Li_(6)PS_(5)Cl is a highly wanted sulfide-solid-electrolyte(SSE)for developing all-solid-state lithium batteries,due to its high ionic conductivity,good processability and abundant compositional elements.However,its c...Li_(6)PS_(5)Cl is a highly wanted sulfide-solid-electrolyte(SSE)for developing all-solid-state lithium batteries,due to its high ionic conductivity,good processability and abundant compositional elements.However,its cyclability is poor because of harmful side reactions at the Li_(6)PS_(5)Cl/Li interface and growth of lithium dendrites inside Li_(6)PS_(5)Cl phase.Herein,we report a simple interface-engineering remedy to boost the electrochemical performance of Li_(6)PS_(5)Cl,by coating its surface with a Li-compatible electrolyte Li3OCl having low electronic conductivity.The obtainedLi_(6)PS_(5)Cl@Li_(3)OCl core@shell structure exhibits a synergistic effect.Consequently,compared with the bare Li_(6)PS_(5)Cl,this composite electrolyte exhibits great performance improvements:1)In Li|electrolyte|Li symmetric cells,the critical current density at 30℃gets increased from 0.6 mA cm^(-2)to 1.6 mA cm^(-2),and the lifetime gets prolonged from 320 h to 1400 h at the cycling current of 0.2 mA cm^(-2)or from 10 h to 900 h at the cycling current of 0.5 mA cm^(-2);2)In Li|electrolyte|NCM721 full cells running at 30℃,the cycling capacity at 0.2 C(or 0.5 C)gets enhanced by 20%(or from unfeasible to be feasible)for 100 cycles and the rate capability reaches up to 2 C from 0.2 C;and in full cells running at 60℃,the cycling capacity is increased by 7%at 0.2 C and the rate capability is enhanced to 3.0 C from 0.5 C.The experimental studies and theoretical computations show that the performance enhancements are due to the confined electron penetration and suppressed lithium dendrites growth at theLi_(6)PS_(5)Cl@Li_(3)OCl interface.展开更多
Weak water stability and lithium reactivity are two major stability issues of sulfide solid-state electrolytes(SSEs)for all-solid-state lithium metal batteries.Here,we report on nano-sized boron nitride(BN)-coated Li_...Weak water stability and lithium reactivity are two major stability issues of sulfide solid-state electrolytes(SSEs)for all-solid-state lithium metal batteries.Here,we report on nano-sized boron nitride(BN)-coated Li_(5.7)PS_(4.7)Cl_(1.3)(BN@LPSC1.3)sulfide SSE,which exhibits reduced H_(2)S emission and improved ionic conductivity retention after relative humidity 1.2%-1.5%ambient condition exposure.Furthermore,BN can partially react with lithium metal to create stable Li_(3)N,resulting in BN@LPSC1.3 showing reduced reactivity against lithium metal and a higher critical current density of 2.2mA/cm^(2).The Li/BN@LPSC/Li symmetrical battery also shows considerably greater stability for>2000 h at a current density of 0.1mA/cm^(2).Despite the high cathode mass loading of 13.38mg/cm^(2),the LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)/BN@LPSC1.3/Li all-solidstate lithium metal battery achieves 84.34%capacity retention even after 500 cycles at 0.1 C and room temperature(25℃).展开更多
All-solid-state batteries(ASSB) with lithium anode have attracted ever-increasing attention towards developing safer batteries with high energy densities.While great advancement has been achieved in developing solid e...All-solid-state batteries(ASSB) with lithium anode have attracted ever-increasing attention towards developing safer batteries with high energy densities.While great advancement has been achieved in developing solid electrolytes(SE) with superb ionic conductivity rivalling that of the current liquid technology,it has yet been very difficult in their successful application to ASSBs with sustaining rate and cyclic performances.Here in this work,we have realized a stable ASSB using the Li_(6.25)PS_(5.25)Cl_(0.75) fast ionconducting electrolyte together with LiNbO_(3) coated LiCoO_(2) as cathode and lithium foil as the anode.The effective diffusion coefficient of Li-ions in the battery is higher than 10^(-12) cm^(2) s^(-1),and the significantly enhanced electrochemical matching at the cathode-electrolyte interface was essential to enable long-term stability against high oxidation potential,with the LCO@LNO/Li_(6.25)PS_(5.25)Cl_(0.75)/Li battery to retain 74.12% capacity after 430 cycles at 100 μA cm-2 and 59.7% of capacity after 800 cycles at 50 μA cm^(-2),at a high charging cut-off voltage of 4.2 V.This demonstrates that the Li_(6.25)PS_(5.25)Cl_(0.75) can be an excellent electrolyte for the realization of stable ASSBs with high-voltage cathodes and metallic lithium as anode,once the electrochemical compatibility between cathode and electrolyte can be addressed with a suitable buffer coating.展开更多
All-solid-state lithium-metal batteries(ASSLMBs)are widely considered as the ultimately advanced lithium batteries owing to their improved energy density and enhanced safety features.Among various solid electrolytes,s...All-solid-state lithium-metal batteries(ASSLMBs)are widely considered as the ultimately advanced lithium batteries owing to their improved energy density and enhanced safety features.Among various solid electrolytes,sulfide solid electrolyte(SSE)Li_(6)PS_(5)Cl has garnered significant attention.However,its application is limited by its poor cyclability and low critical current density(CCD).In this study,we introduce a novel approach to enhance the performance of Li_(6)PS_(5)Cl by doping it with fluorine,using lithium fluoride nanoparticles(LiFs)as the doping precursor.The F-doped electrolyte Li_(6)PS_(5)Cl-0.2LiF(nano)shows a doubled CCD,from 0.5 to 1.0 mA/cm^(2) without compromising the ionic conductivity;in fact,conductivity is enhanced from 2.82 to 3.30 mS/cm,contrary to the typical performance decline seen in conventionally doped Li_(6)PS_(5)Cl electrolytes.In symmetric Li|SSE|Li cells,the lifetime of Li_(6)PS_(5)Cl-0.2LiF(nano)is 4 times longer than that of Li_(6)PS_(5)Cl,achieving 1500 h vs.371 h under a charging/discharging current density of 0.2 mA/cm^(2).In Li|SSE|LiNbO_(3)@NCM721 full cells,which are tested under a cycling rate of 0.1 C at 30℃,the lifetime of Li_(6)PS_(5)Cl-0.2LiF(nano)is four times that of Li_(6)PS_(5)Cl,reaching 100 cycles vs.26 cycles.Therefore,the doping of nano-LiF off ers a promising approach to developing high-performance Li_(6)PS_(5)Cl for ASSLMBs.展开更多
LiNi_(0.8)Co_(0.15)Al_(0.05)O_(2)(NCA) is a promising cathode for sulfide-based solid-state lithium batteries(ASSLBs)profiting from its high specific capacity and voltage plateau, which yielding high energy density. H...LiNi_(0.8)Co_(0.15)Al_(0.05)O_(2)(NCA) is a promising cathode for sulfide-based solid-state lithium batteries(ASSLBs)profiting from its high specific capacity and voltage plateau, which yielding high energy density. However, the inferior interfacial stability between the bare NCA and sulfides limits its electrochemical performance. Hereien, the dual-electrolyte layer is proposed to mitigate this effect and enhance the battery performances of NCA-based ASSLIBs. The Li_(3)InCl_6 wih high conductivity and excellent electrochemcial stability act both as an ion additives to promote Li-ion diffusion across the interface in the cathode and as a buffer layer between the cathode layer and the solid electrolyte layer to avoid side reactions and improve the interface stability. The corresponding battery exhibits high discharge capacities and superior cyclabilities at both room and elevated temperatures. It exhibits discharge performance of 237.04 and216.07 m Ah/g at 0.1 and 0.5 C, respectively, when cycled at 60 ℃, and sustains 95.9% of the capacity after100 cycles at 0.5 C. The work demonstrates a simple strategy to ensure the superior performances of NCA in sulfide-based ASSLBs.展开更多
Li_(2)ZrCl_(6)(LZC) solid-state electrolytes(SSEs) have been recognized as a candidate halide SSEs for allsolid-state Li batteries(ASSLBs) with high energy density and safety due to its great compatibility with4V-clas...Li_(2)ZrCl_(6)(LZC) solid-state electrolytes(SSEs) have been recognized as a candidate halide SSEs for allsolid-state Li batteries(ASSLBs) with high energy density and safety due to its great compatibility with4V-class cathodes and low bill-of-material(BOM) cost.However,despite the benefits,the poor chemical/electrochemical stability of LZC against Li metal causes the deterioration of Li/LZC interface,which has a detrimental inhibition on Li^(+) transport in ASSLBs.Herein,we report a composite SSE combining by LZC and argyrodite buffer layer(Li_(6)PS_(5)Cl,LPSC) that prevent the unfavorable interaction between LZC and Li metal.The Li/LPSC-LZC-LPSC/Li symmetric cell stably cycles for over 1000 h at 0.3 mA/cm^(2)(0.15mAh/cm^(2)) and has a high critical current density(CCD) value of 2.1 mA/cm^(2)at 25 ℃,Under high temperature(60℃) which promotes the reaction between Li and LZC,symmetric cell fabricated with composite SSE also display stable cycling performance over 1200h at 0.3 mAh/cm^(2).Especially,the Li/NCM ASSLBs fabricated with composite SSE exhibit a high initial coulombic efficiency,as well as superior cycling and rate performance.This simple and efficient strategy will be instrumental in the development of halidebased high-performance ASSLBs.展开更多
Selenium,an element belonging to the same group in the periodic table as sulfur,has a high electronic conductivity(1×10^(-5)S/cm)and a high volumetric energy density(3253 mA h/cm^(3)),which is a prospective catho...Selenium,an element belonging to the same group in the periodic table as sulfur,has a high electronic conductivity(1×10^(-5)S/cm)and a high volumetric energy density(3253 mA h/cm^(3)),which is a prospective cathode material for high-energy all-solid-state rechargeable batteries.However,its wide use is hindered by large volume expansion and low utilization rate.In this work,Se-infused nitrogen-doped hierarchical meso-microporous carbon composites(Se/NHPC)are prepared by a melt-diffusion process.Amorphous Se is uniformly dispersed in meso-micropores of NHPC with a high mass loading of 81%.All-solid-state Li-Se batteries fabricated by using Se/NHPC as the cathode,a Li-In alloy as the anode,and Li_(6)PS_(5)Cl as the solid-state electrolyte,deliver a highly reversible capacity of 621 m Ah/g(92%of theoretical capacity),a good rate capability and a high capacity retention value of 80.9%after 100 cycles.It is found that the capacity decay of Se cathode is mainly related to the interfacial degradation and the separation of Se from the carbon substrate,as suggested by the continuous increase of interfacial resistance and the structural transformation from amorphous Senchains to Se8rings initial discharge/charge cycle and then to the trigonally crystalline Se chains structure after the long-term cycles.展开更多
All-solid-state lithium metal batteries(ASSLMBs)featuring sulfide solid electrolytes(SEs)are recognized as the most promising next-generation energy storage technology because of their exceptional safety and much-impr...All-solid-state lithium metal batteries(ASSLMBs)featuring sulfide solid electrolytes(SEs)are recognized as the most promising next-generation energy storage technology because of their exceptional safety and much-improved energy density.However,lithium dendrite growth in sulfide SEs and their poor air stability have posed significant obstacles to the advancement of sulfide-based ASSLMBs.Here,a thin layer(approximately 5 nm)of g-C_(3)N_(4)is coated on the surface of a sulfide SE(Li_(6)PS_(5)Cl),which not only lowers the electronic conductivity of Li_(6)PS_(5)Cl but also achieves remarkable interface stability by facilitating the in situ formation of ion-conductive Li3N at the Li/Li_(6)PS_(5)Cl interface.Additionally,the g-C_(3)N_(4)coating on the surface can substantially reduce the formation of H_(2)S when Li_(6)PS_(5)Cl is exposed to humid air.As a result,Li-Li symmetrical cells using g-C_(3)N_(4)-coated Li_(6)PS_(5)Cl stably cycle for 1000 h with a current density of 0.2 mA cm^(-2).ASSLMBs paired with LiNbO_(3)-coated LiNi_(0.6)Mn_(0.2)Co_(0.2)O_(2)exhibit a capacity of 132.8 mAh g^(-1)at 0.1 C and a high-capacity retention of 99.1%after 200 cycles.Furthermore,g-C_(3)N_(4)-coated Li_(6)PS_(5)Cl effectively mitigates the self-discharge behavior observed in ASSLMBs.This surface-coating approach for sulfide solid electrolytes opens the door to the practical implementation of sulfide-based ASSLMBs.展开更多
The practical applications of high-capacity alloy-type anode materials in sodium-ion batteries(SIBs)are challenged by their vast volume effects and resulting unstable electrode-electrolyte interphases during discharge...The practical applications of high-capacity alloy-type anode materials in sodium-ion batteries(SIBs)are challenged by their vast volume effects and resulting unstable electrode-electrolyte interphases during discharge-charge cycling.Taking red phosphorus(P)/carbon anode material as an example,we report an on-site conversion reaction to intentionally eliminate the volume effect-dominated surface P and yield an ionically conducting layer of Na3PS4solid-state electrolyte on the composite.Such a surface reconstruction can significantly suppress the electrode swelling and simultaneously enable the activation energy of interfacial Na+transfer as low as 36.7 k J mol^(-1),resulting in excellent electrode stability and ultrafast reaction kinetics.Consequently,excellent cycling performance(510 mA h g^(-1)at 5 A g^(-1)after 1000 cycles with a tiny capacity fading rate of 0.016%per cycle)and outstanding rate capability(484 mA h g^(-1)at 10 A g^(-1)are achieved in half cells.When coupled with Na_(3)V_(2)(PO4)3cathode,the full cells exhibit 100%capacity retention over 200 cycles at 5C with an average Coulombic efficiency of 99.93%and a high energy density of 125.5 W h kg^(-1)at a power density of 8215.6 W kg^(-1)(charge or discharge within~49 s).Remarkably,the full cell can steadily operate at a high areal capacity of 1.9 mA h cm^(-2),the highest level among red P-based full SIBs ever reported.展开更多
FeS_(2) shows significant potential as cathode material for all-solid-state lithium batteries(ASSLBs)due to its high theoretical specific capacity,low cost,and environmental friendliness.However,the poor ion/electron ...FeS_(2) shows significant potential as cathode material for all-solid-state lithium batteries(ASSLBs)due to its high theoretical specific capacity,low cost,and environmental friendliness.However,the poor ion/electron conductivity and large volume variation effect of FeS_(2) inhibit its practical applications.Here,the influence of particle size of FeS_(2) on the corresponding sulfide-based solid-state batteries is carefully investigated by tuning FeS_(2) size.Moreover,low operating temperature is chosen to mitigate the large volume changes during cycling in the battery.S-FeS_(2) with smaller particle sizes delivers superior electrochemical performances than that of the larger L-FeS_(2) in Li_(5.5)PS_(4.5)Cl_(1.5)-based ASSLBs under different operating temperatures.S-FeS_(2) shows stable discharge capacities during 50 cycles with a current density of 0.1 m A/cm^(2)under -20℃.When the current density rises to 1.0 m A/cm^(2),it delivers an initial discharge capacity of 146.9 m Ah/g and maintains 63% of the capacity after 100 cycles.This work contributes to constructing ASSLBs enables excellent electrochemical performances under extreme operating temperatures.展开更多
While sulfide solid electrolytes such as Na_(11)Sn_(2)PS_(12)can allow fast transport of Na+ions,their utilization in solid sodium ion batteries is rather unsuccessful since they are not electrochemically compatible t...While sulfide solid electrolytes such as Na_(11)Sn_(2)PS_(12)can allow fast transport of Na+ions,their utilization in solid sodium ion batteries is rather unsuccessful since they are not electrochemically compatible to both high-voltage cathodes and sodium metal anode.In this work,we devise an effective approach toward realizing solid sodium ion batteries,using the Na_(11)Sn_(2)PS_(12)electrolyte and slurry-coated NASICON-type Na_(3)MnTi(PO_(4))_(3)@C as high-voltage cathode,highly beneficial for low processing cost and high content/loading of active cathode matter.We report that through significantly improved integrity of electrolyte-cathode interface,such solid sodium ion batteries can deliver outstanding cycling and rate performance,with a charge voltage resilience up to 4.1 V,a high cathode discharge capacity of 128.7 mAh g^(-1)against the Na_(3)MnTi(PO_(4))_(3)@C in cathode is achieved at 0.05 C,and capacity retention ratio of 82%with a rate of 0.1 C is realized after prolonged cycling at room temperature.Besides,we demonstrate that such a solid sodium ion battery can even perform at a sub-zero Celsius temperature of-10℃,when the conventional control cell using liquid electrolyte completely fail to function.This work is to offer a dependable avenue in engineering next generation of safe solid ion batteries based on highly sustainable and much cheaper material resources.展开更多
硫化物Li_(3)PS_(4)是重要的含硫快离子导体,锂离子电导率高,机械性能优异,化学兼容性好,属于全固态电池中一类重要的固态电解质.Li_(3)PS_(4)具有多种晶体结构(玻璃态、α相、β相、γ相),而晶体结构对于材料离子电导率有决定性的影响...硫化物Li_(3)PS_(4)是重要的含硫快离子导体,锂离子电导率高,机械性能优异,化学兼容性好,属于全固态电池中一类重要的固态电解质.Li_(3)PS_(4)具有多种晶体结构(玻璃态、α相、β相、γ相),而晶体结构对于材料离子电导率有决定性的影响,因此探究不同Li_(3)PS_(4)晶体结构的合成条件及其转变过程对固态电解质的应用有重要意义.本文通过原位变温Raman和室温X射线衍射(XRD)分析发现,通过球磨法所得glass-Li_(3)PS_(4)在首次升温过程中(240℃)优先转变为亚稳态的β-Li_(3)PS_(4),此时冷却到室温能保持β相结构,并具有较高的离子电导率(0.65 mS cm^(-1)).当烧结温度继续升高(>480℃),β相会转变为离子电导率更高但热力学不稳定的α-Li_(3)PS_(4),在后续的降温过程中,α相会直接转变为热力学更稳定但离子电导率差的γ-Li_(3)PS_(4).此外,γ-Li_(3)PS_(4)和β-Li_(3)PS_(4)具有一定的结构记忆效应,即使经历二次低温烧结后(240℃)也能维持其固有的结构.以上结果表明,首次烧结温度对于Li_(3)PS_(4)材料的结构和离子电导率具有重要的影响,合理控制烧结温度能够成功制备出具有更高离子电导率的β-Li_(3)PS_(4)固态电解质.此外,所制备的β-Li_(3)PS_(4)固态电解质对锂表现出相对优异的界面性能.展开更多
基金supported by the National Key Research and Development Program of China (2018YFE0111600)Haihe Laboratory of Sustainable Chemical Transformations for financial supportpartially supported by the Graduate Top-notch Innovation Award Plan in Liberal Arts and Science of Tianjin University for the Year of 2023 (B2-2023-012)
文摘Li_(6)PS_(5)Cl is a highly wanted sulfide-solid-electrolyte(SSE)for developing all-solid-state lithium batteries,due to its high ionic conductivity,good processability and abundant compositional elements.However,its cyclability is poor because of harmful side reactions at the Li_(6)PS_(5)Cl/Li interface and growth of lithium dendrites inside Li_(6)PS_(5)Cl phase.Herein,we report a simple interface-engineering remedy to boost the electrochemical performance of Li_(6)PS_(5)Cl,by coating its surface with a Li-compatible electrolyte Li3OCl having low electronic conductivity.The obtainedLi_(6)PS_(5)Cl@Li_(3)OCl core@shell structure exhibits a synergistic effect.Consequently,compared with the bare Li_(6)PS_(5)Cl,this composite electrolyte exhibits great performance improvements:1)In Li|electrolyte|Li symmetric cells,the critical current density at 30℃gets increased from 0.6 mA cm^(-2)to 1.6 mA cm^(-2),and the lifetime gets prolonged from 320 h to 1400 h at the cycling current of 0.2 mA cm^(-2)or from 10 h to 900 h at the cycling current of 0.5 mA cm^(-2);2)In Li|electrolyte|NCM721 full cells running at 30℃,the cycling capacity at 0.2 C(or 0.5 C)gets enhanced by 20%(or from unfeasible to be feasible)for 100 cycles and the rate capability reaches up to 2 C from 0.2 C;and in full cells running at 60℃,the cycling capacity is increased by 7%at 0.2 C and the rate capability is enhanced to 3.0 C from 0.5 C.The experimental studies and theoretical computations show that the performance enhancements are due to the confined electron penetration and suppressed lithium dendrites growth at theLi_(6)PS_(5)Cl@Li_(3)OCl interface.
基金financial support from the Science and Technology Project of Shenzhen(Nos.JCYJ20210324094206019 and JCYJ20210324094000001).
文摘Weak water stability and lithium reactivity are two major stability issues of sulfide solid-state electrolytes(SSEs)for all-solid-state lithium metal batteries.Here,we report on nano-sized boron nitride(BN)-coated Li_(5.7)PS_(4.7)Cl_(1.3)(BN@LPSC1.3)sulfide SSE,which exhibits reduced H_(2)S emission and improved ionic conductivity retention after relative humidity 1.2%-1.5%ambient condition exposure.Furthermore,BN can partially react with lithium metal to create stable Li_(3)N,resulting in BN@LPSC1.3 showing reduced reactivity against lithium metal and a higher critical current density of 2.2mA/cm^(2).The Li/BN@LPSC/Li symmetrical battery also shows considerably greater stability for>2000 h at a current density of 0.1mA/cm^(2).Despite the high cathode mass loading of 13.38mg/cm^(2),the LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)/BN@LPSC1.3/Li all-solidstate lithium metal battery achieves 84.34%capacity retention even after 500 cycles at 0.1 C and room temperature(25℃).
基金supported in part by the 1000 Talents Program of China,the Zhengzhou Materials Genome Institute(ZMGI)the Natural Science Foundation of China(Nos.51001091,91233101)the Fundamental Research Program from the Ministry of Science and Technology of China(no.2014CB931704)。
文摘All-solid-state batteries(ASSB) with lithium anode have attracted ever-increasing attention towards developing safer batteries with high energy densities.While great advancement has been achieved in developing solid electrolytes(SE) with superb ionic conductivity rivalling that of the current liquid technology,it has yet been very difficult in their successful application to ASSBs with sustaining rate and cyclic performances.Here in this work,we have realized a stable ASSB using the Li_(6.25)PS_(5.25)Cl_(0.75) fast ionconducting electrolyte together with LiNbO_(3) coated LiCoO_(2) as cathode and lithium foil as the anode.The effective diffusion coefficient of Li-ions in the battery is higher than 10^(-12) cm^(2) s^(-1),and the significantly enhanced electrochemical matching at the cathode-electrolyte interface was essential to enable long-term stability against high oxidation potential,with the LCO@LNO/Li_(6.25)PS_(5.25)Cl_(0.75)/Li battery to retain 74.12% capacity after 430 cycles at 100 μA cm-2 and 59.7% of capacity after 800 cycles at 50 μA cm^(-2),at a high charging cut-off voltage of 4.2 V.This demonstrates that the Li_(6.25)PS_(5.25)Cl_(0.75) can be an excellent electrolyte for the realization of stable ASSBs with high-voltage cathodes and metallic lithium as anode,once the electrochemical compatibility between cathode and electrolyte can be addressed with a suitable buffer coating.
基金supported by the National Key Research and Development Program of China(No.2018YFE0111600)the Haihe Laboratory of Sustainable Chemical Transformations(No.CYZC202307)for financial support。
文摘All-solid-state lithium-metal batteries(ASSLMBs)are widely considered as the ultimately advanced lithium batteries owing to their improved energy density and enhanced safety features.Among various solid electrolytes,sulfide solid electrolyte(SSE)Li_(6)PS_(5)Cl has garnered significant attention.However,its application is limited by its poor cyclability and low critical current density(CCD).In this study,we introduce a novel approach to enhance the performance of Li_(6)PS_(5)Cl by doping it with fluorine,using lithium fluoride nanoparticles(LiFs)as the doping precursor.The F-doped electrolyte Li_(6)PS_(5)Cl-0.2LiF(nano)shows a doubled CCD,from 0.5 to 1.0 mA/cm^(2) without compromising the ionic conductivity;in fact,conductivity is enhanced from 2.82 to 3.30 mS/cm,contrary to the typical performance decline seen in conventionally doped Li_(6)PS_(5)Cl electrolytes.In symmetric Li|SSE|Li cells,the lifetime of Li_(6)PS_(5)Cl-0.2LiF(nano)is 4 times longer than that of Li_(6)PS_(5)Cl,achieving 1500 h vs.371 h under a charging/discharging current density of 0.2 mA/cm^(2).In Li|SSE|LiNbO_(3)@NCM721 full cells,which are tested under a cycling rate of 0.1 C at 30℃,the lifetime of Li_(6)PS_(5)Cl-0.2LiF(nano)is four times that of Li_(6)PS_(5)Cl,reaching 100 cycles vs.26 cycles.Therefore,the doping of nano-LiF off ers a promising approach to developing high-performance Li_(6)PS_(5)Cl for ASSLMBs.
基金supported by the National Key Research and Development Program (No.2021YFB2500200)the National Natural Science Foundation of China (No.52177214)supported by China Fujian Energy Devices Science and Technology Innovation Laboratory Open Fund (No.21C-OP202211)。
文摘LiNi_(0.8)Co_(0.15)Al_(0.05)O_(2)(NCA) is a promising cathode for sulfide-based solid-state lithium batteries(ASSLBs)profiting from its high specific capacity and voltage plateau, which yielding high energy density. However, the inferior interfacial stability between the bare NCA and sulfides limits its electrochemical performance. Hereien, the dual-electrolyte layer is proposed to mitigate this effect and enhance the battery performances of NCA-based ASSLIBs. The Li_(3)InCl_6 wih high conductivity and excellent electrochemcial stability act both as an ion additives to promote Li-ion diffusion across the interface in the cathode and as a buffer layer between the cathode layer and the solid electrolyte layer to avoid side reactions and improve the interface stability. The corresponding battery exhibits high discharge capacities and superior cyclabilities at both room and elevated temperatures. It exhibits discharge performance of 237.04 and216.07 m Ah/g at 0.1 and 0.5 C, respectively, when cycled at 60 ℃, and sustains 95.9% of the capacity after100 cycles at 0.5 C. The work demonstrates a simple strategy to ensure the superior performances of NCA in sulfide-based ASSLBs.
基金B.Tian acknowledges the financial support from the Science and Technology Project of Shenzhen(No.JCYJ20210324094206019)X.Huang acknowledges the financial support from the National Natural Science Foundation of China(No.52102284)+2 种基金Z.Yu acknowledges Department of Science and Technology of Guangxi Province(Nos.AB21220027,AD19110077)Guangxi Key Laboratory of Manufacturing Systems Foundation(No.20-065-40-005Z)Engineering Research Center Foundation of Electronic Information Materials and Devices(No.EIMD-AA202005).
文摘Li_(2)ZrCl_(6)(LZC) solid-state electrolytes(SSEs) have been recognized as a candidate halide SSEs for allsolid-state Li batteries(ASSLBs) with high energy density and safety due to its great compatibility with4V-class cathodes and low bill-of-material(BOM) cost.However,despite the benefits,the poor chemical/electrochemical stability of LZC against Li metal causes the deterioration of Li/LZC interface,which has a detrimental inhibition on Li^(+) transport in ASSLBs.Herein,we report a composite SSE combining by LZC and argyrodite buffer layer(Li_(6)PS_(5)Cl,LPSC) that prevent the unfavorable interaction between LZC and Li metal.The Li/LPSC-LZC-LPSC/Li symmetric cell stably cycles for over 1000 h at 0.3 mA/cm^(2)(0.15mAh/cm^(2)) and has a high critical current density(CCD) value of 2.1 mA/cm^(2)at 25 ℃,Under high temperature(60℃) which promotes the reaction between Li and LZC,symmetric cell fabricated with composite SSE also display stable cycling performance over 1200h at 0.3 mAh/cm^(2).Especially,the Li/NCM ASSLBs fabricated with composite SSE exhibit a high initial coulombic efficiency,as well as superior cycling and rate performance.This simple and efficient strategy will be instrumental in the development of halidebased high-performance ASSLBs.
基金supported by the National Natural Science Foundation of China(Nos.51902188,52272224)Innovation Capacity Improvement Project of Small and Medium-Sized Technology-Based Enterprise of Shandong Province(No.2021TSGC1149)+2 种基金Youth Innovation Team Project of Shandong Provincial Education Department(No.10000082295015)Natural Science Doctoral Foundation of Shandong Province(No.ZR2019BEM019)the Future Program for Young Scholar of Shandong University。
文摘Selenium,an element belonging to the same group in the periodic table as sulfur,has a high electronic conductivity(1×10^(-5)S/cm)and a high volumetric energy density(3253 mA h/cm^(3)),which is a prospective cathode material for high-energy all-solid-state rechargeable batteries.However,its wide use is hindered by large volume expansion and low utilization rate.In this work,Se-infused nitrogen-doped hierarchical meso-microporous carbon composites(Se/NHPC)are prepared by a melt-diffusion process.Amorphous Se is uniformly dispersed in meso-micropores of NHPC with a high mass loading of 81%.All-solid-state Li-Se batteries fabricated by using Se/NHPC as the cathode,a Li-In alloy as the anode,and Li_(6)PS_(5)Cl as the solid-state electrolyte,deliver a highly reversible capacity of 621 m Ah/g(92%of theoretical capacity),a good rate capability and a high capacity retention value of 80.9%after 100 cycles.It is found that the capacity decay of Se cathode is mainly related to the interfacial degradation and the separation of Se from the carbon substrate,as suggested by the continuous increase of interfacial resistance and the structural transformation from amorphous Senchains to Se8rings initial discharge/charge cycle and then to the trigonally crystalline Se chains structure after the long-term cycles.
基金supported by Beijing Natural Science Foundation(JQ22028)National Natural Science Foundation of China(U21A2080)+1 种基金Jilin Province Science and Technology Major Project(20210301021GX)Ministry of Science and Technology Rare Earth Special(2022YFB3506300).
文摘All-solid-state lithium metal batteries(ASSLMBs)featuring sulfide solid electrolytes(SEs)are recognized as the most promising next-generation energy storage technology because of their exceptional safety and much-improved energy density.However,lithium dendrite growth in sulfide SEs and their poor air stability have posed significant obstacles to the advancement of sulfide-based ASSLMBs.Here,a thin layer(approximately 5 nm)of g-C_(3)N_(4)is coated on the surface of a sulfide SE(Li_(6)PS_(5)Cl),which not only lowers the electronic conductivity of Li_(6)PS_(5)Cl but also achieves remarkable interface stability by facilitating the in situ formation of ion-conductive Li3N at the Li/Li_(6)PS_(5)Cl interface.Additionally,the g-C_(3)N_(4)coating on the surface can substantially reduce the formation of H_(2)S when Li_(6)PS_(5)Cl is exposed to humid air.As a result,Li-Li symmetrical cells using g-C_(3)N_(4)-coated Li_(6)PS_(5)Cl stably cycle for 1000 h with a current density of 0.2 mA cm^(-2).ASSLMBs paired with LiNbO_(3)-coated LiNi_(0.6)Mn_(0.2)Co_(0.2)O_(2)exhibit a capacity of 132.8 mAh g^(-1)at 0.1 C and a high-capacity retention of 99.1%after 200 cycles.Furthermore,g-C_(3)N_(4)-coated Li_(6)PS_(5)Cl effectively mitigates the self-discharge behavior observed in ASSLMBs.This surface-coating approach for sulfide solid electrolytes opens the door to the practical implementation of sulfide-based ASSLMBs.
基金support from the National Natural Science Foundation of China(51976143)the Guangdong Key Areas Research and Development Program(2020B090904001 and 2019B090909003)。
文摘The practical applications of high-capacity alloy-type anode materials in sodium-ion batteries(SIBs)are challenged by their vast volume effects and resulting unstable electrode-electrolyte interphases during discharge-charge cycling.Taking red phosphorus(P)/carbon anode material as an example,we report an on-site conversion reaction to intentionally eliminate the volume effect-dominated surface P and yield an ionically conducting layer of Na3PS4solid-state electrolyte on the composite.Such a surface reconstruction can significantly suppress the electrode swelling and simultaneously enable the activation energy of interfacial Na+transfer as low as 36.7 k J mol^(-1),resulting in excellent electrode stability and ultrafast reaction kinetics.Consequently,excellent cycling performance(510 mA h g^(-1)at 5 A g^(-1)after 1000 cycles with a tiny capacity fading rate of 0.016%per cycle)and outstanding rate capability(484 mA h g^(-1)at 10 A g^(-1)are achieved in half cells.When coupled with Na_(3)V_(2)(PO4)3cathode,the full cells exhibit 100%capacity retention over 200 cycles at 5C with an average Coulombic efficiency of 99.93%and a high energy density of 125.5 W h kg^(-1)at a power density of 8215.6 W kg^(-1)(charge or discharge within~49 s).Remarkably,the full cell can steadily operate at a high areal capacity of 1.9 mA h cm^(-2),the highest level among red P-based full SIBs ever reported.
基金supported by the National Key Research and Development Program(No.2021YFB2400300)the National Natural Science Foundation of China(No.52177214)supported by China Fujian Energy Devices Science and Technology Innovation Laboratory Open Fund(No.21C-OP202211)。
文摘FeS_(2) shows significant potential as cathode material for all-solid-state lithium batteries(ASSLBs)due to its high theoretical specific capacity,low cost,and environmental friendliness.However,the poor ion/electron conductivity and large volume variation effect of FeS_(2) inhibit its practical applications.Here,the influence of particle size of FeS_(2) on the corresponding sulfide-based solid-state batteries is carefully investigated by tuning FeS_(2) size.Moreover,low operating temperature is chosen to mitigate the large volume changes during cycling in the battery.S-FeS_(2) with smaller particle sizes delivers superior electrochemical performances than that of the larger L-FeS_(2) in Li_(5.5)PS_(4.5)Cl_(1.5)-based ASSLBs under different operating temperatures.S-FeS_(2) shows stable discharge capacities during 50 cycles with a current density of 0.1 m A/cm^(2)under -20℃.When the current density rises to 1.0 m A/cm^(2),it delivers an initial discharge capacity of 146.9 m Ah/g and maintains 63% of the capacity after 100 cycles.This work contributes to constructing ASSLBs enables excellent electrochemical performances under extreme operating temperatures.
基金supported in part by the Zhengzhou Materials Genome Institute,the National Natural Science Foundation of China(nos.51001091,111174256,91233101,51602094,11274100,51602290)the Fundamental Research Program from the Ministry of Science and Technology of China(no.2014CB931704).
文摘While sulfide solid electrolytes such as Na_(11)Sn_(2)PS_(12)can allow fast transport of Na+ions,their utilization in solid sodium ion batteries is rather unsuccessful since they are not electrochemically compatible to both high-voltage cathodes and sodium metal anode.In this work,we devise an effective approach toward realizing solid sodium ion batteries,using the Na_(11)Sn_(2)PS_(12)electrolyte and slurry-coated NASICON-type Na_(3)MnTi(PO_(4))_(3)@C as high-voltage cathode,highly beneficial for low processing cost and high content/loading of active cathode matter.We report that through significantly improved integrity of electrolyte-cathode interface,such solid sodium ion batteries can deliver outstanding cycling and rate performance,with a charge voltage resilience up to 4.1 V,a high cathode discharge capacity of 128.7 mAh g^(-1)against the Na_(3)MnTi(PO_(4))_(3)@C in cathode is achieved at 0.05 C,and capacity retention ratio of 82%with a rate of 0.1 C is realized after prolonged cycling at room temperature.Besides,we demonstrate that such a solid sodium ion battery can even perform at a sub-zero Celsius temperature of-10℃,when the conventional control cell using liquid electrolyte completely fail to function.This work is to offer a dependable avenue in engineering next generation of safe solid ion batteries based on highly sustainable and much cheaper material resources.
文摘硫化物Li_(3)PS_(4)是重要的含硫快离子导体,锂离子电导率高,机械性能优异,化学兼容性好,属于全固态电池中一类重要的固态电解质.Li_(3)PS_(4)具有多种晶体结构(玻璃态、α相、β相、γ相),而晶体结构对于材料离子电导率有决定性的影响,因此探究不同Li_(3)PS_(4)晶体结构的合成条件及其转变过程对固态电解质的应用有重要意义.本文通过原位变温Raman和室温X射线衍射(XRD)分析发现,通过球磨法所得glass-Li_(3)PS_(4)在首次升温过程中(240℃)优先转变为亚稳态的β-Li_(3)PS_(4),此时冷却到室温能保持β相结构,并具有较高的离子电导率(0.65 mS cm^(-1)).当烧结温度继续升高(>480℃),β相会转变为离子电导率更高但热力学不稳定的α-Li_(3)PS_(4),在后续的降温过程中,α相会直接转变为热力学更稳定但离子电导率差的γ-Li_(3)PS_(4).此外,γ-Li_(3)PS_(4)和β-Li_(3)PS_(4)具有一定的结构记忆效应,即使经历二次低温烧结后(240℃)也能维持其固有的结构.以上结果表明,首次烧结温度对于Li_(3)PS_(4)材料的结构和离子电导率具有重要的影响,合理控制烧结温度能够成功制备出具有更高离子电导率的β-Li_(3)PS_(4)固态电解质.此外,所制备的β-Li_(3)PS_(4)固态电解质对锂表现出相对优异的界面性能.
