low cost and high safety;however,their applications are restricted by their poor low-temperature performance.Herein,a low-temperature electrolyte for low-temperature aqueous zinc-ion batteries is designed by introducing low-polarity diglyme into an aqueous solution of Zn(ClO_(4))_(2).The diglyme disrupts the hydrogenbonding network of water and lowers the freezing point of the electrolyte to-105℃.The designed electrolyte achieves ionic conductivity up to16.18 mS cm^(-1)at-45℃.The diglyme and ClO_(4)^(-)reconfigure the solvated structure of Zn^(2+),which is more favorable for the desolvation of Zn^(2+)at low temperatures.In addition,the diglyme effectively suppresses the dendrites,hydrogen evolution reaction,and by-products of the zinc anode,improving the cycle stability of the battery.At-20℃,a Zn‖Zn symmetrical cell is cycled for 5200 h at 1 mA cm^(-2)and 1 mA h cm^(-2),and a Zn‖polyaniline battery achieves an ultra-long cycle life of 10000 times.This study sheds light on the future design of electrolytes with high ionic conductivity and easy desolvation at low temperatures for rechargeable batteries.
基金supported by the National Natural Science Foundation of China(No.U21A20311)the Distinguished Scientist Fellowship Program(DSFP)at King Saud University,Riyadh,Saudi Arabia。
文摘The battery energy density can be improved by raising the operating voltage,however,which may lead to rapid capacity decay due to the continuous electrolyte decomposition and the thickening of electrode electrolyte interphases.To address these challenges,we proposed tripropyl phosphate(TPP)as an additive-regulating Li~+solvation structure to construct a stable Li F–rich electrode carbonate-based electrolyte interphases for sustaining 4.6 V Li||LiCoO_(2)batteries.This optimized interphases could help reduce the resistance and achieve better rate performance and cycling stability.As expected,the Li||LiCoO_(2)battery retained 79.4%capacity after 100 cycles at 0.5 C,while the Li||Li symmetric cell also kept a stable plating/stripping process over 450 h at the current density of 1.0 mA/cm^(2)with a deposited amount of0.5 mAh/cm^(2).
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(51962019)the Natural Science Foundation of Gansu Province(20JR5RA469)+1 种基金the Education Department of Gansu Province:"Star of Innovation"Project for Outstanding Graduate Students(2021CXZX-455)the Lanzhou University of Technology Hongliu First-class Discipline Construction Program。
文摘Tris(trimethylsilyl)borate(TMSB) has been intensively studied to improve the performances of lithiumion batteries. However, it is still an interesting issue needed to be resolved for the research on the Li^(+) solvation structure affected by TMSB additive. Herein, the electrochemical tests, quantum chemistry calculations, potential-resolved in-situ electrochemical impedance spectroscopy measurements and surface analyses were used to explore the effects of Li^(+) solvation structure with TMSB additive on the formation of the cathode electrolyte interface(CEI) film in LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)/Li half cells. The results reveal that the TMSB additive is easy to complex with Li^(+) ion, thus weaken the intermolecular force between Li^(+) ions and ethylene carbonate solvent, which is benefit for the cycle performance. Besides, the changed Li^(+) solvation structure results in a thin and dense CEI film containing compounds with Si–O and B–O bonds which is favorable to the transfer of Li^(+) ions. As a result, the performances of the LNCM811/Li half cells are effectively improved. This research provides a new idea to construct a high-performance CEI film by adjusting the Li^(+) solvation structures.
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 Key Research and Development Program of China(No.2019YFE0118800).
文摘Lithium metal batteries(LMBs)are considered to be one of the most promising high-energy-density battery systems.However,their practical application in carbonate electrolytes is hampered by lithium dendrite growth,resulting in short cycle life.Herein,an electrolyte regulation strategy is developed to improve the cyclability of LMBs in carbonate electrolytes by introducing LiNO3 using trimethyl phosphate with a slightly higher donor number compared to NO_(3)^(-)as a solubilizer.This not only allows the formaion of Li^(+)-coordinated NO3 but also achieves the regulation of electrolyte solvation structures,leading to the formation of robust and ion-conductive solid-electrolyte interphase films with inorganic-rich inner and organic-rich outer layers on the Li metal anodes.As a result,high Coulombic efficiency of 99.1%and stable plating/stripping cycling of Li metal anode in LilCu cells were realized.Furthermore,excellent performance was also demonstrated in Li||LiNi_(0.83)Co_(0.11)Mn_(0.06)O_(2)(NCM83)full cells and Cul/NCM83 anodefree cells using high mass-loading cathodes.This work provides a simple interphase engineering strategy through regulating the electrolyte solvation structures for high-energy-density LMBs.
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the financial support of National Key Research and Development Program of China(2021YFB2400300)National Natural Science Foundation of China(21875198,21875195)+1 种基金the Fundamental Research Funds for the Central Universities(20720190040)the Key Project of Science and Technology of Xiamen(3502Z20201013)。
文摘Sodium metal batteries(SMBs)are expected to become an alternative solution for energy storage and power systems in the future due to their abundant resources,substantial energy–density,and all-climate performance.However,uneven Na deposition and slow charge transfer kinetics still significantly impair their low temperature and rate performance.Herein,we report a non-solvating trifluoromethoxy benzene(PhOCF_(3))that modulates dipole–dipole interactions in the solvation structure.This modulation effectively reduces the affinity between Na+and solvents,promoting an anion-rich solvation sheath formation and significantly enhancing room temperature electrochemical performance in SMBs.Furthermore,temperature-dependent spectroscopic characterizations and molecular dynamics simulations reveal that these dipole–dipole interactions thermodynamically exclude solvent molecules from inner Na^(+)solvation sphere at low temperatures,which endows the electrolyte with exceptional temperature adaptability,leading to remarkable improvement in low temperature SMB performance.Consequently,Na||Vanadium phosphate sodium(NVP)cells with the optimized electrolyte achieve 10,000 cycles at 10 C with capacity retention of 90.2%at 25℃and over 650 cycles at 0.5 C with a capacity of 92.1 mA h g^(−1)at−40℃.This work probed the temperature-responsive property of Na+solvation structure and designed the temperature-adaptive electrolyte by regulating solvation structure via dipole–dipole interactions,offering a valuable guidance for low temperature electrolytes design for SMBs.
基金financially supported by the National Natural Science Foundation of China(No.21703152,21801136,52025013,and 22121005)the National Key R&D Program of China(2021YFB4000200)the Natural Science Foundation of Tianjin(No.19JCQNJC02000)。
文摘Optimizing electrolytes is non-trivial and yet promising strategies to simultaneously address dendrite growth and parasitic reactions for aqueous zinc-ion batteries.Herein,we present a low-cost zwitterionic additive,1-butylsulfonic-3-methylimidazolium(BSM),to enhance conventional ZnSO_(4)electrolytes.Combining experimental characterization and theoretical calculations,the results reveal that the zincophilic sulfonate groups in BSM partially substitute coordinated H_(2)O molecules in the Zn^(2+)hydration shell,thereby optimizing solvation dynamics.Meanwhile,the imidazole groups are preferentially adsorbed onto the zinc anode surface,forming an adaptive layer that guides uniform Zn^(2+)deposition along the(002)crystal orientation,suppresses parasitic reaction,and mitigates dendrite growth.Consequently,the Zn||Zn symmetric cells with BSM electrolyte achieve an exceptional plating/stripping lifespan of 4000 h at 1 mA cm^(-2)(1 mA h cm^(-2))and over 1600 h under elevated current density(5 mA cm^(-2),5 mA h cm^(-2)).Moreover,the Zn||Cu asymmetric cell demonstrates a long cycle life exceeding 1100 cycles while it maintains an average Coulombic efficiency(CE)of above 99.5%.Impressively,the assembled Zn||NH_(4)V_(4)O_(10)(NVO)full cell with BSM modified ZnSO_(4)electrolyte retains 77.6%capacity retention after 1000 cycles at 5 A g^(-1).Thus,this work establishes a dual-regulatory mechanism through zwitterionic additives to enable dendrite-free anodes and ultra-stable aqueous metal batteries.
基金National Natural Science Foundation of China,Grant/Award Numbers:52272295,52071137,51977071,51802040,21802020Science and Technology Innovation Program of Hunan Province,Grant/Award Numbers:2021RC3066,2021RC3067+1 种基金Natural Science Foundation of Hunan Province,Grant/Award Number:2020JJ3004Fundamental Research Funds for the Central Universities。
文摘Although MXene has attracted great interest in diverse fields,it is susceptible to oxidation in water(H_(2)O)with transition metal ions such as Co^(2+),Fe^(2+),and Cu^(2+),which is pronounced at high temperatures.This impedes the preparation of MXene-based composites and their functional applications.Here,this study revealed that Co^(2+)increases the maximum and average atomic charge of H in H_(2)O to improve the reactivity of H_(2)O,which leads to the fact that Co^(2+)catalyzes the oxidation of Ti_(3)C_(2)T_(x)MXene.Furthermore,the addition of N,Ndimethyl formamide(DMF)reduces theH_(2)Oactivity and improves the oxidation stability of Ti_(3)C_(2)T_(x)in the presence of Co^(2+)via preferentially forming coordination bonds with Co^(2+).This strategy is also effective in enhancing the oxidation tolerance of Ti_(3)C_(2)T_(x)to Fe^(2+)in H_(2)O.Moreover,it is feasible to enhance the oxidation stability of Ti2CTx MXene in H_(2)O with the existence of Co^(2+).By virtue of these,the CoO/Ti_(3)C_(2)T_(x)composite was successfully prepared without obvious Ti_(3)C_(2)T_(x)oxidation,which is desirable to harness the advantages of Ti_(3)C_(2)T_(x)as the complementary component for lithium-ion batteries.This work provides a straightforward paradigm to enhance the oxidation resistance of MXene in H_(2)O in the presence of transition metal ions and at high temperatures,which opens a new vista to use MXene for target applications.
