Electrolytes with high-efficiency lithium-ion transfer and reliable safety are of great importance for lithium battery.Although having superior ionic conductivity(10^(−3)–10^(−2) S·cm^(−1)),traditional liquid-st...Electrolytes with high-efficiency lithium-ion transfer and reliable safety are of great importance for lithium battery.Although having superior ionic conductivity(10^(−3)–10^(−2) S·cm^(−1)),traditional liquid-state electrolytes always suffer from low lithium-ion transference number(tLi+<0.4)and thus undesirable battery performances.Herein,the deep eutectic solvent(DES)is vacuum-filtered into the~1 nm interlayer channel of vermiculite(Vr)lamellar framework to fabricate a quasi-solid electrolyte(Vr-DES QSE).We demonstrate that the nanoconfinement effect of interlayer channel could facilitate the opening of solvation shell around lithiumion.Meanwhile,the interaction from channel wall could inhibit the movement of anion.These enable high-efficiency lithium-ion transfer:2.61×10^(−4)S·cm^(−1)at 25℃.Importantly,the tLi+value reaches 0.63,which is 4.5 times of that of bulk DES,and much higher than most present liquid/quasi-solid electrolytes.In addition,Vr-DES QSE shows significantly improved interfacial stability with Li anode as compared with DES.The assembled Li symmetric cell can operate stably for 1000 h at 0.1 mA·cm^(−2).The lithium iron phosphate(LFP)|Vr-DES QSE|Li cell exhibits high capacity of 142.1 mAh·g^(−1)after 200 cycles at 25℃ and 0.5 C,with a capacity retention of 94.5%.The strategy of open solvation shell through nanoconfinement effect of lamellar framework may shed light on the development of advanced electrolytes.展开更多
Electrolyte interface resistance and low ionic conductivity are essential issues for commercializing solid-state lithium metal batteries(SSLMBs).This work details the fabrication of a double-layer solid composite elec...Electrolyte interface resistance and low ionic conductivity are essential issues for commercializing solid-state lithium metal batteries(SSLMBs).This work details the fabrication of a double-layer solid composite electrolyte(DLSCE)for SSLMBs.The composite comprises poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)and poly(methyl methacrylate)(PMMA)combined with 10 wt.%of Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO),synthesized through an ultraviolet curing process.The ionic conductivity of the DLSCE(2.6×10^(-4) S·cm^(-1))at room temperature is the high lithium-ion transference number(0.57),and the tensile strength is 17.8 MPa.When this DLSCE was assembled,the resulted LFP/DLSCE/Li battery exhibited excellent rate performance,with the discharge specific capacities of 162.4,146.9,93.6,and 64.0 mA·h·g^(-1) at 0.1,0.2,0.5,and 1 C,respectively.Furthermore,the DLScE demonstrates remarkable stability with lithium metal batteries,facilitating the stable operation of a Li/Li symmetric battery for over 200 h at both 0.1 and 0.2 mA-cm^(-2).Notably,the formation of lithium dendrites is also effectively inhibited during cycling.This work provides a novel design strategy and preparation method for solid composite electrolytes.展开更多
Solid polymer electrolytes(SPEs)hold great application potential for solid-state lithium metal battery because of the excellent interfacial contact and processibility,but being hampered by the poor room-temperature co...Solid polymer electrolytes(SPEs)hold great application potential for solid-state lithium metal battery because of the excellent interfacial contact and processibility,but being hampered by the poor room-temperature conductivity(~10^(−7)S·cm^(−1))and low lithium-ion transference number(tLi+).Here,a lamellar composite solid electrolyte(Vr-NH_(2)@polyvinylidene fluoride(PVDF)LCSE)withβ-conformation PVDF is fabricated by confining PVDF in the interlayer channel of-NH_(2)modified vermiculite lamellar framework.We demonstrate that the conformation of PVDF can be manipulated by the nanoconfinement effect and the interaction from channel wall.The presence of-NH_(2)groups could induce the formation ofβ-conformation PVDF through electrostatic interaction,which serves as continuous and rapid lithium-ion transfer pathway.As a result,a high room-temperature ionic conductivity of 1.77×10^(−4)S·cm^(−1)is achieved,1-2 orders of magnitude higher than most SPEs.Furthermore,Vr-NH_(2)@PVDF LCSE shows a high tLi+of 0.68 because of the high dielectric constant,~3 times of that of PVDF SPE,and surpassing most of reported SPEs.The LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)||Li cell assembled by Vr-NH_(2)@PVDF LCSE obtains a discharge specific capacity of 137.1 mAh·g^(−1)after 150 cycles with a capacity retention rate of 93%at 1 C and 25℃.This study may pave a new avenue for high-performance SPEs.展开更多
Solid-state polymer electrolytes are considered as an alternative to classic liquid electrolytes,particularly for application in highenergy lithium metal batteries.With respect to common dual-ion conductors,single-ion...Solid-state polymer electrolytes are considered as an alternative to classic liquid electrolytes,particularly for application in highenergy lithium metal batteries.With respect to common dual-ion conductors,single-ion conducting polymer electrolytes(SICPEs)are less affected by lithium dendrites growth and thus are particularly interesting for application in lithium metal batteries.In this work,novel SIC-PEs are developed,based on an ionomer having poly(ethylene-alt-maleimide)backbone and lithium phenylsulfonyl(trifluoromethanesulfonyl)imide pendant moieties,further blended with poly(ethylene oxide)(PEO)and poly(ethylene glycol)dimethyl ether(PEGDME).These SIC-PEs exhibit ionic conductivity around~7×10^(−6)S·cm^(−1) at 70℃,lithium transference number close to unity,and excellent mechanical properties,with fracture toughness over 30 J·cm^(−3).Additionally,the electrolytes show very high resistance against lithium dendrites growth,by cycling for more than 1200 h in Li°symmetric cells at a current density of 0.1 mA·cm^(−2).LiFePO4||Li°cells with these SIC-PEs were cycled at 70℃ and C/10,showing initial capacity of almost 160 mAh·g^(−1)and residual capacity of 45%after 100 cycles.This work shows that single-ion conducting polymer electrolytes based on poly(ethylene-alt-maleimide)backbone are promising materials for application as electrolytes or catholytes in lithium metal polymer batteries.展开更多
The development of lithium(Li)metal batteries has been severely limited by the formation of lithium dendrites and the associated catastrophic failure and inferior Coulombic efficiency which caused by non-uniform or in...The development of lithium(Li)metal batteries has been severely limited by the formation of lithium dendrites and the associated catastrophic failure and inferior Coulombic efficiency which caused by non-uniform or insufficient Li^(+)supply across the electrode-electrolyte interface.Therefore,a rational strategy is to construct a robust electrolyte that can allow efficient and uniform Li^(+)transport to ensure sufficient Li^(+)supply and homogenize the Li plating/stripping.Herein,we report an ion-percolating electrolyte membrane that acts as a stable Li^(+)reservoir to ensure a near-single Li^(+)transference number(0.78)and homogenizes Li^(+)migration to eradicate dendrite growth,endowing Li//LFP cell with an ultrahigh average Coulombic efficiency(ca.99.97%)after cycling for nearly half of a year and superior cycling stability when pairing with LiCoO_(2) with limited Li amount and LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2).These estimable attributes demonstrate significant potential of utility value for the ion-percolating electrolyte.展开更多
With the increasing interest in highly concentrated electrolyte systems,correct determination of the cation transference number is important.Pulsed-field gradient NMR technique,which measures self-diffusion coefficien...With the increasing interest in highly concentrated electrolyte systems,correct determination of the cation transference number is important.Pulsed-field gradient NMR technique,which measures self-diffusion coefficients,is often applied on liquid electrolytes because of the wide accessibility and simple sample preparation.However,since the assumptions of this technique,that is,complete salt dissociation,all ions participating in motion,and all of them moving independently,no longer hold true in concentrated solutions,the transference numbers,thus obtained are often over-estimated.In the present work,impedance spectroscopy at a frequency range of 1 MHz to 0.1 mHz was used to examine the concentration effect on lithium-ion transference number under anion-blocking conditions T abc Liþfor two electrolytes:lithium bis(fluorosulfonyl)imide(LiFSI)in sulfolane(SL)and lithium bis(trifluorosulfonyl)imide(LiTFSI)in tetraglyme(G4).The T abc Liþof the former was almost an order of magnitude higher than that of the latter.It also appeared to increase with increasing concentration while the latter followed an opposite trend.The faster Li^(+)transport in the SL system is attributed to the formation of a liquid structure consisting of extended chains/bridges of SL molecules and the anions,which facilitate a cation-hopping/ligand-exchanged-typed diffusion mechanism by partially decoupling the cations from the anions and solvent molecules.The G4 system,in contrast,is dominated by the formation of long-lived,stable[Li(G4)]+solvation cages that results in a sluggish Li+transport.The difference between the two transport mechanisms is discussed via comparison of the bulk ionic conductivity,viscosity,ion self-diffusion coefficients,and the Onsager transport coefficients.展开更多
Potassium metal battery is a promising alternative to Li-ion battery for large-scale energy storage due to the abundant potassium resources and high energy density.However,it suffers from rapid capacity fading and saf...Potassium metal battery is a promising alternative to Li-ion battery for large-scale energy storage due to the abundant potassium resources and high energy density.However,it suffers from rapid capacity fading and safety issues due to the uncontrolled dendrite growth.Herein,we design a fluorine-free ultra-low concentration electrolyte(ULCE)with the super bulky[BPh_(4)]^(−) anions for stable potassium metal battery.In this special electrolyte,the migration rate of K+in the electrolyte is about six times faster than that of the[BPh_(4)]^(−) anions because of the super bulky structure of the[BPh_(4)]^(−) anions,thus resulting in a high K^(+)transference number of 0.76.This high transference number can effectively make up for the deficiency of K^(+)in ULCE for ensuring the normal operation of the potassium metal battery.In addition,the improved transference number can also promote the uniform distribution of K^(+)flux on the surface of the K metal anode,resulting in uniform K deposition.As a result,this electrolyte achieves a high K plating/stripping Coulombic efficiency of 92.6%over 200 cycles and a stable discharging/charging for 100 cycles under the full battery configuration(K used as the anode and perylene-3,4,9,10-tetracarboxylic dianhydride used as the cathode).展开更多
制备高离子电导率的自支撑单离子传导聚合物电解质仍然面临挑战.本文中,我们通过聚[4,4’(二苯醚基)-5,5’-联苯并咪唑]侧链化学接枝丙烷磺酰(三氟甲基磺酰)亚胺锂,得到自支撑聚合物电解质(PBIg-LiPSI).PBI-g-LiPSI具有优异的成膜性能,...制备高离子电导率的自支撑单离子传导聚合物电解质仍然面临挑战.本文中,我们通过聚[4,4’(二苯醚基)-5,5’-联苯并咪唑]侧链化学接枝丙烷磺酰(三氟甲基磺酰)亚胺锂,得到自支撑聚合物电解质(PBIg-LiPSI).PBI-g-LiPSI具有优异的成膜性能,实验发现,掺杂两性分子1-甲基-3-丙烷磺酰(三氟甲基磺酰)亚胺咪唑内盐(MeImPSI)后,离子电导率和^(7)Li核磁共振峰的化学位移都随着掺杂两性分子的质量分数呈线性递增.PBI-g-LiPSI/MeImPSI(25 wt%)凝胶自支撑单离子传导聚合物电解质的室温离子电导率是0.68 mS cm^(-1),锂离子迁移数是0.95.使用该电解质隔膜的金属锂对称电池在±0.5 mA cm^(-2)@2 mA h cm^(-2)运行2100小时未发生短路,金属锂二次电池可在1C下稳定循环500圈.本工作开发了一种用于金属锂二次电池的两性分子掺杂自支撑单离子传导聚合物电解质.展开更多
Novel gel polymer electrolytes(GPEs)composed of polyvinyl alcohol(PVA)and sodium thiocyanate were developed via a solution casting technique.An ionic liquid(IL),1-ethyl-3-methyl-imidazolium tricyanomethanide([EMIM][TC...Novel gel polymer electrolytes(GPEs)composed of polyvinyl alcohol(PVA)and sodium thiocyanate were developed via a solution casting technique.An ionic liquid(IL),1-ethyl-3-methyl-imidazolium tricyanomethanide([EMIM][TCM]),was doped into a polymer–salt complex system(PVA+NaSCN)to further enhance the conductivity.IL-doped polymer electrolyte(ILDPE)films were characterized using X-ray diffraction(XRD),polarized optical microscopy(POM),Fourier-transform infrared(FTIR)spectroscopy,and conductivity measurements.XRD was performed to check the degree of crystallinity and amorphicity of the ILDPE films,and the amorphicity of GPEs increased with the increase of the IL content.POM was employed to evaluate the changes in the surface morphology due to the inclusion of salt and IL in the PVA.The compositional nature of the GPE films was examined via FTIR studies.The electrical and electrochemical properties were characterized by cyclic voltammetry and electrochemical impedance spectroscopy.The maximum conductivity for the GPE film was estimated to be 1.10×10^(-5) S/cm for 6%(mass fraction)of IL in the polymer–salt complex.The ionic transference number was approximately 0.97.An electrochemical double-layer capacitor(EDLC)was built from optimized GPE films and reduced graphene oxide-based electrodes.The specific capacitance calculated from the cyclic voltammograms of the EDLC cells was 3 F/g.展开更多
With the wide applications of lithium-ion batteries(LIBs)in electronic devices and electric vehicles,it is of great importance to improve their safety and electrochemical performance.Herein,soluble polyimides(PI)conta...With the wide applications of lithium-ion batteries(LIBs)in electronic devices and electric vehicles,it is of great importance to improve their safety and electrochemical performance.Herein,soluble polyimides(PI)containing carboxyl groups(―COOH)were synthesized by a simple one-step method and PI separators with sponge-like,interpenetrating porous structures were prepared via non-solvent induced phase separation(NIPS).The obtained PI separators exhibited excellent thermal stability and fire-resistance properties,with the electrolyte uptake of 344%and good dimensional integrity in air at 200℃.The results showed that the lithium-ion transference number of the obtained PI separator could reach 0.48,which was much higher than that of the Celgard-2400 separator(0.38).The Li/LiFePO_(4) half-cell with the PI separator showed excellent cycle capability and high-rate performance with a high capacity of 121.80 mA·h·g^(-1) at 5 C,which was better than that of the cell with the Celgard-2400 separator(54.3 mA·h·g^(-1)),demonstrating the promising applications of this PI separators in LIBs.展开更多
Lithium metal anode is regarded as the ultimate choice for next-generation energy storage systems,due to the lowest negative electrochemical potential and super high theoretical specific capacity.However,the growth of...Lithium metal anode is regarded as the ultimate choice for next-generation energy storage systems,due to the lowest negative electrochemical potential and super high theoretical specific capacity.However,the growth of lithium dendrite during the cycling process is still one of the most critical bottlenecks for its application.In this work,a slurry-like hybrid electrolyte is proposed towards the application for lithium metal anode,which is composed of a liquid electrolyte part and a nanometric silane-Al2O3 particle part.The hybrid electrolyte shows high ionic conductivity(3.89×10-3 S cm-1 at 25℃)and lithium-ion transference number(0.88).Especially,the resistance of hybrid electrolyte decreases compared to that of liquid electrolyte,while the viscosity of hybrid electrolyte increases.It is demonstrated that the hybrid electrolyte can effectively suppress the growth of lithium dendrite.Stable cycling of Li/Li cells at a current density up to 1 mA cm-2 is possible.The hybrid electrolyte helps to uniform the lithium ion flux inside the battery and partly comes from the formation of a rigid and highly conductive hybrid interfacial layer on the surface of lithium metal.This work not only provides a fresh way to stabilize lithium metal anode but also sheds light on further research for electrolyte optimization and design of lithium metal battery system.展开更多
基金financial support from National Natural Science Foundation of China(No.U2004199)Joint Foundation for Science and Technology Research&Development Plan of Henan Province(Nos.222301420003 and 232301420038)+1 种基金China Postdoctoral Science Foundation(No.2022TQ0293)Key Science and Technology Project of Henan Province(No.221100240200-06).
文摘Electrolytes with high-efficiency lithium-ion transfer and reliable safety are of great importance for lithium battery.Although having superior ionic conductivity(10^(−3)–10^(−2) S·cm^(−1)),traditional liquid-state electrolytes always suffer from low lithium-ion transference number(tLi+<0.4)and thus undesirable battery performances.Herein,the deep eutectic solvent(DES)is vacuum-filtered into the~1 nm interlayer channel of vermiculite(Vr)lamellar framework to fabricate a quasi-solid electrolyte(Vr-DES QSE).We demonstrate that the nanoconfinement effect of interlayer channel could facilitate the opening of solvation shell around lithiumion.Meanwhile,the interaction from channel wall could inhibit the movement of anion.These enable high-efficiency lithium-ion transfer:2.61×10^(−4)S·cm^(−1)at 25℃.Importantly,the tLi+value reaches 0.63,which is 4.5 times of that of bulk DES,and much higher than most present liquid/quasi-solid electrolytes.In addition,Vr-DES QSE shows significantly improved interfacial stability with Li anode as compared with DES.The assembled Li symmetric cell can operate stably for 1000 h at 0.1 mA·cm^(−2).The lithium iron phosphate(LFP)|Vr-DES QSE|Li cell exhibits high capacity of 142.1 mAh·g^(−1)after 200 cycles at 25℃ and 0.5 C,with a capacity retention of 94.5%.The strategy of open solvation shell through nanoconfinement effect of lamellar framework may shed light on the development of advanced electrolytes.
基金supported by the Liuzhou Science and Technology Fund Project(Grant No.2023PRj0103)the National Natural Science Foundation of China(Grant Nos.52161033 and 22262005)+1 种基金the Guangxi Key Laboratory of Automobile Components and Vehicle Technology Fund Project(Grant Nos.2022GKLACVTKF02 and 2023GKLACVTZZ02)the Fund Project of the Key Lab of Guangdong Science and Technology Innovation Strategy Special Fund Project in 2023(Grant No.pdjh2023a0819).
文摘Electrolyte interface resistance and low ionic conductivity are essential issues for commercializing solid-state lithium metal batteries(SSLMBs).This work details the fabrication of a double-layer solid composite electrolyte(DLSCE)for SSLMBs.The composite comprises poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)and poly(methyl methacrylate)(PMMA)combined with 10 wt.%of Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO),synthesized through an ultraviolet curing process.The ionic conductivity of the DLSCE(2.6×10^(-4) S·cm^(-1))at room temperature is the high lithium-ion transference number(0.57),and the tensile strength is 17.8 MPa.When this DLSCE was assembled,the resulted LFP/DLSCE/Li battery exhibited excellent rate performance,with the discharge specific capacities of 162.4,146.9,93.6,and 64.0 mA·h·g^(-1) at 0.1,0.2,0.5,and 1 C,respectively.Furthermore,the DLScE demonstrates remarkable stability with lithium metal batteries,facilitating the stable operation of a Li/Li symmetric battery for over 200 h at both 0.1 and 0.2 mA-cm^(-2).Notably,the formation of lithium dendrites is also effectively inhibited during cycling.This work provides a novel design strategy and preparation method for solid composite electrolytes.
基金National Natural Science Foundation of China(No.U2004199)Joint Foundation for Science and Technology Research&Development Plan of Henan Province(Nos.222301420003 and 232301420038)+1 种基金China Postdoctoral Science Foundation(No.2022TQ0293)Key Science and Technology Project of Henan Province(No.221100240200-06).
文摘Solid polymer electrolytes(SPEs)hold great application potential for solid-state lithium metal battery because of the excellent interfacial contact and processibility,but being hampered by the poor room-temperature conductivity(~10^(−7)S·cm^(−1))and low lithium-ion transference number(tLi+).Here,a lamellar composite solid electrolyte(Vr-NH_(2)@polyvinylidene fluoride(PVDF)LCSE)withβ-conformation PVDF is fabricated by confining PVDF in the interlayer channel of-NH_(2)modified vermiculite lamellar framework.We demonstrate that the conformation of PVDF can be manipulated by the nanoconfinement effect and the interaction from channel wall.The presence of-NH_(2)groups could induce the formation ofβ-conformation PVDF through electrostatic interaction,which serves as continuous and rapid lithium-ion transfer pathway.As a result,a high room-temperature ionic conductivity of 1.77×10^(−4)S·cm^(−1)is achieved,1-2 orders of magnitude higher than most SPEs.Furthermore,Vr-NH_(2)@PVDF LCSE shows a high tLi+of 0.68 because of the high dielectric constant,~3 times of that of PVDF SPE,and surpassing most of reported SPEs.The LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)||Li cell assembled by Vr-NH_(2)@PVDF LCSE obtains a discharge specific capacity of 137.1 mAh·g^(−1)after 150 cycles with a capacity retention rate of 93%at 1 C and 25℃.This study may pave a new avenue for high-performance SPEs.
文摘Solid-state polymer electrolytes are considered as an alternative to classic liquid electrolytes,particularly for application in highenergy lithium metal batteries.With respect to common dual-ion conductors,single-ion conducting polymer electrolytes(SICPEs)are less affected by lithium dendrites growth and thus are particularly interesting for application in lithium metal batteries.In this work,novel SIC-PEs are developed,based on an ionomer having poly(ethylene-alt-maleimide)backbone and lithium phenylsulfonyl(trifluoromethanesulfonyl)imide pendant moieties,further blended with poly(ethylene oxide)(PEO)and poly(ethylene glycol)dimethyl ether(PEGDME).These SIC-PEs exhibit ionic conductivity around~7×10^(−6)S·cm^(−1) at 70℃,lithium transference number close to unity,and excellent mechanical properties,with fracture toughness over 30 J·cm^(−3).Additionally,the electrolytes show very high resistance against lithium dendrites growth,by cycling for more than 1200 h in Li°symmetric cells at a current density of 0.1 mA·cm^(−2).LiFePO4||Li°cells with these SIC-PEs were cycled at 70℃ and C/10,showing initial capacity of almost 160 mAh·g^(−1)and residual capacity of 45%after 100 cycles.This work shows that single-ion conducting polymer electrolytes based on poly(ethylene-alt-maleimide)backbone are promising materials for application as electrolytes or catholytes in lithium metal polymer batteries.
基金National Natural Science Foundation of China,Grant/Award Number:51803054Basic Science Center Project of the National Key R&D Program of China,Grant/Award Number:2021YFB2400400+2 种基金Science and Technology Innovation Program of Hunan Province,Grant/Award Number:2023RC3154Natural Science Foundation of Hunan Province,Grant/Award Numbers:2019JJ50223,2020JJ3022Foundation from Education Department of Hunan Province,Grant/Award Number:19B270。
文摘The development of lithium(Li)metal batteries has been severely limited by the formation of lithium dendrites and the associated catastrophic failure and inferior Coulombic efficiency which caused by non-uniform or insufficient Li^(+)supply across the electrode-electrolyte interface.Therefore,a rational strategy is to construct a robust electrolyte that can allow efficient and uniform Li^(+)transport to ensure sufficient Li^(+)supply and homogenize the Li plating/stripping.Herein,we report an ion-percolating electrolyte membrane that acts as a stable Li^(+)reservoir to ensure a near-single Li^(+)transference number(0.78)and homogenizes Li^(+)migration to eradicate dendrite growth,endowing Li//LFP cell with an ultrahigh average Coulombic efficiency(ca.99.97%)after cycling for nearly half of a year and superior cycling stability when pairing with LiCoO_(2) with limited Li amount and LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2).These estimable attributes demonstrate significant potential of utility value for the ion-percolating electrolyte.
基金This work was supported by US Department of Army and the Joint Center for Energy Storage Research(JCESR),an Energy Innovation Hub funded by Depart-ment of Energy,Basic Energy Science,under an Interagency Agreement No.IAA SN202095.
文摘With the increasing interest in highly concentrated electrolyte systems,correct determination of the cation transference number is important.Pulsed-field gradient NMR technique,which measures self-diffusion coefficients,is often applied on liquid electrolytes because of the wide accessibility and simple sample preparation.However,since the assumptions of this technique,that is,complete salt dissociation,all ions participating in motion,and all of them moving independently,no longer hold true in concentrated solutions,the transference numbers,thus obtained are often over-estimated.In the present work,impedance spectroscopy at a frequency range of 1 MHz to 0.1 mHz was used to examine the concentration effect on lithium-ion transference number under anion-blocking conditions T abc Liþfor two electrolytes:lithium bis(fluorosulfonyl)imide(LiFSI)in sulfolane(SL)and lithium bis(trifluorosulfonyl)imide(LiTFSI)in tetraglyme(G4).The T abc Liþof the former was almost an order of magnitude higher than that of the latter.It also appeared to increase with increasing concentration while the latter followed an opposite trend.The faster Li^(+)transport in the SL system is attributed to the formation of a liquid structure consisting of extended chains/bridges of SL molecules and the anions,which facilitate a cation-hopping/ligand-exchanged-typed diffusion mechanism by partially decoupling the cations from the anions and solvent molecules.The G4 system,in contrast,is dominated by the formation of long-lived,stable[Li(G4)]+solvation cages that results in a sluggish Li+transport.The difference between the two transport mechanisms is discussed via comparison of the bulk ionic conductivity,viscosity,ion self-diffusion coefficients,and the Onsager transport coefficients.
基金supported by the National Natural Science Foundation of China(Nos.21975124 and 52173173)supported by 21C Innovation Laboratory,Contemporary Amperex Technology Ltd(No.21C-OP-202008).
文摘Potassium metal battery is a promising alternative to Li-ion battery for large-scale energy storage due to the abundant potassium resources and high energy density.However,it suffers from rapid capacity fading and safety issues due to the uncontrolled dendrite growth.Herein,we design a fluorine-free ultra-low concentration electrolyte(ULCE)with the super bulky[BPh_(4)]^(−) anions for stable potassium metal battery.In this special electrolyte,the migration rate of K+in the electrolyte is about six times faster than that of the[BPh_(4)]^(−) anions because of the super bulky structure of the[BPh_(4)]^(−) anions,thus resulting in a high K^(+)transference number of 0.76.This high transference number can effectively make up for the deficiency of K^(+)in ULCE for ensuring the normal operation of the potassium metal battery.In addition,the improved transference number can also promote the uniform distribution of K^(+)flux on the surface of the K metal anode,resulting in uniform K deposition.As a result,this electrolyte achieves a high K plating/stripping Coulombic efficiency of 92.6%over 200 cycles and a stable discharging/charging for 100 cycles under the full battery configuration(K used as the anode and perylene-3,4,9,10-tetracarboxylic dianhydride used as the cathode).
基金financially supported by the National Natural Science Foundation of China(22172147)。
文摘制备高离子电导率的自支撑单离子传导聚合物电解质仍然面临挑战.本文中,我们通过聚[4,4’(二苯醚基)-5,5’-联苯并咪唑]侧链化学接枝丙烷磺酰(三氟甲基磺酰)亚胺锂,得到自支撑聚合物电解质(PBIg-LiPSI).PBI-g-LiPSI具有优异的成膜性能,实验发现,掺杂两性分子1-甲基-3-丙烷磺酰(三氟甲基磺酰)亚胺咪唑内盐(MeImPSI)后,离子电导率和^(7)Li核磁共振峰的化学位移都随着掺杂两性分子的质量分数呈线性递增.PBI-g-LiPSI/MeImPSI(25 wt%)凝胶自支撑单离子传导聚合物电解质的室温离子电导率是0.68 mS cm^(-1),锂离子迁移数是0.95.使用该电解质隔膜的金属锂对称电池在±0.5 mA cm^(-2)@2 mA h cm^(-2)运行2100小时未发生短路,金属锂二次电池可在1C下稳定循环500圈.本工作开发了一种用于金属锂二次电池的两性分子掺杂自支撑单离子传导聚合物电解质.
基金Early Career Research Award Scheme of Science and Engineering Research Board,Department of Science and Technology,Government of India(No.ECR/20216/001871)。
文摘Novel gel polymer electrolytes(GPEs)composed of polyvinyl alcohol(PVA)and sodium thiocyanate were developed via a solution casting technique.An ionic liquid(IL),1-ethyl-3-methyl-imidazolium tricyanomethanide([EMIM][TCM]),was doped into a polymer–salt complex system(PVA+NaSCN)to further enhance the conductivity.IL-doped polymer electrolyte(ILDPE)films were characterized using X-ray diffraction(XRD),polarized optical microscopy(POM),Fourier-transform infrared(FTIR)spectroscopy,and conductivity measurements.XRD was performed to check the degree of crystallinity and amorphicity of the ILDPE films,and the amorphicity of GPEs increased with the increase of the IL content.POM was employed to evaluate the changes in the surface morphology due to the inclusion of salt and IL in the PVA.The compositional nature of the GPE films was examined via FTIR studies.The electrical and electrochemical properties were characterized by cyclic voltammetry and electrochemical impedance spectroscopy.The maximum conductivity for the GPE film was estimated to be 1.10×10^(-5) S/cm for 6%(mass fraction)of IL in the polymer–salt complex.The ionic transference number was approximately 0.97.An electrochemical double-layer capacitor(EDLC)was built from optimized GPE films and reduced graphene oxide-based electrodes.The specific capacitance calculated from the cyclic voltammograms of the EDLC cells was 3 F/g.
基金the National Natural Science Foundation of China(Nos.U21A2087,51903038 and 21975040).
文摘With the wide applications of lithium-ion batteries(LIBs)in electronic devices and electric vehicles,it is of great importance to improve their safety and electrochemical performance.Herein,soluble polyimides(PI)containing carboxyl groups(―COOH)were synthesized by a simple one-step method and PI separators with sponge-like,interpenetrating porous structures were prepared via non-solvent induced phase separation(NIPS).The obtained PI separators exhibited excellent thermal stability and fire-resistance properties,with the electrolyte uptake of 344%and good dimensional integrity in air at 200℃.The results showed that the lithium-ion transference number of the obtained PI separator could reach 0.48,which was much higher than that of the Celgard-2400 separator(0.38).The Li/LiFePO_(4) half-cell with the PI separator showed excellent cycle capability and high-rate performance with a high capacity of 121.80 mA·h·g^(-1) at 5 C,which was better than that of the cell with the Celgard-2400 separator(54.3 mA·h·g^(-1)),demonstrating the promising applications of this PI separators in LIBs.
基金supported by the National Key R&D Program of China(Grant No.2016YFB0100100)supports from the National Natural Science Foundation of China(Grant No.51872305)。
文摘Lithium metal anode is regarded as the ultimate choice for next-generation energy storage systems,due to the lowest negative electrochemical potential and super high theoretical specific capacity.However,the growth of lithium dendrite during the cycling process is still one of the most critical bottlenecks for its application.In this work,a slurry-like hybrid electrolyte is proposed towards the application for lithium metal anode,which is composed of a liquid electrolyte part and a nanometric silane-Al2O3 particle part.The hybrid electrolyte shows high ionic conductivity(3.89×10-3 S cm-1 at 25℃)and lithium-ion transference number(0.88).Especially,the resistance of hybrid electrolyte decreases compared to that of liquid electrolyte,while the viscosity of hybrid electrolyte increases.It is demonstrated that the hybrid electrolyte can effectively suppress the growth of lithium dendrite.Stable cycling of Li/Li cells at a current density up to 1 mA cm-2 is possible.The hybrid electrolyte helps to uniform the lithium ion flux inside the battery and partly comes from the formation of a rigid and highly conductive hybrid interfacial layer on the surface of lithium metal.This work not only provides a fresh way to stabilize lithium metal anode but also sheds light on further research for electrolyte optimization and design of lithium metal battery system.
