An anion-rich electric double layer(EDL)region is favorable for fabricating an inorganic-rich solid-electrolyte interphase(SEI)towards stable lithium metal anode in ester electrolyte.Herein,cetyltrimethylammonium brom...An anion-rich electric double layer(EDL)region is favorable for fabricating an inorganic-rich solid-electrolyte interphase(SEI)towards stable lithium metal anode in ester electrolyte.Herein,cetyltrimethylammonium bromide(CTAB),a cationic surfactant,is adopted to draw more anions into EDL by ionic interactions that shield the repelling force on anions during lithium plating.In situ electrochemical surface-enhanced Raman spectroscopy results combined with molecular dynamics simulations validate the enrichment of NO_(3)^(−)/FSI−anions in the EDL region due to the positively charged CTA^(+).In-depth analysis of SEI structure by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry results confirmed the formation of the inorganic-rich SEI,which helps improve the kinetics of Li^(+)transfer,lower the charge transfer activation energy,and homogenize Li deposition.As a result,the Li||Li symmetric cell in the designed electrolyte displays a prolongated cycling time from 500 to 1300 h compared to that in the blank electrolyte at 0.5 mA cm^(-2) with a capacity of 1 mAh cm^(-2).Moreover,Li||LiFePO_(4) and Li||LiCoO_(2) with a high cathode mass loading of>10 mg cm^(-2) can be stably cycled over 180 cycles.展开更多
Rechargeable magnesium(Mg)-metal batteries have brought great expect to overcome the safety and energy density concerns of typical lithium-ion batteries.However,interracial passivation of the Mgmetal anode impairs the...Rechargeable magnesium(Mg)-metal batteries have brought great expect to overcome the safety and energy density concerns of typical lithium-ion batteries.However,interracial passivation of the Mgmetal anode impairs the reversible Mg plating/stripping chemistries,resulting in low Coulombic efficiency and large overpotential.In this work,a facile isobutylamine(IBA)-assisted activation strategy has been proposed and the fundamental mechanism has been unveiled in a specific way of evolving active species and forming MgH_(2)-based solid-electrolyte interphase.After introducing IBA into a typical electrolyte of magnesium bis(trifluoromethanesulfo nyl) imide(Mg(TFSI)_(2)) in diglyme(G2) solvents,electrolyte species of [Mg^(2+)(IBA)5]^(2+) and protonated amine-based cations of [(IBA)H]^(+) have been detected by nuclear magnetic resonance and mass spectra.This not only indicates direct solvation of IBA toward Mg^(2+)but also suggests its ionization,which is central to mitigating the decomposition of G2 and TFSI anions by forming neutrally charged [(IBAH^(+))(TFSI^(-))]~0 and other complex ions.A series of experiments,including cryogenic-electron microscopy,D_(2)O titration-mass spectra,and time of flight secondary ion mass spectrometry results,reveal a thin,non-passivated,and MgH_(2)-containing interphase on the Mg-metal anode.Besides,uniform and dendrite-free Mg electrodeposits have been revealed in composite electrolytes.Benefiting from the activation effects of IBA,the composite electrolyte displays superior electrochemical performance(overpotential is approximately 0.16 V versus 2.00 V for conventional electrolyte;Coulombic efficiency is above 90% versus <10% for conventional electrolyte).This work offers a fresh direction to advanced electrolyte design for next-generation rechargeable batteries.展开更多
In the pursuit of ultrathin polymer electrolyte(<20 μm) for lithium metal batteries, achieving a balance between mechanical strength and interfacial stability is crucial for the longevity of the electrolytes.Herei...In the pursuit of ultrathin polymer electrolyte(<20 μm) for lithium metal batteries, achieving a balance between mechanical strength and interfacial stability is crucial for the longevity of the electrolytes.Herein, 11 μm-thick gel polymer electrolyte is designed via an integrated electrode/electrolyte structure supported by lithium metal anode. Benefiting from an exemplary superiority of excellent mechanical property, high ionic conductivity, and robust interfacial adhesion, the in-situ formed polymer electrolyte reinforced by titanosiloxane networks(ISPTS) embodies multifunctional roles of physical barrier, ionic carrier, and artificial protective layer at the interface. The potent interfacial interactions foster a seamless fusion of the electrode/electrolyte interfaces and enable continuous ion transport. Moreover, the built-in ISPTS electrolyte participates in the formation of gradient solid-electrolyte interphase(SEI) layer, which enhances the SEI's structural integrity against the strain induced by volume fluctuations of lithium anode.Consequently, the resultant 11 μm-thick ISPTS electrolyte enables lithium symmetric cells with cycling stability over 600 h and LiFePO_(4) cells with remarkable capacity retention of 96.6% after 800 cycles.This study provides a new avenue for designing ultrathin polymer electrolytes towards stable, safe,and high-energy–density lithium metal batteries.展开更多
Aqueous zinc ion batteries show prospects for next-generation renewable energy storage devices.However,the practical applications have been limited by the issues derived from Zn anode.As one of serious problems,Zn den...Aqueous zinc ion batteries show prospects for next-generation renewable energy storage devices.However,the practical applications have been limited by the issues derived from Zn anode.As one of serious problems,Zn dendrite growth caused from the uncontrollable Zn deposition is unfavorable.Herein,with the aim to regulate Zn deposition,an artificial solid–electrolyte interface is subtly engineered with a perovskite type material,BaTiO3,which can be polarized,and its polarization could be switched under the external electric field.Resulting from the aligned dipole in BaTiO3 layer,zinc ions could move in order during cycling process.Regulated Zn migration at the anode/electrolyte interface contributes to the even Zn stripping/plating and confined Zn dendrite growth.As a result,the reversible Zn plating/stripping processes for over 2000 h have been achieved at 1 mA cm^(−2) with capacity of 1 mAh cm−2.Furthermore,this anode endowing the electric dipoles shows enhanced cycling stability for aqueous Zn-MnO2 batteries.The battery can deliver nearly 100%Coulombic efficiency at 2 Ag^(−1) after 300 cycles.展开更多
Aluminum(Al) metal has been regarded as a promising anode for rechargeable batteries because of its natural abundance and high theoretical specific capacity. However, rechargeable aluminum batteries(RABs) using A1 met...Aluminum(Al) metal has been regarded as a promising anode for rechargeable batteries because of its natural abundance and high theoretical specific capacity. However, rechargeable aluminum batteries(RABs) using A1 metal as anode display poor cycling performances owing to interface problems between anode and electrolyte. The solid-electrolyte interphase(SEI) layer on the anode has been confirmed to be essential for improving cycling performances of rechargeable batteries. Therefore, we immerse the Al metal in ionic liquid electrolyte for some time before it is used as anode to remove the passive film and expose fresh Al to the electrolyte. Then the reactions of exposed Al, acid, oxygen and water in electrolyte are occurred to form an SEI layer in the cycle. Al/electrolyte/V_2 O_5 full batteries with the thin, uniform and stable SEI layer on Al metal anode perform high discharge capacity and coulombic efficiency(CE). This work illustrates that an SEI layer is formed on Al metal anode in the cycle using a simple and effective pretreatment process and results in superior cycling performances for RABs.展开更多
Aqueous rechargeable batteries have attracted enormous attention owning to their intrinsic characteristics of non-flammability, low cost, and the superior ionic conductivity of the aqueous electrolyte.However, the nar...Aqueous rechargeable batteries have attracted enormous attention owning to their intrinsic characteristics of non-flammability, low cost, and the superior ionic conductivity of the aqueous electrolyte.However, the narrow electrochemical stability window(1.23 V), imposed by hydrogen and oxygen evolution, constrains the overall energy density of batteries. The revolutionary "water-in-salt” electrolytes considerably expand the electrochemical stability window to 3 or even 4 volts, giving rise to a new series of high-voltage aqueous metal-ion chemistries. Herein, the recent advances in "water-in-salt” electrolytes for aqueous monovalent-ion(Li^(+), Na^(+), K^(+)) rechargeable batteries have been systematically reviewed. Meanwhile, the corresponding reaction mechanisms, electrochemical performances and the existing challenges and opportunities are also highlighted.展开更多
A series of Si/C composites were fabricated based on pitch and Si powders with particle sizes of 30, 100, 500, and 3000 nm. The size effects of the Si particles in the Si/C composites were investigated for lithium-ion...A series of Si/C composites were fabricated based on pitch and Si powders with particle sizes of 30, 100, 500, and 3000 nm. The size effects of the Si particles in the Si/C composites were investigated for lithium-ion battery anodes. The nanoscale Si and Si/C composites exhibited good capacity retentions. Scanning electron microscopy showed that exterior and interior cracks emerging owing to volume expansion as well as parasitic reactions with the electrolyte could well explain the performance failure.展开更多
Potassium-ion batteries(PIBs)have been considered as one of the most promising alternatives to lithiumion batteries(LIBs)in view of their competitive energy density with significantly reduced product cost.Moreover,all...Potassium-ion batteries(PIBs)have been considered as one of the most promising alternatives to lithiumion batteries(LIBs)in view of their competitive energy density with significantly reduced product cost.Moreover,alloy-type materials are expected as a high-performance anode of PIBs thanks to their intrinsic chemical stability as well as high theoretical specific capacity.Unfortunately,the serious incompatibility between alloy-type active materials and electrolytes,especially for the formation of unstable solidelectrolyte interfacial(SEI)films,often leads to insufficient cycle life.Herein,the formation mechanism of SEI films in the K-storage systems based on carbon sphere confined Sb anode(Sb@CS)were investigated in commercially available electrolytes.Physical characterizations and theoretical calculation revealed that the solvents in the dilute electrolyte of 0.8 M KPF_(6)/EC+DEC were excessively decomposed on the interface to generate unstable SEI and thus result in inferior K-storage stability.On the contrary,a salt-concentrated electrolyte(3 M KFSI/DME)can generate inorganic-dominated stable SEI due to the preferential decomposition of anions.As a result,the prepared Sb@CS in the matched 3 M KFSI/DME electrolyte delivered a high reversible capacity of 467.8 m A h g^(-1)after 100 cycles at 100 m A g^(-1),with a slow capacity decay of 0.19%per cycle from the 10th to the 100th cycle.These findings are of great significance for revealing the interfacial reaction between electrodes and electrolytes as well as improving the stability of Sb-based anode materials for PIBs.展开更多
Lithium-oxygen(Li-O) battery is considered as one of the most promising alternatives because of its ultrahigh theoretical energy density. However, their cycling stability is severely restricted by the uncontrollable d...Lithium-oxygen(Li-O) battery is considered as one of the most promising alternatives because of its ultrahigh theoretical energy density. However, their cycling stability is severely restricted by the uncontrollable dendrite growth and serious oxygen corrosion issue on Li surface. Herein, a sulfur-modified Li surface can be successfully constructed via chemical reaction of guanylthiourea(GTU) molecule on Li,which can induce the selectively fast decomposition of lithium bis(trifluoromethanesulfonyl)imide(LiTFSI) to form a smooth and stable inorganics-rich solid-electrolyte interphase(IR-SEI) during the subsequent electrochemical process. Such an IR-SEI cannot only offer a highly reversible and stable Li plating/stripping chemistry with dendrite-free property(10 mA cm^(-2)-10 mAh cm^(-2), > 0.5 years;3 mA cm^(-2)-3 m Ah cm^(-2), > 1 year) but also endows the Li metal an anti-oxygen corrosion function, thereby significantly improving the cycling stability of Li-Obatteries. This work provides a new idea for constructing functional solid-electrolyte interphase(SEI) to achieve highly stable Li metal anode.展开更多
基金financial support from Singapore Ministry of Education under its AcRF Tier 2 Grant No MOE-T2EP10123-0001Singapore National Research Foundation Investigatorship under Grant No NRF-NRFI08-2022-0009Academic Excellence Foundation of BUAA for PhD Students(applicant:Hongfei Xu).
文摘An anion-rich electric double layer(EDL)region is favorable for fabricating an inorganic-rich solid-electrolyte interphase(SEI)towards stable lithium metal anode in ester electrolyte.Herein,cetyltrimethylammonium bromide(CTAB),a cationic surfactant,is adopted to draw more anions into EDL by ionic interactions that shield the repelling force on anions during lithium plating.In situ electrochemical surface-enhanced Raman spectroscopy results combined with molecular dynamics simulations validate the enrichment of NO_(3)^(−)/FSI−anions in the EDL region due to the positively charged CTA^(+).In-depth analysis of SEI structure by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry results confirmed the formation of the inorganic-rich SEI,which helps improve the kinetics of Li^(+)transfer,lower the charge transfer activation energy,and homogenize Li deposition.As a result,the Li||Li symmetric cell in the designed electrolyte displays a prolongated cycling time from 500 to 1300 h compared to that in the blank electrolyte at 0.5 mA cm^(-2) with a capacity of 1 mAh cm^(-2).Moreover,Li||LiFePO_(4) and Li||LiCoO_(2) with a high cathode mass loading of>10 mg cm^(-2) can be stably cycled over 180 cycles.
基金National Natural Science Foundation of China (22279068, 51972187)Natural Science Foundation of Shandong Province (ZR2021QE166)Qingdao New Energy Shandong Laboratory Open Project (QNESL OP202312)。
文摘Rechargeable magnesium(Mg)-metal batteries have brought great expect to overcome the safety and energy density concerns of typical lithium-ion batteries.However,interracial passivation of the Mgmetal anode impairs the reversible Mg plating/stripping chemistries,resulting in low Coulombic efficiency and large overpotential.In this work,a facile isobutylamine(IBA)-assisted activation strategy has been proposed and the fundamental mechanism has been unveiled in a specific way of evolving active species and forming MgH_(2)-based solid-electrolyte interphase.After introducing IBA into a typical electrolyte of magnesium bis(trifluoromethanesulfo nyl) imide(Mg(TFSI)_(2)) in diglyme(G2) solvents,electrolyte species of [Mg^(2+)(IBA)5]^(2+) and protonated amine-based cations of [(IBA)H]^(+) have been detected by nuclear magnetic resonance and mass spectra.This not only indicates direct solvation of IBA toward Mg^(2+)but also suggests its ionization,which is central to mitigating the decomposition of G2 and TFSI anions by forming neutrally charged [(IBAH^(+))(TFSI^(-))]~0 and other complex ions.A series of experiments,including cryogenic-electron microscopy,D_(2)O titration-mass spectra,and time of flight secondary ion mass spectrometry results,reveal a thin,non-passivated,and MgH_(2)-containing interphase on the Mg-metal anode.Besides,uniform and dendrite-free Mg electrodeposits have been revealed in composite electrolytes.Benefiting from the activation effects of IBA,the composite electrolyte displays superior electrochemical performance(overpotential is approximately 0.16 V versus 2.00 V for conventional electrolyte;Coulombic efficiency is above 90% versus <10% for conventional electrolyte).This work offers a fresh direction to advanced electrolyte design for next-generation rechargeable batteries.
基金National Natural Science Foundation of China (22222902, 22209062)Natural Science Foundation of the Jiangsu Higher Education Institutions of China (22KJB150004)+1 种基金Youth Talent Promotion Project of Jiangsu Association for Science and Technology of China (JSTJ-2022-023)Undergraduate Innovation and Entrepreneurship Training Program (202310320066Z)。
文摘In the pursuit of ultrathin polymer electrolyte(<20 μm) for lithium metal batteries, achieving a balance between mechanical strength and interfacial stability is crucial for the longevity of the electrolytes.Herein, 11 μm-thick gel polymer electrolyte is designed via an integrated electrode/electrolyte structure supported by lithium metal anode. Benefiting from an exemplary superiority of excellent mechanical property, high ionic conductivity, and robust interfacial adhesion, the in-situ formed polymer electrolyte reinforced by titanosiloxane networks(ISPTS) embodies multifunctional roles of physical barrier, ionic carrier, and artificial protective layer at the interface. The potent interfacial interactions foster a seamless fusion of the electrode/electrolyte interfaces and enable continuous ion transport. Moreover, the built-in ISPTS electrolyte participates in the formation of gradient solid-electrolyte interphase(SEI) layer, which enhances the SEI's structural integrity against the strain induced by volume fluctuations of lithium anode.Consequently, the resultant 11 μm-thick ISPTS electrolyte enables lithium symmetric cells with cycling stability over 600 h and LiFePO_(4) cells with remarkable capacity retention of 96.6% after 800 cycles.This study provides a new avenue for designing ultrathin polymer electrolytes towards stable, safe,and high-energy–density lithium metal batteries.
基金the partial financial support from the National Natural Science Foundation of China(21935003 and 21805182)National Key Research and Development Plan(2016YFB0901503)+1 种基金Shanghai Pujiang Program(18PJ1403800)the support from the Hundreds of Talents program of Sun Yat-sen University。
文摘Aqueous zinc ion batteries show prospects for next-generation renewable energy storage devices.However,the practical applications have been limited by the issues derived from Zn anode.As one of serious problems,Zn dendrite growth caused from the uncontrollable Zn deposition is unfavorable.Herein,with the aim to regulate Zn deposition,an artificial solid–electrolyte interface is subtly engineered with a perovskite type material,BaTiO3,which can be polarized,and its polarization could be switched under the external electric field.Resulting from the aligned dipole in BaTiO3 layer,zinc ions could move in order during cycling process.Regulated Zn migration at the anode/electrolyte interface contributes to the even Zn stripping/plating and confined Zn dendrite growth.As a result,the reversible Zn plating/stripping processes for over 2000 h have been achieved at 1 mA cm^(−2) with capacity of 1 mAh cm−2.Furthermore,this anode endowing the electric dipoles shows enhanced cycling stability for aqueous Zn-MnO2 batteries.The battery can deliver nearly 100%Coulombic efficiency at 2 Ag^(−1) after 300 cycles.
基金supported by the National Basic Research Program of China (No. 2015CB251100)the Program for New Century Excellent Talents in University (NCET-13-0033)+1 种基金the Beijing Co-construction Project (No. 20150939014)the Beijing Higher Institution Engineering Research Center of Power Battery and Chemical Energy Materials
文摘Aluminum(Al) metal has been regarded as a promising anode for rechargeable batteries because of its natural abundance and high theoretical specific capacity. However, rechargeable aluminum batteries(RABs) using A1 metal as anode display poor cycling performances owing to interface problems between anode and electrolyte. The solid-electrolyte interphase(SEI) layer on the anode has been confirmed to be essential for improving cycling performances of rechargeable batteries. Therefore, we immerse the Al metal in ionic liquid electrolyte for some time before it is used as anode to remove the passive film and expose fresh Al to the electrolyte. Then the reactions of exposed Al, acid, oxygen and water in electrolyte are occurred to form an SEI layer in the cycle. Al/electrolyte/V_2 O_5 full batteries with the thin, uniform and stable SEI layer on Al metal anode perform high discharge capacity and coulombic efficiency(CE). This work illustrates that an SEI layer is formed on Al metal anode in the cycle using a simple and effective pretreatment process and results in superior cycling performances for RABs.
基金support from the China Postdoctoral Science Foundation Funded Project (2019M661464)the supported by the Australian Research Council (ARC) through the Discovery Project (DP180102297)+1 种基金the Future Fellow Project (FT180100705)the ARC Research Hub for Integrated Energy Storage Solutions (IH180100020)。
文摘Aqueous rechargeable batteries have attracted enormous attention owning to their intrinsic characteristics of non-flammability, low cost, and the superior ionic conductivity of the aqueous electrolyte.However, the narrow electrochemical stability window(1.23 V), imposed by hydrogen and oxygen evolution, constrains the overall energy density of batteries. The revolutionary "water-in-salt” electrolytes considerably expand the electrochemical stability window to 3 or even 4 volts, giving rise to a new series of high-voltage aqueous metal-ion chemistries. Herein, the recent advances in "water-in-salt” electrolytes for aqueous monovalent-ion(Li^(+), Na^(+), K^(+)) rechargeable batteries have been systematically reviewed. Meanwhile, the corresponding reaction mechanisms, electrochemical performances and the existing challenges and opportunities are also highlighted.
基金Project supported from the“Strategic Priority Research Program”of the Chinese Academy of Sciences(Grant No.XDA09010102)
文摘A series of Si/C composites were fabricated based on pitch and Si powders with particle sizes of 30, 100, 500, and 3000 nm. The size effects of the Si particles in the Si/C composites were investigated for lithium-ion battery anodes. The nanoscale Si and Si/C composites exhibited good capacity retentions. Scanning electron microscopy showed that exterior and interior cracks emerging owing to volume expansion as well as parasitic reactions with the electrolyte could well explain the performance failure.
基金support from the National Natural Science Foundation of China(21771107,21902077)the Natural Science Foundation of Jiangsu Province(BK20190381,BK20201287)。
文摘Potassium-ion batteries(PIBs)have been considered as one of the most promising alternatives to lithiumion batteries(LIBs)in view of their competitive energy density with significantly reduced product cost.Moreover,alloy-type materials are expected as a high-performance anode of PIBs thanks to their intrinsic chemical stability as well as high theoretical specific capacity.Unfortunately,the serious incompatibility between alloy-type active materials and electrolytes,especially for the formation of unstable solidelectrolyte interfacial(SEI)films,often leads to insufficient cycle life.Herein,the formation mechanism of SEI films in the K-storage systems based on carbon sphere confined Sb anode(Sb@CS)were investigated in commercially available electrolytes.Physical characterizations and theoretical calculation revealed that the solvents in the dilute electrolyte of 0.8 M KPF_(6)/EC+DEC were excessively decomposed on the interface to generate unstable SEI and thus result in inferior K-storage stability.On the contrary,a salt-concentrated electrolyte(3 M KFSI/DME)can generate inorganic-dominated stable SEI due to the preferential decomposition of anions.As a result,the prepared Sb@CS in the matched 3 M KFSI/DME electrolyte delivered a high reversible capacity of 467.8 m A h g^(-1)after 100 cycles at 100 m A g^(-1),with a slow capacity decay of 0.19%per cycle from the 10th to the 100th cycle.These findings are of great significance for revealing the interfacial reaction between electrodes and electrolytes as well as improving the stability of Sb-based anode materials for PIBs.
基金the financial support from the National Natural Science Foundation of China(U1805254,21773192,22072117,22179112)。
文摘Lithium-oxygen(Li-O) battery is considered as one of the most promising alternatives because of its ultrahigh theoretical energy density. However, their cycling stability is severely restricted by the uncontrollable dendrite growth and serious oxygen corrosion issue on Li surface. Herein, a sulfur-modified Li surface can be successfully constructed via chemical reaction of guanylthiourea(GTU) molecule on Li,which can induce the selectively fast decomposition of lithium bis(trifluoromethanesulfonyl)imide(LiTFSI) to form a smooth and stable inorganics-rich solid-electrolyte interphase(IR-SEI) during the subsequent electrochemical process. Such an IR-SEI cannot only offer a highly reversible and stable Li plating/stripping chemistry with dendrite-free property(10 mA cm^(-2)-10 mAh cm^(-2), > 0.5 years;3 mA cm^(-2)-3 m Ah cm^(-2), > 1 year) but also endows the Li metal an anti-oxygen corrosion function, thereby significantly improving the cycling stability of Li-Obatteries. This work provides a new idea for constructing functional solid-electrolyte interphase(SEI) to achieve highly stable Li metal anode.
