The rapid development of electric vehicles and portable energy storage systems demands improvements in the energy density and cost-effectiveness of lithium-ion batteries,a domain in which Lithium-rich layered cathode(...The rapid development of electric vehicles and portable energy storage systems demands improvements in the energy density and cost-effectiveness of lithium-ion batteries,a domain in which Lithium-rich layered cathode(LLO)materials inherently excel.However,these materials face practical challenges,such as low initial Coulombic efficiency,inferior cycle/rate performance,and voltage decline during cycling,which limit practical application.Our study introduces a surface multi-component integration strategy that incorporates oxygen vacancies into the pristine LLO material Li1.2Mn_(0.6)Ni_(0.2)O_(2).This process involves a brief citric acid treatment followed by calcination,aiming to explore rate-dependent degradation behavior.The induced surface oxygen vacancies can reduce surface oxygen partial pressure and diminish the generation of O_(2)and other highly reactive oxygen species on the surface,thereby facilitating the activation of Li ions trapped in tetrahedral sites while overcoming transport barriers.Additionally,the formation of a spinel-like phase with 3D Li+diffusion channels significantly improves Li^(+)diffusion kinetics and stabilizes the surface structure.The optimally modified sample boasts a discharge capacity of 299.5 mA h g^(-1)at a 0.1 C and 251.6 mA h g^(-1)at a 1 C during the initial activation cycle,with an impressive capacity of 222.1 mA h g^(-1)at a 5 C.Most notably,it retained nearly 70%of its capacity after 300 cycles at this elevated rate.This straightforward,effective,and highly viable modification strategy provides a crucial resolution for overcoming challenges associated with LLO materials,making them more suitable for practical application.展开更多
Layered lithium-rich manganese-based oxide(LRMO)has the limitation of inevitable evolution of lattice oxygen release and layered structure transformation.Herein,a multilayer reconstruction strategy is applied to LRMO ...Layered lithium-rich manganese-based oxide(LRMO)has the limitation of inevitable evolution of lattice oxygen release and layered structure transformation.Herein,a multilayer reconstruction strategy is applied to LRMO via facile pyrolysis of potassium Prussian blue.The multilayer interface is visually observed using an atomic-resolution scanning transmission electron microscope and a high-resolution transmission electron microscope.Combined with the electrochemical characterization,the redox of lattice oxygen is suppressed during the initial charging.In situ X-ray diffraction and the high-resolution transmission electron microscope demonstrate that the suppressed evolution of lattice oxygen eliminates the variation in the unit cell parameters during initial(de)lithiation,which further prevents lattice distortion during long cycling.As a result,the initial Coulombic efficiency of the modified LRMO is up to 87.31%,and the rate capacity and long-term cycle stability also improved considerably.In this work,a facile surface reconstruction strategy is used to suppress vigorous anionic redox,which is expected to stimulate material design in high-performance lithium ion batteries.展开更多
As promising energy storage systems,lithium-sulfur(Li-S)batteries have attracted significant attention because of their ultra-high energy densities.However,Li-S battery suffers problems related to the complex phase co...As promising energy storage systems,lithium-sulfur(Li-S)batteries have attracted significant attention because of their ultra-high energy densities.However,Li-S battery suffers problems related to the complex phase conversion that occurs during the charge-discharge process,particularly the deposition of solid Li2S from the liquid-phase polysulfides,which greatly limits its practical application.In this paper,edge-rich MoS2/C hollow microspheres(Edg-MoS2/C HMs)were designed and used to functionalize separator for Li-S battery,resulting in the uniform deposition of Li2S.The microspheres were fabricated through the facile hydrothermal treatment of MoO3-aniline nanowires and a subsequent carbonization process.The obtained Edg-MoS2/C HMs have a strong chemical absorption capability and high density of Li2S binding sites,and exhibit excellent electrocatalytic performance and can effectively hinder the polysulfide shuttle effect and guide the uniform nucleation and growth of Li2S.Furthermore,we demonstrate that the Edg-MoS2/C HMs can effectively regulate the deposition of Li2S and significantly improve the reversibility of the phase conversion of the active sulfur species,especially at high sulfur loadings and high C-rates.As a result,a cell containing a separator functionalized with Edg-MoS2/C HMs exhibited an initial discharge capacity of 935 mAh g-1 at 1.0 C and maintained a capacity of 494 mAh g-1 after 1000 cycles with a sulfur loading of 1.7 mg cm-2.Impressively,at a high sulfur loading of 6.1 mg cm-2 and high rate of 0.5 C,the cell still delivered a high reversible discharge capacity of 478 mAh g-1 after 300 cycles.This work provides fresh insights into energy storage systems related to complex phase conversions.展开更多
In this study we report a series of nickel-rich layered cathodes LiNi1-2xCoxMnxO2（x = 0.075, 0.05,0.025） prepared from chlorides solution via ultrasonic spray pyrolysis. SEM images illustrate that the samples are su...In this study we report a series of nickel-rich layered cathodes LiNi1-2xCoxMnxO2（x = 0.075, 0.05,0.025） prepared from chlorides solution via ultrasonic spray pyrolysis. SEM images illustrate that the samples are submicron-sized particles and the particle sizes increase with the increase of Ni content.LiNi0.85Co0.075Mn0.075O2 delivers a discharge capacity of 174.9 mAh g-1 with holding 93% reversible capacity at 1 C after 80 cycles, and can maintain a discharge capacity of 175.3 mAh g-1 at 5 C rate. With increasing Ni content, the initial specific capacity increases while the cycling and rate performance degrades in some extent. These satisfying results demonstrate that spray pyrolysis is a powerful and efficient synthesis technology for producing Ni-rich layered cathode（Ni content 〉 80%）.展开更多
For constructing next-generation lithium-ion batteries with advanced performances,pursuit of highcapacity Li-rich cathodes has caused considerable attention.So far,the low discharge specific capacity and serious capac...For constructing next-generation lithium-ion batteries with advanced performances,pursuit of highcapacity Li-rich cathodes has caused considerable attention.So far,the low discharge specific capacity and serious capacity fading are strangling the development of Fe-based Li-rich materials.To activate the extra-capacity of Fe-based Li-rich cathode materials,a facile molten salt method is exploited using an alkaline mixture of LiOH–LiNO3–Li2O2 in this work.The prepared Li1.09(Fe0.2Ni0.3Mn0.5)0.91O2 material yields high discharge specific capacity and good cycling stability.The discharge specific capacity shows an upward tendency at 0.1 C.After 60 cycles,a high reversible specific capacity of ~250 m Ah g-1is delivered.The redox of Fe3+/Fe4+and Mn3+/Mn4+are gradually activated during cycling.Notably,the redox reaction of Fe2+/Fe3+can be observed reversibly below 2 V,which is quite different from the material prepared by a traditional co-precipitation method.The stable morphology of fine nanoparticles(100–300 nm)is considered benefiting for the distinctive electrochemical performances of Li1.09(Fe0.2Ni0.3Mn0.5)0.91O2.This study demonstrates that molten salt method is an inexpensive and effective approach to activate the extra capacity of Fe-based Li-rich cathode material for high-performance lithium-ion batteries.展开更多
基金supported by the National Key R&D Program of China(2021YFB2401800)the National Natural Science Foundation of China(21875022,22179008)+4 种基金the Yibin‘Jie Bang Gua Shuai’(2022JB004)the support from the Beijing Nova Program(20230484241)the support from the Postdoctoral Fellowship Program of CPSF(GZB20230931)the support from the 4B7B beam line of Beijing Synchrotron Radiation Facility(2021-BEPC-PT-005924,2021-BEPC-PT-005967)BL08U1A beam line of Shanghai Synchrotron Radiation Facility(2021-SSRF-PT-017710)。
文摘The rapid development of electric vehicles and portable energy storage systems demands improvements in the energy density and cost-effectiveness of lithium-ion batteries,a domain in which Lithium-rich layered cathode(LLO)materials inherently excel.However,these materials face practical challenges,such as low initial Coulombic efficiency,inferior cycle/rate performance,and voltage decline during cycling,which limit practical application.Our study introduces a surface multi-component integration strategy that incorporates oxygen vacancies into the pristine LLO material Li1.2Mn_(0.6)Ni_(0.2)O_(2).This process involves a brief citric acid treatment followed by calcination,aiming to explore rate-dependent degradation behavior.The induced surface oxygen vacancies can reduce surface oxygen partial pressure and diminish the generation of O_(2)and other highly reactive oxygen species on the surface,thereby facilitating the activation of Li ions trapped in tetrahedral sites while overcoming transport barriers.Additionally,the formation of a spinel-like phase with 3D Li+diffusion channels significantly improves Li^(+)diffusion kinetics and stabilizes the surface structure.The optimally modified sample boasts a discharge capacity of 299.5 mA h g^(-1)at a 0.1 C and 251.6 mA h g^(-1)at a 1 C during the initial activation cycle,with an impressive capacity of 222.1 mA h g^(-1)at a 5 C.Most notably,it retained nearly 70%of its capacity after 300 cycles at this elevated rate.This straightforward,effective,and highly viable modification strategy provides a crucial resolution for overcoming challenges associated with LLO materials,making them more suitable for practical application.
基金This work was financially supported by the High‐level Talents'Discipline Construction Fund of Shandong University(31370089963078)the Shandong Provincial Science and Technology Major Project(2018JM RH0211 and 2017CXGC1010)+3 种基金the Research Funds of Shandong University(10000089395121)the Natural Science Foundation of Shandong Province(ZR2019MEM052 and ZR2017MEM002)The National Natural Science Foundation of China(grant no.52002287)the Start‐up Funding of Wenzhou University are acknowledged.
文摘Layered lithium-rich manganese-based oxide(LRMO)has the limitation of inevitable evolution of lattice oxygen release and layered structure transformation.Herein,a multilayer reconstruction strategy is applied to LRMO via facile pyrolysis of potassium Prussian blue.The multilayer interface is visually observed using an atomic-resolution scanning transmission electron microscope and a high-resolution transmission electron microscope.Combined with the electrochemical characterization,the redox of lattice oxygen is suppressed during the initial charging.In situ X-ray diffraction and the high-resolution transmission electron microscope demonstrate that the suppressed evolution of lattice oxygen eliminates the variation in the unit cell parameters during initial(de)lithiation,which further prevents lattice distortion during long cycling.As a result,the initial Coulombic efficiency of the modified LRMO is up to 87.31%,and the rate capacity and long-term cycle stability also improved considerably.In this work,a facile surface reconstruction strategy is used to suppress vigorous anionic redox,which is expected to stimulate material design in high-performance lithium ion batteries.
基金financially supported by National Natural Science Foundation of China (No. 51672083)Program of Shanghai Academic/Technology Research Leader (18XD1401400)+3 种基金Basic Research Program of Shanghai (17JC1404702)Leading talents in Shanghai in 2018The 111 project (B14018)the Fundamental Research Funds for the Central Universities (222201718002)
文摘As promising energy storage systems,lithium-sulfur(Li-S)batteries have attracted significant attention because of their ultra-high energy densities.However,Li-S battery suffers problems related to the complex phase conversion that occurs during the charge-discharge process,particularly the deposition of solid Li2S from the liquid-phase polysulfides,which greatly limits its practical application.In this paper,edge-rich MoS2/C hollow microspheres(Edg-MoS2/C HMs)were designed and used to functionalize separator for Li-S battery,resulting in the uniform deposition of Li2S.The microspheres were fabricated through the facile hydrothermal treatment of MoO3-aniline nanowires and a subsequent carbonization process.The obtained Edg-MoS2/C HMs have a strong chemical absorption capability and high density of Li2S binding sites,and exhibit excellent electrocatalytic performance and can effectively hinder the polysulfide shuttle effect and guide the uniform nucleation and growth of Li2S.Furthermore,we demonstrate that the Edg-MoS2/C HMs can effectively regulate the deposition of Li2S and significantly improve the reversibility of the phase conversion of the active sulfur species,especially at high sulfur loadings and high C-rates.As a result,a cell containing a separator functionalized with Edg-MoS2/C HMs exhibited an initial discharge capacity of 935 mAh g-1 at 1.0 C and maintained a capacity of 494 mAh g-1 after 1000 cycles with a sulfur loading of 1.7 mg cm-2.Impressively,at a high sulfur loading of 6.1 mg cm-2 and high rate of 0.5 C,the cell still delivered a high reversible discharge capacity of 478 mAh g-1 after 300 cycles.This work provides fresh insights into energy storage systems related to complex phase conversions.
基金financial support of the National Basic Research Program of China (2014CB643406)the National Natural Science Foundation of China (51674296, 51704332)+1 种基金the National Postdoctoral Program for Innovative Talents (BX201700290)the Fundamental Research Funds for the Central Universities of Central South University (2017zzts125)
文摘In this study we report a series of nickel-rich layered cathodes LiNi1-2xCoxMnxO2（x = 0.075, 0.05,0.025） prepared from chlorides solution via ultrasonic spray pyrolysis. SEM images illustrate that the samples are submicron-sized particles and the particle sizes increase with the increase of Ni content.LiNi0.85Co0.075Mn0.075O2 delivers a discharge capacity of 174.9 mAh g-1 with holding 93% reversible capacity at 1 C after 80 cycles, and can maintain a discharge capacity of 175.3 mAh g-1 at 5 C rate. With increasing Ni content, the initial specific capacity increases while the cycling and rate performance degrades in some extent. These satisfying results demonstrate that spray pyrolysis is a powerful and efficient synthesis technology for producing Ni-rich layered cathode（Ni content 〉 80%）.
基金supported by the Nature Science Foundations of Hebei Province (B2016210071, B2016210111)the Natural Science Foundation of Hebei Education Department (QN2016057, ZD2015082, ZC2016045)+3 种基金the National College Students’ Innovative Entrepreneurial Training Project of Chinasupported by the Chinese National 973 Program (2015CB251106)the Joint Funds of the National Natural Science Foundation of China (U1564206)Major achievements Transformation Project for Central University in Beijing
文摘For constructing next-generation lithium-ion batteries with advanced performances,pursuit of highcapacity Li-rich cathodes has caused considerable attention.So far,the low discharge specific capacity and serious capacity fading are strangling the development of Fe-based Li-rich materials.To activate the extra-capacity of Fe-based Li-rich cathode materials,a facile molten salt method is exploited using an alkaline mixture of LiOH–LiNO3–Li2O2 in this work.The prepared Li1.09(Fe0.2Ni0.3Mn0.5)0.91O2 material yields high discharge specific capacity and good cycling stability.The discharge specific capacity shows an upward tendency at 0.1 C.After 60 cycles,a high reversible specific capacity of ~250 m Ah g-1is delivered.The redox of Fe3+/Fe4+and Mn3+/Mn4+are gradually activated during cycling.Notably,the redox reaction of Fe2+/Fe3+can be observed reversibly below 2 V,which is quite different from the material prepared by a traditional co-precipitation method.The stable morphology of fine nanoparticles(100–300 nm)is considered benefiting for the distinctive electrochemical performances of Li1.09(Fe0.2Ni0.3Mn0.5)0.91O2.This study demonstrates that molten salt method is an inexpensive and effective approach to activate the extra capacity of Fe-based Li-rich cathode material for high-performance lithium-ion batteries.
