Despite the dazzling theoretical capacity,the devasting electrochemical activity of Li_(2)MnO_(3)(LMO)caused by the difficult oxidation of Mn4+impedes its practical application as the lithium-ion battery(LIB)cathode.T...Despite the dazzling theoretical capacity,the devasting electrochemical activity of Li_(2)MnO_(3)(LMO)caused by the difficult oxidation of Mn4+impedes its practical application as the lithium-ion battery(LIB)cathode.The efficacious activation of the Li_(2)MnO_(3) by importing electrochemically active Mn3+ions or morphological engineering is instrumental to its lithium storage activity and structural integrity upon cycling.Herein,we propose a conceptual strategy with metal-organic frameworks(MOFs)as self-sacrificial templates to prepare oxygen-deficient Li_(2)MnO_(3)(O_v-LMO)for exalted lithium storage performance.Attributed to optimized morphological features,LMO materials derived from Mn-BDC(H_(2)BDC=1,4-dicarboxybenzene)delivered superior cycling/rate performances compared with their counterparts derived from Mn-BTC(H_(3)BTC=1,3,5-benzenetricarboxylicacid)and Mn-PTC(H_(4)PTC=pyromellitic acid).Both experimental and theoretical studies elucidate the efficacious activation of primitive LMO materials toward advanced lithium storage by importing oxygen deficiencies.Impressively,O_v-LMO derived from Mn-BDC(O_v-BDC-LMO)delivered intriguing reversible capacities(179.2 mA h g^(-1)at 20 mA g^(-1)after 200 cycles and 100.1 mA h g^(-1)at 80 mA g^(-1)after 300 cycles),which can be attributed to the small particle size that shortens pathways for Li+/electron transport,the enhanced redox activity induced by abundant oxygen vacancies,and the optimized electronic configuration that contributes to the faster lithium diffusivity.This work provides insights into the rational design of LMO by morphological and atomic modulation to direct its activation and practical application as an advanced LIB cathode.展开更多
Some special fields,such as deep-sea exploration,require batteries and their electrode materials to withstand extremely high pressure.As the cathode material has the highest energy density,Li-excess Mn-based materials...Some special fields,such as deep-sea exploration,require batteries and their electrode materials to withstand extremely high pressure.As the cathode material has the highest energy density,Li-excess Mn-based materials are also likely to be utilized in such an environment.However,the effect of pressure on the crystal structure and migration barrier of this kind of material is still not clear at present.Therefore,in this study,we investigate the properties of the matrix material of Li-excess Mn-based material,Li_(2)MnO_(3),under high pressure.The equation of state,bulk modulus,and steady-state volume of Li_(2)MnO_(3) are predicted by the method of first principles calculation.The calculations of unit cells at different pressures reveal that the cell parameters suffer anisotropic compression under high pressure.During compression,Li-O bond is more easily compressed than Mn-O bond.The results from the climbing image nudged elastic band(CINEB)method show that the energy barrier of Li^(+)migration in the lithium layer increases with pressure increasing.Our study can provide useful information for utilizing Li-excess Mn-based materials under high pressure.展开更多
Ni-rich layered cathodes(LiNi_xCo_yMn_(2)O_(2))have recently drawn much attention due to their high specific capacities.However,the poor rate capability of LiNi_xCo_yMn_(2)O_(2),which is mainly originated from the two...Ni-rich layered cathodes(LiNi_xCo_yMn_(2)O_(2))have recently drawn much attention due to their high specific capacities.However,the poor rate capability of LiNi_xCo_yMn_(2)O_(2),which is mainly originated from the twodimensional diffusion of Li ions in the Li slab and Li^(+)/Ni^(2+)cation mixing that hinder the Li^(+)diffusion,has limited their practical application where high power density is needed.Here we integrated Li_(2)MnO_(3)nanodomains into the layered structure of a typical Ni-rich LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)material,which minimized the Li^(+)/Ni^(2+)cationic disordering,and more importantly,established grain boundaries within the NCM811 matrix,thus providing a three-dimensional diffusion channel for Li ions.Accordingly,an average Li-ion diffusion coefficient(D_(Li+))of the Li_(2)MnO_(3)-integrated LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811-I)during charge/discharge was calculated to be approximately 6*10^(-10)cm~2 S^(-1),two times of that in the bare NCM811(3*10^(-10)cm~2 S^(-1)).The capacity delivered by the NCM811-I(154.5 mAh g^(-1))was higher than that of NCM811(141.3 mAh g^(-1))at 2 C,and the capacity retention of NCM811-I increased by 13.6%after100 cycles at 0.1 C and 13.4%after 500 cycles at 1 C compared to NCM811.This work provides a valuable routine to improve the rate capability of Ni-rich cathode materials,which may be applied to other oxide cathodes with sluggish Li-ion transportation.展开更多
Though oxygen defects are associated with deteriorated structures and aggravated cycling performance in traditional layered cathodes,the role of oxygen defects is still ambiguous in Li-rich layered oxides due to the i...Though oxygen defects are associated with deteriorated structures and aggravated cycling performance in traditional layered cathodes,the role of oxygen defects is still ambiguous in Li-rich layered oxides due to the involvement of oxygen redox.Herein,a Co-free Li-rich layered oxide Li_(1.286)Ni_(0.071)Mn_(0.643)O_(2)has been prepared by a co-precipitation method to systematically investigate the undefined effects of the oxygen defects.A significant O_(2)release and the propagation of oxygen vacancies were detected by operando differential electrochemical mass spectroscopy(DEMS)and electron energy loss spectroscopy(EELS),respectively.Scanning transmission electron microscopy-high angle annular dark field(STEMHAADF)reveals the oxygen vacancies fusing to nanovoids and monitors a stepwise electrochemical activation process of the large Li_(2)MnO_(3)domain upon cycling.Combined with the quantitative analysis conducted by the energy dispersive spectrometer(EDS),existed nano-scale oxygen defects actually expose more surface to the electrolyte for facilitating the electrochemical activation and subsequently increasing available capacity.Overall,this work persuasively elucidates the function of oxygen defects on oxygen redox in Co-free Li-rich layered oxides.展开更多
Cobalt-free Li-rich layered oxides(LLOs)such as Li_(2)MnO_(3) have attracted extensive attention owing to their high specific capacity and low cost.Nonetheless,numerous problems such as continuous voltage fading and c...Cobalt-free Li-rich layered oxides(LLOs)such as Li_(2)MnO_(3) have attracted extensive attention owing to their high specific capacity and low cost.Nonetheless,numerous problems such as continuous voltage fading and capacity decay have become stumbling blocks in its commercial application.In this study,we propose an effective dual-site doping strategy by choosing Mo as the cation and F as the anion to enhance the capacity and cycling performance.The researchdemonstrates that the cycling stability of LLOs enhances with the doping ratio of Mo,and their capacity increases with the doping ratio of F.It is because Mo as a pillar enhances the structural stability and F doping is conducive to the activation of Li;MnO;.What’s more,dual-site doping also promotes the diffusion of Li;and reduces the internal resistance of the electrode.Due to these improvements,the 5F3M sample still maintains a discharge capacity of 190.98 mAh g;after 100 cycles at 200 mA g^(-1),which is much higher than 165.29 mAh g;of the Pristine sample.This discovery provides a new way to develop advanced layered oxide cathodes for both Na-and Li-ion batteries.展开更多
基金the financial support from the Special Funds for the Cultivation of Guangdong College Students’Scientific and Technological Innovation(“Climbing Program”Special Funds,pdjh2023b0145)the Research and Development Plan Project in Key Fields of Guangdong Province(2020B0101030005)+1 种基金the Applied special project of Guangdong Provincial Science and Technology Plan(2017B090917002)the Basic and Applied Basic Research Fund of Guangdong Province(2019B1515120027)。
文摘Despite the dazzling theoretical capacity,the devasting electrochemical activity of Li_(2)MnO_(3)(LMO)caused by the difficult oxidation of Mn4+impedes its practical application as the lithium-ion battery(LIB)cathode.The efficacious activation of the Li_(2)MnO_(3) by importing electrochemically active Mn3+ions or morphological engineering is instrumental to its lithium storage activity and structural integrity upon cycling.Herein,we propose a conceptual strategy with metal-organic frameworks(MOFs)as self-sacrificial templates to prepare oxygen-deficient Li_(2)MnO_(3)(O_v-LMO)for exalted lithium storage performance.Attributed to optimized morphological features,LMO materials derived from Mn-BDC(H_(2)BDC=1,4-dicarboxybenzene)delivered superior cycling/rate performances compared with their counterparts derived from Mn-BTC(H_(3)BTC=1,3,5-benzenetricarboxylicacid)and Mn-PTC(H_(4)PTC=pyromellitic acid).Both experimental and theoretical studies elucidate the efficacious activation of primitive LMO materials toward advanced lithium storage by importing oxygen deficiencies.Impressively,O_v-LMO derived from Mn-BDC(O_v-BDC-LMO)delivered intriguing reversible capacities(179.2 mA h g^(-1)at 20 mA g^(-1)after 200 cycles and 100.1 mA h g^(-1)at 80 mA g^(-1)after 300 cycles),which can be attributed to the small particle size that shortens pathways for Li+/electron transport,the enhanced redox activity induced by abundant oxygen vacancies,and the optimized electronic configuration that contributes to the faster lithium diffusivity.This work provides insights into the rational design of LMO by morphological and atomic modulation to direct its activation and practical application as an advanced LIB cathode.
基金Project supported by the Research on High Power Flexible Battery in All Sea Depth,China (Grant No.2020-XXXXXX-246-00)。
文摘Some special fields,such as deep-sea exploration,require batteries and their electrode materials to withstand extremely high pressure.As the cathode material has the highest energy density,Li-excess Mn-based materials are also likely to be utilized in such an environment.However,the effect of pressure on the crystal structure and migration barrier of this kind of material is still not clear at present.Therefore,in this study,we investigate the properties of the matrix material of Li-excess Mn-based material,Li_(2)MnO_(3),under high pressure.The equation of state,bulk modulus,and steady-state volume of Li_(2)MnO_(3) are predicted by the method of first principles calculation.The calculations of unit cells at different pressures reveal that the cell parameters suffer anisotropic compression under high pressure.During compression,Li-O bond is more easily compressed than Mn-O bond.The results from the climbing image nudged elastic band(CINEB)method show that the energy barrier of Li^(+)migration in the lithium layer increases with pressure increasing.Our study can provide useful information for utilizing Li-excess Mn-based materials under high pressure.
基金supported by the Ministry of Science and Technology of the People’s Republic of China(2016YFA0202500)the National Natural Science Foundation of China(52072185)+1 种基金the 111 project(B12015)the National Natural Science Foundation of China(21703147 and U1401248)。
文摘Ni-rich layered cathodes(LiNi_xCo_yMn_(2)O_(2))have recently drawn much attention due to their high specific capacities.However,the poor rate capability of LiNi_xCo_yMn_(2)O_(2),which is mainly originated from the twodimensional diffusion of Li ions in the Li slab and Li^(+)/Ni^(2+)cation mixing that hinder the Li^(+)diffusion,has limited their practical application where high power density is needed.Here we integrated Li_(2)MnO_(3)nanodomains into the layered structure of a typical Ni-rich LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)material,which minimized the Li^(+)/Ni^(2+)cationic disordering,and more importantly,established grain boundaries within the NCM811 matrix,thus providing a three-dimensional diffusion channel for Li ions.Accordingly,an average Li-ion diffusion coefficient(D_(Li+))of the Li_(2)MnO_(3)-integrated LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811-I)during charge/discharge was calculated to be approximately 6*10^(-10)cm~2 S^(-1),two times of that in the bare NCM811(3*10^(-10)cm~2 S^(-1)).The capacity delivered by the NCM811-I(154.5 mAh g^(-1))was higher than that of NCM811(141.3 mAh g^(-1))at 2 C,and the capacity retention of NCM811-I increased by 13.6%after100 cycles at 0.1 C and 13.4%after 500 cycles at 1 C compared to NCM811.This work provides a valuable routine to improve the rate capability of Ni-rich cathode materials,which may be applied to other oxide cathodes with sluggish Li-ion transportation.
基金supported by the National Natural Science Foundation of China(52272253)the"Lingyan"Research and Development Plan of Zhejiang Province(2022C01071)+2 种基金the S&T Innovation 2025 Major Special Programme of Ningbo(2018B10081)the Natural Science Foundation of Ningbo(202003N4030)the Youth Innovation Promotion Association of Chinese Academy of Sciences(2022299)。
文摘Though oxygen defects are associated with deteriorated structures and aggravated cycling performance in traditional layered cathodes,the role of oxygen defects is still ambiguous in Li-rich layered oxides due to the involvement of oxygen redox.Herein,a Co-free Li-rich layered oxide Li_(1.286)Ni_(0.071)Mn_(0.643)O_(2)has been prepared by a co-precipitation method to systematically investigate the undefined effects of the oxygen defects.A significant O_(2)release and the propagation of oxygen vacancies were detected by operando differential electrochemical mass spectroscopy(DEMS)and electron energy loss spectroscopy(EELS),respectively.Scanning transmission electron microscopy-high angle annular dark field(STEMHAADF)reveals the oxygen vacancies fusing to nanovoids and monitors a stepwise electrochemical activation process of the large Li_(2)MnO_(3)domain upon cycling.Combined with the quantitative analysis conducted by the energy dispersive spectrometer(EDS),existed nano-scale oxygen defects actually expose more surface to the electrolyte for facilitating the electrochemical activation and subsequently increasing available capacity.Overall,this work persuasively elucidates the function of oxygen defects on oxygen redox in Co-free Li-rich layered oxides.
基金financially supported by the National Natural Science Foundation of China(52004070 and 51874104)the National Key R&D Program of China(2011YFB0700600)。
文摘Cobalt-free Li-rich layered oxides(LLOs)such as Li_(2)MnO_(3) have attracted extensive attention owing to their high specific capacity and low cost.Nonetheless,numerous problems such as continuous voltage fading and capacity decay have become stumbling blocks in its commercial application.In this study,we propose an effective dual-site doping strategy by choosing Mo as the cation and F as the anion to enhance the capacity and cycling performance.The researchdemonstrates that the cycling stability of LLOs enhances with the doping ratio of Mo,and their capacity increases with the doping ratio of F.It is because Mo as a pillar enhances the structural stability and F doping is conducive to the activation of Li;MnO;.What’s more,dual-site doping also promotes the diffusion of Li;and reduces the internal resistance of the electrode.Due to these improvements,the 5F3M sample still maintains a discharge capacity of 190.98 mAh g;after 100 cycles at 200 mA g^(-1),which is much higher than 165.29 mAh g;of the Pristine sample.This discovery provides a new way to develop advanced layered oxide cathodes for both Na-and Li-ion batteries.
