High-capacity lithium-containing alloy anodes(e.g.,Li4.4Si,Li4.4Sn,and Li3P)enable lithium-free cathodes(e.g.,Sulfur,V2O5,and FeF3)to produce next-generation lithium-ion batteries(LIBs)with high energy density.Herein,...High-capacity lithium-containing alloy anodes(e.g.,Li4.4Si,Li4.4Sn,and Li3P)enable lithium-free cathodes(e.g.,Sulfur,V2O5,and FeF3)to produce next-generation lithium-ion batteries(LIBs)with high energy density.Herein,we design a Li3P/C nanocomposite with Li3P ultrafine nanodomains embedded in micrometer-scale porous carbon particles.Benefiting from the unique micro/nanostructure of the Li3P/C nanocomposite,electrons transfer rapidly through the conductive pathway provided by the porous carbon framework and the volume change between Li3P and P is confined in the nanopores of the carbon,which avoids the collapse of the whole Li3P/C composite particles.As expected,the as-achieved Li3P/C nanocomposite provided a high available lithium-ion capacity of 791 mAh/g(calculated based on the mass of Li3P/C)at 0.1 C during the initial delithiation process.Meanwhile,the Li3P/C nanocomposite showed 75%of its 0.5 C capacity at 6 C and stable cycling stability.展开更多
The high Li-ion conductivity of the Li7P3S11 sulfide-based solid electrolyte makes it a promising candidate for all-solid-state lithium batteries. The Li-ion transport over electrode-electrolyte and electrolyteelectro...The high Li-ion conductivity of the Li7P3S11 sulfide-based solid electrolyte makes it a promising candidate for all-solid-state lithium batteries. The Li-ion transport over electrode-electrolyte and electrolyteelectrolyte interfaces, vital for the performance of solid-state batteries, is investigated by impedance spectroscopy and solid-state NMR experiments. An all-solid-state Li-ion battery is assembled with the Li7P3S11 electrolyte, nano-Li2S cathode and Li-In foil anode, showing a relatively large initial discharge capacity of 1139.5 m Ah/g at a current density of 0.064 m A/cm^ 2 retaining 850.0 m Ah/g after 30 cycles. Electrochemical impedance spectroscopy suggests that the decrease in capacity over cycling is due to the increased interfacial resistance between the electrode and the electrolyte. 1D exchange ^7Li NMR quantifies the interfacial Li-ion transport between the uncycled electrode and the electrolyte, resulting in a diffusion coefficient of 1.70(3) ×10^-14cm^2/s at 333 K and an energy barrier of 0.132 e V for the Li-ion transport between Li2S cathode and Li7P3S11 electrolyte. This indicates that the barrier for Li-ion transport over the electrode-electrolyte interface is small. However, the small diffusion coefficient for Li-ion diffusion between the Li2S and the Li7P3S11 suggests that these contact interfaces between electrode and electrolyte are relatively scarce, challenging the performance of these solid-state batteries.展开更多
The effect of Al-substitution on the electrochemical performances of Li3V2(PO4)3 cathode materials was studied.Samples with stoichiometric proportion of Li3AlxV2-x(PO4)3(x=0,0.05,0.10)were prepared by adding Al(NO3)3 ...The effect of Al-substitution on the electrochemical performances of Li3V2(PO4)3 cathode materials was studied.Samples with stoichiometric proportion of Li3AlxV2-x(PO4)3(x=0,0.05,0.10)were prepared by adding Al(NO3)3 in the raw materials of Li3V2(PO4)3.The XRD analysis shows that the Al-substituted Li3V2(PO4)3 has the same monoclinic structure as the un-substituted Li3V2(PO4)3.The SEM images show that Al-substituted Li3V2(PO4)3 has regular and uniform particles.The electrochemical measurements show that Al-substitution can improve the rate capability of cathode materials.The Li3Al0.05V1.95(PO4)3 sample shows the best high-rate performance.The discharge capacity at 1C rate is 119 mA·h/g with 30th capacity retention rate about 92.97%.The electrode reaction reversibility and electronic conductivity are enhanced,and the charge transfer resistance decreases through Al-substitution.The improved electrochemical performances of Al-substituted Li3V2(PO4)3 cathode materials offer some favorable properties for their commercial application.展开更多
Achievement of lithium(Li)metal anode with thin thickness(e.g.,≤30µm)is highly desirable for rechargeable high energy density batteries.However,the fabrication and application of such thin Li metal foil electrod...Achievement of lithium(Li)metal anode with thin thickness(e.g.,≤30µm)is highly desirable for rechargeable high energy density batteries.However,the fabrication and application of such thin Li metal foil electrode remain challenging due to the poor mechanical processibility and inferior electrochemical performance of metallic Li.Here,mechanico-chemical synthesis of robust ultrathin Li/Li_(3)P(LLP)composite foils(~15µm)is demonstrated by employing repeated mechanical rolling/stacking operations using red P and metallic Li as raw materials.The in-situ formed Li+-conductive Li_(3)P nanoparticles in metallic Li matrix and their tight bonding strengthen the mechanical durability and enable the successful fabrication of free-standing ultrathin Li metal composite foil.Besides,it also reduces the electrochemical Li nucleation barrier and homogenizes Li plating/stripping behavior.When matching to high-voltage LiCoO_(2),the full cell with a low negative/positive(N/P)capacity ratio of~1.5 offers a high energy density of~522 W·h·kg^(-1) at 0.5 C based on the mass of cathode and anode.Taking into account its facile manufacturing,potentially low cost,and good electrochemical performance,we believe that such an ultrathin composite Li metal foil design with nanoparticle-dispersion-strengthened mechanism may boost the development of high energy density Li metal batteries.展开更多
Silicon(Si)is a promising anode candidate for next-generation lithium-ion batteries(LIBs)due to its high theoretical capacity.Solar Si photovoltaic waste possesses good purity and high output.Using it as the raw mater...Silicon(Si)is a promising anode candidate for next-generation lithium-ion batteries(LIBs)due to its high theoretical capacity.Solar Si photovoltaic waste possesses good purity and high output.Using it as the raw material for battery anodes can synchronously solve the problem of solid waste pollution and enable high energy density LIBs.A critical issue impeding the practical application of Si is the undesirable side reactions at the electrolyte-particle interface and the resulting increase in impedance during cycling.Herein,a Si-P core shell structure with chemical bonding at the Si-P interface is fabricated through a simple mechanical alloying reaction between red P and solar Si photovoltaic waste.The P nanoshell with thickness within 15 nm converts to Li3P during the initial lithiation process and maintains its phase on cycling.The as-formed Li3P nanolayer functions as a stable,ionically conductive protective layer that reduces the direct contact between Si and electrolytes,and thus suppresses undesired side reactions.The Si-P nanocomposite exhibits stable electrochemical cycling with a high reversible capacity of 1,178 mAh g^(−1)after 500 cycles at 1,200 mA g^(−1),as well as excellent rate capability(912 mAh g^(−1)at 2 C).With 15 wt%addition to graphite,a graphite/Si-P hybrid electrode shows a high overall reversible specific capacity of 447 mAh g^(−1)and 88.3%capacity retention after 100 cycles at high areal capacity of 2.64 mAh cm^(−2) at 100 mA g^(−1),indicating its promise as a drop-in anode in practical LIBs.展开更多
The application of all-solid-state Li-metal batteries with solid oxide electrolytes is hindered by interfacial issues,especially the solid electrolyte/Li-metal interface.This work introduced a uniform indium film laye...The application of all-solid-state Li-metal batteries with solid oxide electrolytes is hindered by interfacial issues,especially the solid electrolyte/Li-metal interface.This work introduced a uniform indium film layer on the surface of Na^(+)super ionic conductor(NASICON)solid electrolyte Li_(1.5)Al_(0.5)Ge_(1.5)P_(3)O_(12)(LAGP),which promotes the intimate contact between Li metal and solid electrolyte and hinders the side reactions at the interface.Electrochemical impedance spectra show that the battery with coated solid electrolyte presents a smaller interfacial resistance and maintains stability after a long cycling time.By contrast,the baseline battery with a pure LAGP pellet shows a contact loss after cycling with the vibration of interfacial impedance.The Li symmetric cells with indium-modified solid electrolyte present stable cycling behavior over 400 h at 0.1 and 0.2 mA·cm^(−2).The all-solid-state Li-metal batteries with a Li anode,indium coating LAGP and two kinds of cathodes,namely carbon nanotubes(CNTs)and LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811),are prepared and tested.The CNTs cathode for Li-O2 and Li-air batteries has a higher specific capacity than traditional Li-ion battery cathodes.The Li-NCM811 batteries deliver an initial Coulombic efficiency of about 75%,with 82%capacity retention after 20 cycles.展开更多
基金This work was supported by the National Natural Science Foundation of China(No.51802105)and Innovation Fund of Wuhan National Laboratory for Optoelectronics.E.M.acknowledges support from the Fundamental Research Funds for the Central Universities(HUST:2019JYCXJJ014).The authors would like to thank the Analytical and Testing Center of Huazhong University of Science and Technology as well as the Center for Nanoscale Characterization&Devices of Wuhan National Laboratory for Optoelectronics for providing the facilities to conduct the characterization.
文摘High-capacity lithium-containing alloy anodes(e.g.,Li4.4Si,Li4.4Sn,and Li3P)enable lithium-free cathodes(e.g.,Sulfur,V2O5,and FeF3)to produce next-generation lithium-ion batteries(LIBs)with high energy density.Herein,we design a Li3P/C nanocomposite with Li3P ultrafine nanodomains embedded in micrometer-scale porous carbon particles.Benefiting from the unique micro/nanostructure of the Li3P/C nanocomposite,electrons transfer rapidly through the conductive pathway provided by the porous carbon framework and the volume change between Li3P and P is confined in the nanopores of the carbon,which avoids the collapse of the whole Li3P/C composite particles.As expected,the as-achieved Li3P/C nanocomposite provided a high available lithium-ion capacity of 791 mAh/g(calculated based on the mass of Li3P/C)at 0.1 C during the initial delithiation process.Meanwhile,the Li3P/C nanocomposite showed 75%of its 0.5 C capacity at 6 C and stable cycling stability.
基金funding from the European Research Council under the European Union’s Seventh Framework Programme (FP/2007-2013)/ERC Grant Agreement no.[307161] of M.W.
文摘The high Li-ion conductivity of the Li7P3S11 sulfide-based solid electrolyte makes it a promising candidate for all-solid-state lithium batteries. The Li-ion transport over electrode-electrolyte and electrolyteelectrolyte interfaces, vital for the performance of solid-state batteries, is investigated by impedance spectroscopy and solid-state NMR experiments. An all-solid-state Li-ion battery is assembled with the Li7P3S11 electrolyte, nano-Li2S cathode and Li-In foil anode, showing a relatively large initial discharge capacity of 1139.5 m Ah/g at a current density of 0.064 m A/cm^ 2 retaining 850.0 m Ah/g after 30 cycles. Electrochemical impedance spectroscopy suggests that the decrease in capacity over cycling is due to the increased interfacial resistance between the electrode and the electrolyte. 1D exchange ^7Li NMR quantifies the interfacial Li-ion transport between the uncycled electrode and the electrolyte, resulting in a diffusion coefficient of 1.70(3) ×10^-14cm^2/s at 333 K and an energy barrier of 0.132 e V for the Li-ion transport between Li2S cathode and Li7P3S11 electrolyte. This indicates that the barrier for Li-ion transport over the electrode-electrolyte interface is small. However, the small diffusion coefficient for Li-ion diffusion between the Li2S and the Li7P3S11 suggests that these contact interfaces between electrode and electrolyte are relatively scarce, challenging the performance of these solid-state batteries.
基金Project(GuiJiaoRen[2007]71)supported by the Research Funds of the Guangxi Key Laboratory of Environmental Engineering,Protection and Assessment Program to Sponsor Teams for Innovation in the Construction of Talent Highlands in Guangxi Institutions of Higher Learning,China
文摘The effect of Al-substitution on the electrochemical performances of Li3V2(PO4)3 cathode materials was studied.Samples with stoichiometric proportion of Li3AlxV2-x(PO4)3(x=0,0.05,0.10)were prepared by adding Al(NO3)3 in the raw materials of Li3V2(PO4)3.The XRD analysis shows that the Al-substituted Li3V2(PO4)3 has the same monoclinic structure as the un-substituted Li3V2(PO4)3.The SEM images show that Al-substituted Li3V2(PO4)3 has regular and uniform particles.The electrochemical measurements show that Al-substitution can improve the rate capability of cathode materials.The Li3Al0.05V1.95(PO4)3 sample shows the best high-rate performance.The discharge capacity at 1C rate is 119 mA·h/g with 30th capacity retention rate about 92.97%.The electrode reaction reversibility and electronic conductivity are enhanced,and the charge transfer resistance decreases through Al-substitution.The improved electrochemical performances of Al-substituted Li3V2(PO4)3 cathode materials offer some favorable properties for their commercial application.
基金Y.S.acknowledges the financial support by National Natural Science Foundation of China(No.52272207)L.F.thanks the financial support by National Natural Science Foundation of China(No.22209031)+1 种基金Guizhou Provincial Basic Research Program(Natural Science)(No.QKHJC-ZK[2023]YB046)Natural Science Special Foundation of Guizhou University(No.X2022122 Special Post B).
文摘Achievement of lithium(Li)metal anode with thin thickness(e.g.,≤30µm)is highly desirable for rechargeable high energy density batteries.However,the fabrication and application of such thin Li metal foil electrode remain challenging due to the poor mechanical processibility and inferior electrochemical performance of metallic Li.Here,mechanico-chemical synthesis of robust ultrathin Li/Li_(3)P(LLP)composite foils(~15µm)is demonstrated by employing repeated mechanical rolling/stacking operations using red P and metallic Li as raw materials.The in-situ formed Li+-conductive Li_(3)P nanoparticles in metallic Li matrix and their tight bonding strengthen the mechanical durability and enable the successful fabrication of free-standing ultrathin Li metal composite foil.Besides,it also reduces the electrochemical Li nucleation barrier and homogenizes Li plating/stripping behavior.When matching to high-voltage LiCoO_(2),the full cell with a low negative/positive(N/P)capacity ratio of~1.5 offers a high energy density of~522 W·h·kg^(-1) at 0.5 C based on the mass of cathode and anode.Taking into account its facile manufacturing,potentially low cost,and good electrochemical performance,we believe that such an ultrathin composite Li metal foil design with nanoparticle-dispersion-strengthened mechanism may boost the development of high energy density Li metal batteries.
基金This work was supported by National Key R&D Program of China(2018YFB0905400)Major Technological Innovation Project of Hubei Science and Technology Department(2019AAA164)+2 种基金Y.S.acknowledges the financial support by the Innovation Fund of Wuhan National Laboratory for Optoelectronics of Huazhong University of Science and Technology.Z.W.S acknowledges the support of the Singapore National Research Foundation(NRF-NRFF2017-04)This work was also supported by the Ministry of Science and Technology of China(2019YFE0100200)the Tsinghua University Initiative Scientific Research Program(2019Z02UTY06).
文摘Silicon(Si)is a promising anode candidate for next-generation lithium-ion batteries(LIBs)due to its high theoretical capacity.Solar Si photovoltaic waste possesses good purity and high output.Using it as the raw material for battery anodes can synchronously solve the problem of solid waste pollution and enable high energy density LIBs.A critical issue impeding the practical application of Si is the undesirable side reactions at the electrolyte-particle interface and the resulting increase in impedance during cycling.Herein,a Si-P core shell structure with chemical bonding at the Si-P interface is fabricated through a simple mechanical alloying reaction between red P and solar Si photovoltaic waste.The P nanoshell with thickness within 15 nm converts to Li3P during the initial lithiation process and maintains its phase on cycling.The as-formed Li3P nanolayer functions as a stable,ionically conductive protective layer that reduces the direct contact between Si and electrolytes,and thus suppresses undesired side reactions.The Si-P nanocomposite exhibits stable electrochemical cycling with a high reversible capacity of 1,178 mAh g^(−1)after 500 cycles at 1,200 mA g^(−1),as well as excellent rate capability(912 mAh g^(−1)at 2 C).With 15 wt%addition to graphite,a graphite/Si-P hybrid electrode shows a high overall reversible specific capacity of 447 mAh g^(−1)and 88.3%capacity retention after 100 cycles at high areal capacity of 2.64 mAh cm^(−2) at 100 mA g^(−1),indicating its promise as a drop-in anode in practical LIBs.
文摘The application of all-solid-state Li-metal batteries with solid oxide electrolytes is hindered by interfacial issues,especially the solid electrolyte/Li-metal interface.This work introduced a uniform indium film layer on the surface of Na^(+)super ionic conductor(NASICON)solid electrolyte Li_(1.5)Al_(0.5)Ge_(1.5)P_(3)O_(12)(LAGP),which promotes the intimate contact between Li metal and solid electrolyte and hinders the side reactions at the interface.Electrochemical impedance spectra show that the battery with coated solid electrolyte presents a smaller interfacial resistance and maintains stability after a long cycling time.By contrast,the baseline battery with a pure LAGP pellet shows a contact loss after cycling with the vibration of interfacial impedance.The Li symmetric cells with indium-modified solid electrolyte present stable cycling behavior over 400 h at 0.1 and 0.2 mA·cm^(−2).The all-solid-state Li-metal batteries with a Li anode,indium coating LAGP and two kinds of cathodes,namely carbon nanotubes(CNTs)and LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811),are prepared and tested.The CNTs cathode for Li-O2 and Li-air batteries has a higher specific capacity than traditional Li-ion battery cathodes.The Li-NCM811 batteries deliver an initial Coulombic efficiency of about 75%,with 82%capacity retention after 20 cycles.
