Improving the reversibility of anionic redox and inhibiting irreversible oxygen evolution are the main challenges in the application of high reversible capacity Li-rich Mn-based cathode materials.A facile synchronous ...Improving the reversibility of anionic redox and inhibiting irreversible oxygen evolution are the main challenges in the application of high reversible capacity Li-rich Mn-based cathode materials.A facile synchronous lithiation strategy combining the advantages of yttrium doping and LiYO_(2) surface coating is proposed.Yttrium doping effectively suppresses the oxygen evolution during the delithiation process by increasing the energy barrier of oxygen evolution reaction through strong Y–O bond energy.LiYO_(2) nanocoating has the function of structural constraint and protection,that protecting the lattice oxygen exposed to the surface,thus avoiding irreversible oxidation.As an Li^(+) conductor,LiYO_(2) nano-coating can provide a fast Li^(+) transfer channel,which enables the sample to have excellent rate performance.The synergistic effect of Y doping and nano-LiYO_(2) coating integration suppresses the oxygen release from the surface,accelerates the diffusion of Li^(+)from electrolyte to electrode and decreases the interfacial side reactions,enabling the lithium ion batteries to obtain good electrochemical performance.The lithium-ion full cell employing the Y-1 sample(cathode)and commercial graphite(anode)exhibit an excellent specific energy density of 442.9 Wh kg^(-1) at a current density of 0.1C,with very stable safety performance,which can be used in a wide temperature range(60 to-15℃)stable operation.This result illustrates a new integration strategy for advanced cathode materials to achieve high specific energy density.展开更多
Iron-substituted cobalt-free lithium-rich manganese-based materials,with advantages of high specific capacity,high safety,and low cost,have been considered as the potential cathodes for lithium ion batteries.However,c...Iron-substituted cobalt-free lithium-rich manganese-based materials,with advantages of high specific capacity,high safety,and low cost,have been considered as the potential cathodes for lithium ion batteries.However,challenges,such as poor cycle stability and fast voltage fade during cycling under high potential,hinder these materials from commercialization.Here,we developed a method to directly coat LiF on the particle surface of Li_(1.2)Ni_(0.15)Fe_(0.1)Mn_(0.55O2).A uniform and flat film was successfully formed with a thickness about 3 nm,which can effect-ively protect the cathode material from irreversible phase transition during the deintercalation of Li^(+).After surface coating with 0.5wt%LiF,the cycling stability of Li_(1.2)Ni_(0.15)Fe_(0.1)Mn_(0.55O2) cycled at high potential was significantly improved and the voltage fade was largely suppressed.展开更多
Lithium-rich oxide compounds have been recognized as promising cathode materials for high performance Li-ion batteries,owing to their high specific capacity.However,it remains a great challenge to achieve the fully re...Lithium-rich oxide compounds have been recognized as promising cathode materials for high performance Li-ion batteries,owing to their high specific capacity.However,it remains a great challenge to achieve the fully reversible anionic redox reactions to realize high capacity,high stability,and low voltage hysteresis for lithiumrich cathode materials.Therefore,it is critically important to comprehensively understand and control the anionic redox chemistry of lithium-rich cathode materials,including atomic structure design,and nano-scale materials engineering technologies.Herein,we summarize the recent research progress of lithium-rich cathode materials with a focus on redox chemistry.Particularly,we highlight the oxygen-based redox reactions in lithium-rich metal oxides,with critical views of designing next generation oxygen redox lithium cathode materials.Furthermore,we purposed the most promising strategies for improving the performances of lithium-rich cathode materials with a technology-spectrum from the atomic scale to nano-scale.展开更多
Lithium-rich oxide is one of the most promising cathodes that meet high energy density requirement for batteries of the future, but its phase transformation from layer to spinel structure caused by the lattice instabi...Lithium-rich oxide is one of the most promising cathodes that meet high energy density requirement for batteries of the future, but its phase transformation from layer to spinel structure caused by the lattice instability presents severe challenge to cycling stability and the actually accessible capacity. The currently available approaches to suppress this undesired irreversible process often resort to limit the high voltages that lithium-rich oxide is exposed to. However, cycling stability thus improved is at the expense of the eventual energy output. In this work, we identified a new mechanism that is directly responsible for the lithium-rich oxide phase transformation and established a clear correlation between the successive consumption of Li+on anode due to incessant interphase repairing and the over-delithiation of lithium-rich oxide cathode. This new mechanism enables a simple but effective solution to the cathode degradation, in which an electrolyte additive is used to build a dense and protective interphase on anode with the intention to minimize Li depletion at cathode. The application of this new interphase effectively suppresses both electrolyte decomposition at anode and the phase transformation of lithium-rich oxide cathode, leading to high capacity and cycling stability.展开更多
Lithium-rich materials possess the ultra-high specific capacity,but the redox of oxygen is not completely reversible,resulting in voltage attenuation and structural instability.A stepwise co-precipitation method is us...Lithium-rich materials possess the ultra-high specific capacity,but the redox of oxygen is not completely reversible,resulting in voltage attenuation and structural instability.A stepwise co-precipitation method is used for the first time in this paper to achieve the control of the two-phase distribution through controlling the distribution of transition metal elements and realize the modification of particle surface structure without the aid of heterologous ions.The results of characterization tests show that the content of LiMO_(2) phase inside the particles and the content of Li_(2)MnO_(3) phase on the surface of the particles are successfully increased,and the surface induced formation of Li_(4)Mn_(5)O_(12) spinel phase or some disorderly ternary.The electrochemical performance of the modified sample is as follows:LR(pristine)shows specific discharge capacity of 72.7 mA·h·g^(−1)after 500 cycles at 1 C,while GR(modified sample)shows specific discharge capacity of 137.5 mA·h·g^(−1) at 1 C,and the discharge mid-voltage of GR still remains above 3 V when cycling to 220 cycles at 1 C(mid-voltage of LR remains above 3 V when cycling to 160 cycles at 1 C).Therefore,deliberately regulating the local state of the two phases is a successful way to reinforced the material structure and inhibition the voltage attenuation.展开更多
The felsic volcanogenic tuffs named"green-bean rocks"(GBRs),characterized by a green or yellowish green color,are widely distributed in the western Yangtze platform and have a high lithium content(286-957 pp...The felsic volcanogenic tuffs named"green-bean rocks"(GBRs),characterized by a green or yellowish green color,are widely distributed in the western Yangtze platform and have a high lithium content(286-957 ppm).This paper studies the ages,origin and tectonic setting of the GBRs in the Sichuan basin on the western margin of the Yangtze platform through the whole-rock geochemistry and zircon trace elements by using U-Pb dating and Hf-O isotopes.The GBR samples from the Quxian and Beibei sections yielded zircon U-Pb ages of 245.5±1.8 Ma and 244.8±2.2 Ma.These samples can be used as the isochronous stratigraphic marker of the Early-Middle Triassic boundary(EMTB)for regional correlation.The whole-rock and zircon geochemistry,and zircon Hf-O isotopes exhibited S-type geochemical affinities with high positiveδ^(18)0 values(9.28‰-11.98‰),low negativeε_(Hf)(t)values(-13.87 to-6.79),and T_(DM)^(2)ages of 2150-1703 Ma,indicating that the lithium-rich GBRs were generated by the remelting of the pre-existing ancient Paleoproterozoic layer without mantle source contamination in the arcrelated/orogenic tectonic setting.The results of this study demonstrate that the lithium-rich GBRs in the western Yangtze platform were derived from arc volcanic eruptions along the Sanjiang orogen,triggered by the closure of the eastern Paleo-Tethys Ocean and the syn-collision between the continental Indochina and Yangtze blocks at ca.247 Ma.This was marked by a major shift from I-type magmas with intermediateε_(Hf)(t)values to S-type magmas with low negativeε_(Hf)(t)values.Collectively,our results provide new insights into the origin of the GBRs and decodes the closure of the eastern Paleo-Tethys.展开更多
Lithium-ion batteries are considered a promising energy storage technology in portable electronics and electric vehicles due to their high energy density,competitive cost,and environmental friendliness.Improving catho...Lithium-ion batteries are considered a promising energy storage technology in portable electronics and electric vehicles due to their high energy density,competitive cost,and environmental friendliness.Improving cathode materials is an effective way to meet the demand for better batteries,of which the utilization of high-voltage cathode materials is an important development trend.In recent years,lithium-rich layered oxides have gained great attention due to their desirable energy density.This review presents the relationships between lattice structure and electrochemical properties,the underlying degradation mechanisms,and corresponding modification strategies.The recent progress and strategies are then highlighted,including element doping,surface coating,morphology design,size control,etc.Finally,a concise perspective for future developments and practical applications of lithium-rich layered oxides has been provided.展开更多
Lithium-rich cathode oxides with capability to realize multivalent cationic and anionic redox reactions have attracted much attention as promising candidate electrode materials for high energy density lithium ion batt...Lithium-rich cathode oxides with capability to realize multivalent cationic and anionic redox reactions have attracted much attention as promising candidate electrode materials for high energy density lithium ion batteries because of their ultrahigh specific capacity. However, redox reaction mechanisms, especially for the anionic redox reaction of these materials, are still not very clear. Meanwhile, several pivotal challenges associated with the redox reactions mechanisms, such as structural instability and limited cycle life, hinder the practical applications of these high-capacity lithium-rich cathode oxides. Herein, we review the lithium-rich oxides with various crystal structures. The multivalent cationic/anionic redox reaction mechanisms of several representative high capacity lithium-rich cathode oxides are discussed, attempting to understand the origins of the high lithium storage capacities of these materials. In addition, we provide perspectives for the further development of these lithium-rich cathode oxides based on multivalent cationic and anionic redox reactions, focusing on addressing the fundamental problems and promoting their practical applications.展开更多
The voltage decay of lithium-rich layered oxides(LLOs)is still one of the key challenges for their application in commercial battery although these materials possess the advantages of high specific capacity and low co...The voltage decay of lithium-rich layered oxides(LLOs)is still one of the key challenges for their application in commercial battery although these materials possess the advantages of high specific capacity and low cost.In this work,the relationship between voltage decay and tap density of LLOs has been focused.The voltage decay can be significantly suppressed with the increasing tap density as well as the homogenization of the primary or secondary particle size of agglomerated spherical LLOs.Experimental results have shown that an extreme small voltage decay of 0.98 m V cycle^(-1)can be obtained through adjusting the tap density of agglomerated spherical LLOs to 1.99 g cm^(-3),in which the size of primary and secondary particles are uniform.Our work offers a new insight towards the voltage decay and capacity fading of LLOs through precursor preparation process,promoting their application in the real battery in the future.展开更多
基金This work was supported by the Fundamental Research Funds for the Central Universities(DUT20LAB123 and DUT20LAB307)the Natural Science Foundation of Jiangsu Province(BK20191167).
文摘Improving the reversibility of anionic redox and inhibiting irreversible oxygen evolution are the main challenges in the application of high reversible capacity Li-rich Mn-based cathode materials.A facile synchronous lithiation strategy combining the advantages of yttrium doping and LiYO_(2) surface coating is proposed.Yttrium doping effectively suppresses the oxygen evolution during the delithiation process by increasing the energy barrier of oxygen evolution reaction through strong Y–O bond energy.LiYO_(2) nanocoating has the function of structural constraint and protection,that protecting the lattice oxygen exposed to the surface,thus avoiding irreversible oxidation.As an Li^(+) conductor,LiYO_(2) nano-coating can provide a fast Li^(+) transfer channel,which enables the sample to have excellent rate performance.The synergistic effect of Y doping and nano-LiYO_(2) coating integration suppresses the oxygen release from the surface,accelerates the diffusion of Li^(+)from electrolyte to electrode and decreases the interfacial side reactions,enabling the lithium ion batteries to obtain good electrochemical performance.The lithium-ion full cell employing the Y-1 sample(cathode)and commercial graphite(anode)exhibit an excellent specific energy density of 442.9 Wh kg^(-1) at a current density of 0.1C,with very stable safety performance,which can be used in a wide temperature range(60 to-15℃)stable operation.This result illustrates a new integration strategy for advanced cathode materials to achieve high specific energy density.
基金financially supported by the project of International Science&Technology Cooperation of China(No.2019YFE0100200)。
文摘Iron-substituted cobalt-free lithium-rich manganese-based materials,with advantages of high specific capacity,high safety,and low cost,have been considered as the potential cathodes for lithium ion batteries.However,challenges,such as poor cycle stability and fast voltage fade during cycling under high potential,hinder these materials from commercialization.Here,we developed a method to directly coat LiF on the particle surface of Li_(1.2)Ni_(0.15)Fe_(0.1)Mn_(0.55O2).A uniform and flat film was successfully formed with a thickness about 3 nm,which can effect-ively protect the cathode material from irreversible phase transition during the deintercalation of Li^(+).After surface coating with 0.5wt%LiF,the cycling stability of Li_(1.2)Ni_(0.15)Fe_(0.1)Mn_(0.55O2) cycled at high potential was significantly improved and the voltage fade was largely suppressed.
基金financial support by the Australian Research Council(ARC)Discovery Project(DP200101249)。
文摘Lithium-rich oxide compounds have been recognized as promising cathode materials for high performance Li-ion batteries,owing to their high specific capacity.However,it remains a great challenge to achieve the fully reversible anionic redox reactions to realize high capacity,high stability,and low voltage hysteresis for lithiumrich cathode materials.Therefore,it is critically important to comprehensively understand and control the anionic redox chemistry of lithium-rich cathode materials,including atomic structure design,and nano-scale materials engineering technologies.Herein,we summarize the recent research progress of lithium-rich cathode materials with a focus on redox chemistry.Particularly,we highlight the oxygen-based redox reactions in lithium-rich metal oxides,with critical views of designing next generation oxygen redox lithium cathode materials.Furthermore,we purposed the most promising strategies for improving the performances of lithium-rich cathode materials with a technology-spectrum from the atomic scale to nano-scale.
基金supported by the National Natural Science Foundation of China(Grant No.21872058)the Key Project of Science and Technology in Guangdong Province(2017A010106006)
文摘Lithium-rich oxide is one of the most promising cathodes that meet high energy density requirement for batteries of the future, but its phase transformation from layer to spinel structure caused by the lattice instability presents severe challenge to cycling stability and the actually accessible capacity. The currently available approaches to suppress this undesired irreversible process often resort to limit the high voltages that lithium-rich oxide is exposed to. However, cycling stability thus improved is at the expense of the eventual energy output. In this work, we identified a new mechanism that is directly responsible for the lithium-rich oxide phase transformation and established a clear correlation between the successive consumption of Li+on anode due to incessant interphase repairing and the over-delithiation of lithium-rich oxide cathode. This new mechanism enables a simple but effective solution to the cathode degradation, in which an electrolyte additive is used to build a dense and protective interphase on anode with the intention to minimize Li depletion at cathode. The application of this new interphase effectively suppresses both electrolyte decomposition at anode and the phase transformation of lithium-rich oxide cathode, leading to high capacity and cycling stability.
基金financially supported by the National Natural Science Foundation of China (Nos. 51972023 and 51572024)
文摘Lithium-rich materials possess the ultra-high specific capacity,but the redox of oxygen is not completely reversible,resulting in voltage attenuation and structural instability.A stepwise co-precipitation method is used for the first time in this paper to achieve the control of the two-phase distribution through controlling the distribution of transition metal elements and realize the modification of particle surface structure without the aid of heterologous ions.The results of characterization tests show that the content of LiMO_(2) phase inside the particles and the content of Li_(2)MnO_(3) phase on the surface of the particles are successfully increased,and the surface induced formation of Li_(4)Mn_(5)O_(12) spinel phase or some disorderly ternary.The electrochemical performance of the modified sample is as follows:LR(pristine)shows specific discharge capacity of 72.7 mA·h·g^(−1)after 500 cycles at 1 C,while GR(modified sample)shows specific discharge capacity of 137.5 mA·h·g^(−1) at 1 C,and the discharge mid-voltage of GR still remains above 3 V when cycling to 220 cycles at 1 C(mid-voltage of LR remains above 3 V when cycling to 160 cycles at 1 C).Therefore,deliberately regulating the local state of the two phases is a successful way to reinforced the material structure and inhibition the voltage attenuation.
基金the Geological Investigation Work project of China Geological Survey(Grant No.DD20190172)the National Key R&D Plan of China(Grant No.2017YFC0602806).
文摘The felsic volcanogenic tuffs named"green-bean rocks"(GBRs),characterized by a green or yellowish green color,are widely distributed in the western Yangtze platform and have a high lithium content(286-957 ppm).This paper studies the ages,origin and tectonic setting of the GBRs in the Sichuan basin on the western margin of the Yangtze platform through the whole-rock geochemistry and zircon trace elements by using U-Pb dating and Hf-O isotopes.The GBR samples from the Quxian and Beibei sections yielded zircon U-Pb ages of 245.5±1.8 Ma and 244.8±2.2 Ma.These samples can be used as the isochronous stratigraphic marker of the Early-Middle Triassic boundary(EMTB)for regional correlation.The whole-rock and zircon geochemistry,and zircon Hf-O isotopes exhibited S-type geochemical affinities with high positiveδ^(18)0 values(9.28‰-11.98‰),low negativeε_(Hf)(t)values(-13.87 to-6.79),and T_(DM)^(2)ages of 2150-1703 Ma,indicating that the lithium-rich GBRs were generated by the remelting of the pre-existing ancient Paleoproterozoic layer without mantle source contamination in the arcrelated/orogenic tectonic setting.The results of this study demonstrate that the lithium-rich GBRs in the western Yangtze platform were derived from arc volcanic eruptions along the Sanjiang orogen,triggered by the closure of the eastern Paleo-Tethys Ocean and the syn-collision between the continental Indochina and Yangtze blocks at ca.247 Ma.This was marked by a major shift from I-type magmas with intermediateε_(Hf)(t)values to S-type magmas with low negativeε_(Hf)(t)values.Collectively,our results provide new insights into the origin of the GBRs and decodes the closure of the eastern Paleo-Tethys.
基金The authors gratefully acknowledge financial support from National Key Research and Development Program of China(No.2019YFA0210600)Shanghai Rising-Star Program(No.20QA1406600).
文摘Lithium-ion batteries are considered a promising energy storage technology in portable electronics and electric vehicles due to their high energy density,competitive cost,and environmental friendliness.Improving cathode materials is an effective way to meet the demand for better batteries,of which the utilization of high-voltage cathode materials is an important development trend.In recent years,lithium-rich layered oxides have gained great attention due to their desirable energy density.This review presents the relationships between lattice structure and electrochemical properties,the underlying degradation mechanisms,and corresponding modification strategies.The recent progress and strategies are then highlighted,including element doping,surface coating,morphology design,size control,etc.Finally,a concise perspective for future developments and practical applications of lithium-rich layered oxides has been provided.
基金supported by the National Key Research and Development Program of China (2016YFA202500)the “One Hundred Talent Project” of the Chinese Academy of Sciencesthe National Natural Science Foundation of China (11675255)
文摘Lithium-rich cathode oxides with capability to realize multivalent cationic and anionic redox reactions have attracted much attention as promising candidate electrode materials for high energy density lithium ion batteries because of their ultrahigh specific capacity. However, redox reaction mechanisms, especially for the anionic redox reaction of these materials, are still not very clear. Meanwhile, several pivotal challenges associated with the redox reactions mechanisms, such as structural instability and limited cycle life, hinder the practical applications of these high-capacity lithium-rich cathode oxides. Herein, we review the lithium-rich oxides with various crystal structures. The multivalent cationic/anionic redox reaction mechanisms of several representative high capacity lithium-rich cathode oxides are discussed, attempting to understand the origins of the high lithium storage capacities of these materials. In addition, we provide perspectives for the further development of these lithium-rich cathode oxides based on multivalent cationic and anionic redox reactions, focusing on addressing the fundamental problems and promoting their practical applications.
基金financially supported by the Beijing Natural Science Foundation(JQ19003)National Key R&D Program of China(grant no.2018YFB0104300)+4 种基金National Natural Science Foundation of China(grant no 51622202,21603009,and 21875007)Beijing Natural Science Foundation(B)(KZ201910005002)Beijing Natural Science Foundation(L182009)Project of Youth Talent Plan of Beijing Municipal Education Commission(CIT&TCD201804013)High-grade discipline construction of Beijing(PXM2019-014204-500031)。
文摘The voltage decay of lithium-rich layered oxides(LLOs)is still one of the key challenges for their application in commercial battery although these materials possess the advantages of high specific capacity and low cost.In this work,the relationship between voltage decay and tap density of LLOs has been focused.The voltage decay can be significantly suppressed with the increasing tap density as well as the homogenization of the primary or secondary particle size of agglomerated spherical LLOs.Experimental results have shown that an extreme small voltage decay of 0.98 m V cycle^(-1)can be obtained through adjusting the tap density of agglomerated spherical LLOs to 1.99 g cm^(-3),in which the size of primary and secondary particles are uniform.Our work offers a new insight towards the voltage decay and capacity fading of LLOs through precursor preparation process,promoting their application in the real battery in the future.
