Chloride solid electrolytes possess multiple advantages for the construction of safe,energy-dense allsolid-state sodium batteries,but presently the chlorides with sufficiently high cost-competitiveness for commerciali...Chloride solid electrolytes possess multiple advantages for the construction of safe,energy-dense allsolid-state sodium batteries,but presently the chlorides with sufficiently high cost-competitiveness for commercialization almost all exhibit low Na-ion conductivities of around 10^(-5)S cm^(-1)or lower.Here,we report a chloride solid electrolyte,Na_(2.7)ZFCl_(5.3)O_(0.7),which reaches a Na-ion conductivity of 2.29×10^(-4)S cm^(-1)at 25℃without involving overly expensive raw materials such as rare-earth chlorides or Na_(2)S.In addition to the efficient ion transport,Na_(2.7)ZrCl_(5.3)O_(0.7)also shows an excellent deformability surpassing that of the widely studied Na_(3)PS_(4),Na_(3)SbS_(4),and Na_(2)ZrCl_(6)solid electrolytes.The combination of these advantages allows the all-solid-state cell based on Na_(2.7)ZrCl_(5.3)O_(0.7)and NaCrO_(2)to realize stable room-temperature cycling at a much higher specific current than those based on other non-viscoelastic chloride solid electrolytes in literature(120 mA g^(-1)vs.12-55 mA g^(-1));after 100 cycles at such a high rate,the Na_(2.7)ZFCl_(5.3)O_(0.7)-based cell can still deliver a discharge capacity of 80 mAh g^(-1)at25℃.展开更多
Augmenting the working voltage is an effective way to maximize the energy density of Ni-rich layered Li[Ni_(0.8)Co_(0.1)Mn_(0.1)]O_(2)(NCM)to approach its theoretical capacity.However,NCM suffers from structural degra...Augmenting the working voltage is an effective way to maximize the energy density of Ni-rich layered Li[Ni_(0.8)Co_(0.1)Mn_(0.1)]O_(2)(NCM)to approach its theoretical capacity.However,NCM suffers from structural degradation in deep delithiation state,which is often accompanied by severe surface lattice oxygen loss and transition metal dissolution,leading to restricted cycle life.Herein,a facile and effective surfacestrengthening strategy is proposed,in which Mn(OH)_(2)nanoshells are uniformly grown on the NCM surface as a Li~+capturer and then converted to thin spinel Li_(4)Mn_5O_(12)layers during subsequent hightemperature sintering.The resultant Li_(4)Mn_5O_(12)layers can enhance cathode-electrolyte interface electrochemical stability with inhibited electrolyte corrosion and accelerated Li~+kinetics.The theoretical calculations confirms that the Mn-O bonds formed at the interfaces can effectively decrease the oxygen activity,thereby further inhibiting the lattice oxygen release and structural degradation caused by the irreversible phase transition.Consequently,the Li_(4)Mn_5O_(12)-coated NCM displays high capacity retention of 80.3%and 94.9%at 1 C and 5 C compared to the pristine NCM(52.5%and 10.1%)after 200 cycles and can operate stably at 2.7-4.6 V and 60℃.The spinel Li_(4)Mn_5O_(12)-coating demonstrates an effective route to enhance the structural/electrochemical stability of NCM for next-generation advanced lithium-ion batteries.展开更多
基金the financial support from the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0450201)the National Key R&D Program of China(2018YFA0209600)+2 种基金USTC Research Funds of the Double FirstClass Initiative(YD2060002033)the Fundamental Research Funds for the Central Universities(WK2060000060)the National Synchrotron Radiation Laboratory(KY2060000199)。
文摘Chloride solid electrolytes possess multiple advantages for the construction of safe,energy-dense allsolid-state sodium batteries,but presently the chlorides with sufficiently high cost-competitiveness for commercialization almost all exhibit low Na-ion conductivities of around 10^(-5)S cm^(-1)or lower.Here,we report a chloride solid electrolyte,Na_(2.7)ZFCl_(5.3)O_(0.7),which reaches a Na-ion conductivity of 2.29×10^(-4)S cm^(-1)at 25℃without involving overly expensive raw materials such as rare-earth chlorides or Na_(2)S.In addition to the efficient ion transport,Na_(2.7)ZrCl_(5.3)O_(0.7)also shows an excellent deformability surpassing that of the widely studied Na_(3)PS_(4),Na_(3)SbS_(4),and Na_(2)ZrCl_(6)solid electrolytes.The combination of these advantages allows the all-solid-state cell based on Na_(2.7)ZrCl_(5.3)O_(0.7)and NaCrO_(2)to realize stable room-temperature cycling at a much higher specific current than those based on other non-viscoelastic chloride solid electrolytes in literature(120 mA g^(-1)vs.12-55 mA g^(-1));after 100 cycles at such a high rate,the Na_(2.7)ZFCl_(5.3)O_(0.7)-based cell can still deliver a discharge capacity of 80 mAh g^(-1)at25℃.
基金financial support from the Key Research and Development Project in Shaanxi Province(2023-YBGY-446)the Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering(No.2022SX-TD003)+1 种基金the Natural Science Basic Research Program of Shaanxi(No.2024JC-YBQN-0108)the Key Laboratory of Interface Science and Engineering in Advanced Materials,Ministry of Education(KLISEAM202202)。
文摘Augmenting the working voltage is an effective way to maximize the energy density of Ni-rich layered Li[Ni_(0.8)Co_(0.1)Mn_(0.1)]O_(2)(NCM)to approach its theoretical capacity.However,NCM suffers from structural degradation in deep delithiation state,which is often accompanied by severe surface lattice oxygen loss and transition metal dissolution,leading to restricted cycle life.Herein,a facile and effective surfacestrengthening strategy is proposed,in which Mn(OH)_(2)nanoshells are uniformly grown on the NCM surface as a Li~+capturer and then converted to thin spinel Li_(4)Mn_5O_(12)layers during subsequent hightemperature sintering.The resultant Li_(4)Mn_5O_(12)layers can enhance cathode-electrolyte interface electrochemical stability with inhibited electrolyte corrosion and accelerated Li~+kinetics.The theoretical calculations confirms that the Mn-O bonds formed at the interfaces can effectively decrease the oxygen activity,thereby further inhibiting the lattice oxygen release and structural degradation caused by the irreversible phase transition.Consequently,the Li_(4)Mn_5O_(12)-coated NCM displays high capacity retention of 80.3%and 94.9%at 1 C and 5 C compared to the pristine NCM(52.5%and 10.1%)after 200 cycles and can operate stably at 2.7-4.6 V and 60℃.The spinel Li_(4)Mn_5O_(12)-coating demonstrates an effective route to enhance the structural/electrochemical stability of NCM for next-generation advanced lithium-ion batteries.
