Single-ion conducting solid polymer electrolytes are expected to play a vital role in the realization of solid-state Li metal batteries.In this work,a lithiated Nafion(Li-Nafion)-garnet ceramic Li6.25La3 Zr2 Al0.25O12...Single-ion conducting solid polymer electrolytes are expected to play a vital role in the realization of solid-state Li metal batteries.In this work,a lithiated Nafion(Li-Nafion)-garnet ceramic Li6.25La3 Zr2 Al0.25O12(LLZAO)composite solid electrolyte(CSE)membrane with 30μm thickness was prepared for the first time.By employing X-ray photoelectron spectroscopy and transmission electron microscope,the interaction between LLZAO and Li-Nafion was investigated.It is found that the LLZAO interacts with the Li-Nafion to form a space charge layer at the interface between LLZAO and Li-Nafion.The space charge layer reduces the migration barrier of Li-ions and improves the ionic conductivity of the CSE membrane.The CSE membrane containing 10 wt%LLZAO exhibits the highest ionic conductivity of2.26×10-4 S cm-1 at 30℃among the pristine Li-Nafion membrane,the membrane containing 5 wt%,20 wt%,and 30 wt%LLZAO,respectively.It also exhibits a high Li-ion transference number of 0.92,and a broader electrochemical window of 0-+4.8 V vs.Li+/Li than that of 0-+4.0 V vs.Li+/Li for the pristine Li-Nafion membrane.It is observed that the CSE membrane not only inhibits the growth of Li dendrites but also keeps excellent electrochemical stability with the Li electrode.Benefitting from the above merits,the solid-state LiFePO4/Li cell fabricated with the CSE membrane was practically charged and discharged at 30℃.The cell exhibits an initial reversible discharge specific capacity of 160 mAh g-1 with 97%capacity retention after 100 cycles at 0.2 C,and maintains discharge specific capacity of 126 mAh g-1 after500 cycles at 1 C.The CSE membrane prepared with Li-Nafion and LLZAO is proved to be a promising solid electrolyte for advanced solid-state Li metal batteries.展开更多
Garnet ceramic scintillators are a class of inorganic scintillation materials with excellent overall performance.The flexibility of cation substitution in different lattice positions leads to tunable and versatile pro...Garnet ceramic scintillators are a class of inorganic scintillation materials with excellent overall performance.The flexibility of cation substitution in different lattice positions leads to tunable and versatile properties and a wide range of applications.This paper starts with an overview of the development history of the inorganic scintillation materials,followed by a description of major preparation methods and characterization of garnet scintillation ceramics.Great progress obtained in recent years consisting in applying the band-gap and defect engineering strategies to the garnet scintillation ceramics is reviewed.Finally,the respective problems in the preparation and performance of multicomponent garnet single crystals and ceramics and the effective solutions are discussed.The garnet scintillation ceramics with the highest application potential are summarized,and the future development directions are proposed.展开更多
As the fourth-generation light source,solid-state lighting has developed rapidly in the past 30 years due to its advantages of high efficiency and environmental protection.It is widely used in various scenes such as a...As the fourth-generation light source,solid-state lighting has developed rapidly in the past 30 years due to its advantages of high efficiency and environmental protection.It is widely used in various scenes such as automobile headlights,projection displays,industrial production,and remote lighting.High-power,high-brightness white light-emitting diodes(LEDs)and laser diodes(LDs)technology put forward new requirements for the service stability of color conversion materials.Garnet phosphor ceramics have emerged with their unique advantages of withstanding high power excitation density and the flexibly tunable spectrum.In this article,the research progress of garnet based phosphor ceramics for high-power solid-state lighting was comprehensively reviewed.Firstly,the band gap and coordination environment regulations of luminescence centers of garnet phosphor were summarized.Secondly,the improvement of luminous efficacy via defects regulation was discussed.Thirdly,the relationship between the geometric design and the lighting performance was elucidated.Fourthly,the characterization methods of phosphor ceramics for laser lighting were introduced and illustrated.Finally,the development trend of garnet phosphor ceramics in solid state lighting and display was prospected.展开更多
Rechargeable lithium-oxygen （Li-O2） batteries have received intensive research interest due to its ultrahigh energy density, while its cycle stability is still hindered by the high reactivity of the Li anode with ox...Rechargeable lithium-oxygen （Li-O2） batteries have received intensive research interest due to its ultrahigh energy density, while its cycle stability is still hindered by the high reactivity of the Li anode with oxygen and moisture. To alleviate the corrosion of the metallic lithium anodes for achieving a stable Li-O2 battery, and as a proof-of-concept experiment, a distinctive hybrid electrolyte system with an organic/ceramic/organic electrolyte （OCOE） architecture is designed. Importantl~ the cycle number of Li-O2 batteries with OCOE is significantly improved compared with batteries with an organic electrolyte （OE）. This might be attributed to the effective suppression of the lithium anode corrosion caused by the OE degradation and the crossover of oxygen from the cathode. We consider that our facile, low-cost, and highly effective lithium protection strategy presents a new avenue to address the daunting corrosion problem of lithium metal anodes in Li-O2 batteries. In addition, the proposed strategy can be easily extended to other metal-O2 battery systems, such as Na-O2 batteries.展开更多
Terbium aluminum garnet(Tb_(3)Al_(5)O_(12);TAG)ceramics are among the most promising magneto–optical materials owing to their outstanding comprehensive performance.Many works have focused on improving the optical qua...Terbium aluminum garnet(Tb_(3)Al_(5)O_(12);TAG)ceramics are among the most promising magneto–optical materials owing to their outstanding comprehensive performance.Many works have focused on improving the optical quality of TAG ceramics.A key point for improving optical quality is ensuring the accuracy of the stoichiometric ratio and avoiding secondary phases.In this work,0,2,4,or 6 wt%Sc_(2)O_(3) was added to the TAG ceramics to increase the solid solubility.The effects of Sc substitution on the crystal structure,sintering process,microstructure,optical transmittance,and magneto–optical properties of(Tb_(1−x)Sc_(x))_(3)(Al_(1−y)Sc_(y))_(2)Al_(3)O_(12)(TSAG)ceramics are studied in detail.4 wt%Sc2O3:TAG ceramics with an in-line transmittance of 82.2%at 1064 nm and 81.2%at 633 nm were successfully fabricated,and the Verdet constant was 164.4 rad·T^(−1)·m^(−1) at 633 nm.Anti-site defects(ADs)and Sc replacement in TAG are further studied via first-principles calculations to determine the working mechanism of Sc.Both the experimental and calculation results show that the introduction of Sc can effectively increase the solid solubility of TAG ceramics,suppress secondary phases,and hence improve the optical transmittance.展开更多
Transparent ceramics are at the heart of modern magneto-optical materials providing promising opportunities for Faraday isolators.1.0 at%RE:Tb3Ga5O12(rare earth(RE)=Pr,Tm,Dy)transparent ceramics were successfully prep...Transparent ceramics are at the heart of modern magneto-optical materials providing promising opportunities for Faraday isolators.1.0 at%RE:Tb3Ga5O12(rare earth(RE)=Pr,Tm,Dy)transparent ceramics were successfully prepared by air sintering and sequential HIP technique using the coprecipitated powders as the raw material.All the powders have shown to be a pure cubic terbium gallium garnet(TGG)phase and exhibit good dispersion.Additionally,a change could not be observed in particle shape with the different doped ions.After the two-step sintering,all the obtained ceramics have good optical quality,and the in-line transmittances at 1070 nm are higher than 80%.Moreover,no secondary phase can be detected from the microstructures.However,the pores which remain entrapped in the ceramics can be noted.The Verdet constant of ceramic samples is optimized by RE doping,and the Verdet constant at 632.8 nm is about−143 rad·T^(−1)·m^(−1),which is about 5%higher than that of TGG ceramics.Finally,the thermo-optical properties of 1.0 at%RE:TGG transparent ceramics are compared.The annealed TGG ceramic showed the best thermo-optical properties,and the thermally induced depolarization of 1.0 at%Ce:TGG and 1.0 at%Tm:TGG was inferior to that of annealed TGG ceramic.展开更多
In this study,the inequivalent substitution of Ca^(2+)by Li^(+)in the Ca_(3)Co_(2)SiV_(2)O_(12)compound was designed to modulate its sintering characteristics and microwave dielectric properties.The corresponding Ca_(...In this study,the inequivalent substitution of Ca^(2+)by Li^(+)in the Ca_(3)Co_(2)SiV_(2)O_(12)compound was designed to modulate its sintering characteristics and microwave dielectric properties.The corresponding Ca_(3-x)Li_(2x)Co_(2)SiV_(2)O_(12)(CCSV-xLi,0.01≤x≤0.07)ceramics were prepared via the conventional solid-state phase method,which could be densely sintered at a temperature below 1140℃.Rietveld refinement results suggested that all the doped Li occupied the Ca-site as x≤0.05 while superfluous Li positioned at the Co-site of CCSV when x≤0.07.This atomic occupancy had a remarkable effect on the degree of“rattling effect”and thus modulated the relative permittivity of ceramics,constantly increasing at x=0.01-0.05 and slightly decreasing at x=0.07.Raman spectra revealed that Q×f value was closely related to Raman shift and FWHM.Also,the Q×f value was partly influenced by oxygen vacancy concentration.The t_(f)demonstrated an opposite tendency to the bond valence of the A-site and was affected by the“rattling effect”.The CCSV-0.05Li ceramic sintered at 1120℃possessed excellent microwave dielectric properties:εr=12.17,Q×f=56,220 GHz,and t_(f)=-8.5×10^(-6)℃^(-1).展开更多
基金financially supported by the National Key R&D Program of China(Grant no.2016YFB0100100)Strategic Priority Research Program of the Chinese Academy of Sciences(Grant no.XDA17020404)+2 种基金Strategic Priority Research Program of the Chinese Academy of Sciences(Grant no.XDA09010203)R&D Projects in Key Areas of Guangdong Province(Grant no.2019B090908001)DICP&QIBEBT(Grant no.DICP&QIBEBT UN201702)。
文摘Single-ion conducting solid polymer electrolytes are expected to play a vital role in the realization of solid-state Li metal batteries.In this work,a lithiated Nafion(Li-Nafion)-garnet ceramic Li6.25La3 Zr2 Al0.25O12(LLZAO)composite solid electrolyte(CSE)membrane with 30μm thickness was prepared for the first time.By employing X-ray photoelectron spectroscopy and transmission electron microscope,the interaction between LLZAO and Li-Nafion was investigated.It is found that the LLZAO interacts with the Li-Nafion to form a space charge layer at the interface between LLZAO and Li-Nafion.The space charge layer reduces the migration barrier of Li-ions and improves the ionic conductivity of the CSE membrane.The CSE membrane containing 10 wt%LLZAO exhibits the highest ionic conductivity of2.26×10-4 S cm-1 at 30℃among the pristine Li-Nafion membrane,the membrane containing 5 wt%,20 wt%,and 30 wt%LLZAO,respectively.It also exhibits a high Li-ion transference number of 0.92,and a broader electrochemical window of 0-+4.8 V vs.Li+/Li than that of 0-+4.0 V vs.Li+/Li for the pristine Li-Nafion membrane.It is observed that the CSE membrane not only inhibits the growth of Li dendrites but also keeps excellent electrochemical stability with the Li electrode.Benefitting from the above merits,the solid-state LiFePO4/Li cell fabricated with the CSE membrane was practically charged and discharged at 30℃.The cell exhibits an initial reversible discharge specific capacity of 160 mAh g-1 with 97%capacity retention after 100 cycles at 0.2 C,and maintains discharge specific capacity of 126 mAh g-1 after500 cycles at 1 C.The CSE membrane prepared with Li-Nafion and LLZAO is proved to be a promising solid electrolyte for advanced solid-state Li metal batteries.
基金supported by the International Partnership Program of Chinese Academy of Sciences(Grant No.121631KYSB20200039)the International Cooperation Project of Shanghai Science and Technology Commission(Grant No.20520750200)+3 种基金the National Key R&D Program of China(Grant No.2021YFE0104800)the Key Research Project of the Frontier Science of the Chinese Academy of Sciences(Grant No.QYZDB-SSWJSC022)Partial support of the Czech Ministry of Education,Youth and Sports under Project SOLID21 CZ.02.1.(Grant No.01/0.0/0.0/16_019/0000760)Czech Science Foundation project(Grant No.GA21-17731S).
文摘Garnet ceramic scintillators are a class of inorganic scintillation materials with excellent overall performance.The flexibility of cation substitution in different lattice positions leads to tunable and versatile properties and a wide range of applications.This paper starts with an overview of the development history of the inorganic scintillation materials,followed by a description of major preparation methods and characterization of garnet scintillation ceramics.Great progress obtained in recent years consisting in applying the band-gap and defect engineering strategies to the garnet scintillation ceramics is reviewed.Finally,the respective problems in the preparation and performance of multicomponent garnet single crystals and ceramics and the effective solutions are discussed.The garnet scintillation ceramics with the highest application potential are summarized,and the future development directions are proposed.
基金This work was financially supported from the National Key Re-search and Development Program of China(No.2021YFB3501700)the National Natural Science Foundation of China(Nos.52202135,61975070,51902143 and 61971207)+7 种基金the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)the Key Research and Development Project of Jiangsu Province(Nos.BE2021040 and BE2019033)the Natural Science Foundation of Jiangsu Province(Nos.BK20191467 and BK20221226)the Postgrad-uate Research&Practice Innovation Program of Jiangsu Province(No.KYCX21_2568)the International S&T Cooperation Program of Jiangsu Province(Nos.BZ2019063,BZ2020045 and BZ2020030)the Natural Science Foundation of the Jiangsu Higher Education In-stitutes of China(Nos.19KJB430018 and 20KJA430003)the Special Project for Technology Innovation of Xuzhou City(Nos.KC19250,KC20201,KC20244 and KC21379)Open Project of State Key Laboratory of Advanced Materials and Electronic Components(No.FHR-JS-202011017).The authors would like to show great appreci-ation to Prof.Ole Bjarlin Jensen from the Technical University of Denmark for his long-term support and guidance on diode laser-related knowledge and technique.
文摘As the fourth-generation light source,solid-state lighting has developed rapidly in the past 30 years due to its advantages of high efficiency and environmental protection.It is widely used in various scenes such as automobile headlights,projection displays,industrial production,and remote lighting.High-power,high-brightness white light-emitting diodes(LEDs)and laser diodes(LDs)technology put forward new requirements for the service stability of color conversion materials.Garnet phosphor ceramics have emerged with their unique advantages of withstanding high power excitation density and the flexibly tunable spectrum.In this article,the research progress of garnet based phosphor ceramics for high-power solid-state lighting was comprehensively reviewed.Firstly,the band gap and coordination environment regulations of luminescence centers of garnet phosphor were summarized.Secondly,the improvement of luminous efficacy via defects regulation was discussed.Thirdly,the relationship between the geometric design and the lighting performance was elucidated.Fourthly,the characterization methods of phosphor ceramics for laser lighting were introduced and illustrated.Finally,the development trend of garnet phosphor ceramics in solid state lighting and display was prospected.
文摘Rechargeable lithium-oxygen （Li-O2） batteries have received intensive research interest due to its ultrahigh energy density, while its cycle stability is still hindered by the high reactivity of the Li anode with oxygen and moisture. To alleviate the corrosion of the metallic lithium anodes for achieving a stable Li-O2 battery, and as a proof-of-concept experiment, a distinctive hybrid electrolyte system with an organic/ceramic/organic electrolyte （OCOE） architecture is designed. Importantl~ the cycle number of Li-O2 batteries with OCOE is significantly improved compared with batteries with an organic electrolyte （OE）. This might be attributed to the effective suppression of the lithium anode corrosion caused by the OE degradation and the crossover of oxygen from the cathode. We consider that our facile, low-cost, and highly effective lithium protection strategy presents a new avenue to address the daunting corrosion problem of lithium metal anodes in Li-O2 batteries. In addition, the proposed strategy can be easily extended to other metal-O2 battery systems, such as Na-O2 batteries.
基金supported by the National Key R&D Program of China(Grant No.2023YFB3812000)the General Project of Shanghai Natural Science Foundation(Grant No.22ZR1471500)the Prospective Basic Research and Applied Basic Research of Hengdian Group.
文摘Terbium aluminum garnet(Tb_(3)Al_(5)O_(12);TAG)ceramics are among the most promising magneto–optical materials owing to their outstanding comprehensive performance.Many works have focused on improving the optical quality of TAG ceramics.A key point for improving optical quality is ensuring the accuracy of the stoichiometric ratio and avoiding secondary phases.In this work,0,2,4,or 6 wt%Sc_(2)O_(3) was added to the TAG ceramics to increase the solid solubility.The effects of Sc substitution on the crystal structure,sintering process,microstructure,optical transmittance,and magneto–optical properties of(Tb_(1−x)Sc_(x))_(3)(Al_(1−y)Sc_(y))_(2)Al_(3)O_(12)(TSAG)ceramics are studied in detail.4 wt%Sc2O3:TAG ceramics with an in-line transmittance of 82.2%at 1064 nm and 81.2%at 633 nm were successfully fabricated,and the Verdet constant was 164.4 rad·T^(−1)·m^(−1) at 633 nm.Anti-site defects(ADs)and Sc replacement in TAG are further studied via first-principles calculations to determine the working mechanism of Sc.Both the experimental and calculation results show that the introduction of Sc can effectively increase the solid solubility of TAG ceramics,suppress secondary phases,and hence improve the optical transmittance.
基金supported by the National Key R&D Program of China(Grant No.2017YFB0310500)the NSFC-RFBR Cooperative Research Project(Grant No.61911530135)+1 种基金the Key Research Project of the Frontier Science of the Chinese Academy of Sciences(No.QYZDB-SSW-JSC022)supported partially by the Ministry of High Education and Science of the Russian Federation and the State Task executed in the Institute of Applied Physics RAS(Project No.00352019-0015)。
文摘Transparent ceramics are at the heart of modern magneto-optical materials providing promising opportunities for Faraday isolators.1.0 at%RE:Tb3Ga5O12(rare earth(RE)=Pr,Tm,Dy)transparent ceramics were successfully prepared by air sintering and sequential HIP technique using the coprecipitated powders as the raw material.All the powders have shown to be a pure cubic terbium gallium garnet(TGG)phase and exhibit good dispersion.Additionally,a change could not be observed in particle shape with the different doped ions.After the two-step sintering,all the obtained ceramics have good optical quality,and the in-line transmittances at 1070 nm are higher than 80%.Moreover,no secondary phase can be detected from the microstructures.However,the pores which remain entrapped in the ceramics can be noted.The Verdet constant of ceramic samples is optimized by RE doping,and the Verdet constant at 632.8 nm is about−143 rad·T^(−1)·m^(−1),which is about 5%higher than that of TGG ceramics.Finally,the thermo-optical properties of 1.0 at%RE:TGG transparent ceramics are compared.The annealed TGG ceramic showed the best thermo-optical properties,and the thermally induced depolarization of 1.0 at%Ce:TGG and 1.0 at%Tm:TGG was inferior to that of annealed TGG ceramic.
基金the National Undergraduate Innovation and Entrepreneurship Training Program(202310360017 and 202410360018)。
文摘In this study,the inequivalent substitution of Ca^(2+)by Li^(+)in the Ca_(3)Co_(2)SiV_(2)O_(12)compound was designed to modulate its sintering characteristics and microwave dielectric properties.The corresponding Ca_(3-x)Li_(2x)Co_(2)SiV_(2)O_(12)(CCSV-xLi,0.01≤x≤0.07)ceramics were prepared via the conventional solid-state phase method,which could be densely sintered at a temperature below 1140℃.Rietveld refinement results suggested that all the doped Li occupied the Ca-site as x≤0.05 while superfluous Li positioned at the Co-site of CCSV when x≤0.07.This atomic occupancy had a remarkable effect on the degree of“rattling effect”and thus modulated the relative permittivity of ceramics,constantly increasing at x=0.01-0.05 and slightly decreasing at x=0.07.Raman spectra revealed that Q×f value was closely related to Raman shift and FWHM.Also,the Q×f value was partly influenced by oxygen vacancy concentration.The t_(f)demonstrated an opposite tendency to the bond valence of the A-site and was affected by the“rattling effect”.The CCSV-0.05Li ceramic sintered at 1120℃possessed excellent microwave dielectric properties:εr=12.17,Q×f=56,220 GHz,and t_(f)=-8.5×10^(-6)℃^(-1).
