Atomic pair distribution function research on Li_2MnO_3 electrode structure evolution
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摘要
The mechanism research of structure-related reactions on Li_2MnO_3 is important to enhance the electrochemical performance of lithium-manganese-rich layered oxides.Although there are some reports on the structure evolution of Li_2MnO_3 during cycling process,the employed research techniques are very limited,mainly in/ex-situ X-ray diffraction,X-ray absorption and transmission electron microscopy.Here,atomic pair distribution function,a method to study the local atomic arrangement on the basis of average spectroscopic information,is used for the first time to study the local structure evolution of Li_2MnO_3 during electrochemical charge/discharge cycles.The results clearly demonstrate that Mn~(3+)/Mn~(4+) redox couple is activated and Mn ions are reduced during discharging process.Some Mn ions in Mn layers can significantly migrate to Li layers and occupy the octahedral sites.As a result,a portion of inserted Li ions can occupy the face-shared tetrahedron sites,accompanied by the formation of local spinel-like structure.This work provides an important and suitable method based on the average spectroscopic information to investigate the local structure of electrode materials of lithium-ion batteries as well as other advanced battery systems.
The mechanism research of structure-related reactions on Li_2MnO_3 is important to enhance the electrochemical performance of lithium-manganese-rich layered oxides.Although there are some reports on the structure evolution of Li_2MnO_3 during cycling process,the employed research techniques are very limited,mainly in/ex-situ X-ray diffraction,X-ray absorption and transmission electron microscopy.Here,atomic pair distribution function,a method to study the local atomic arrangement on the basis of average spectroscopic information,is used for the first time to study the local structure evolution of Li_2MnO_3 during electrochemical charge/discharge cycles.The results clearly demonstrate that Mn~(3+)/Mn~(4+) redox couple is activated and Mn ions are reduced during discharging process.Some Mn ions in Mn layers can significantly migrate to Li layers and occupy the octahedral sites.As a result,a portion of inserted Li ions can occupy the face-shared tetrahedron sites,accompanied by the formation of local spinel-like structure.This work provides an important and suitable method based on the average spectroscopic information to investigate the local structure of electrode materials of lithium-ion batteries as well as other advanced battery systems.
The mechanism research of structure-related reactions on Li_2MnO_3 is important to enhance the electrochemical performance of lithium-manganese-rich layered oxides.Although there are some reports on the structure evolution of Li_2MnO_3 during cycling process,the employed research techniques are very limited,mainly in/ex-situ X-ray diffraction,X-ray absorption and transmission electron microscopy.Here,atomic pair distribution function,a method to study the local atomic arrangement on the basis of average spectroscopic information,is used for the first time to study the local structure evolution of Li_2MnO_3 during electrochemical charge/discharge cycles.The results clearly demonstrate that Mn~(3+)/Mn~(4+) redox couple is activated and Mn ions are reduced during discharging process.Some Mn ions in Mn layers can significantly migrate to Li layers and occupy the octahedral sites.As a result,a portion of inserted Li ions can occupy the face-shared tetrahedron sites,accompanied by the formation of local spinel-like structure.This work provides an important and suitable method based on the average spectroscopic information to investigate the local structure of electrode materials of lithium-ion batteries as well as other advanced battery systems.
引文
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[16]Yan P,Xiao L,Zheng J,et al.Probing the degradation mechanism of Li2MnO3cathode for Li-ion batteries.Chem Mater 2015;27:975-82.
[17]Kan Y,Hu Y,Lin CK,et al.Migration of Mn cations in delithiated lithium manganese oxides.Phys Chem Chem Phys 2014;16:20697-702.
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[20]Seo DH,Lee J,Urban A,et al.The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials.Nat Chem 2016;8:692-7.
[21]Luo K,Roberts MR,Hao R,et al.Charge-compensation in 3d-transition-metaloxide intercalation cathodes through the generation of localized electron holes on oxygen.Nat Chem 2016;8:684-91.
[22]Luo K,Roberts MR,Guerrini N,et al.Anion redox chemistry in the cobalt free3d transition metal oxide intercalation electrode Li[Li0.2Ni0.2Mn0.6]O2.J Am Chem Soc 2016;138:11211-8.
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[25]Tran N,Croguennec L,Ménétrier M,et al.Mechanisms associated with the‘‘plateau”observed at high voltage for the overlithiated Li1.12(Ni0.425Mn0.425Co0.15)0.88O2system.Chem Mater 2008;20:4815-25.
[26]Yu H,So Y-G,Ren Y,et al.Temperature-sensitive structure evolution of lithium-manganese-rich layered oxides for lithium-ion batteries.J Am Chem Soc 2018;140:15279-89.
[27]Kondracki?,Kulka A,Milewska A,et al.In-situ structural studies of manganese spinel-based cathode materials.Electrochim Acta 2017;227:294-302.
[28]Phillips PJ,Bare?o J,Li Y,et al.On the localized nature of the structural transformations of Li2MnO3following electrochemical cycling.Adv Energy Mater 2015;5:1501252.
[29]Amalraj SF,Burlaka L,Julien CM,et al.Phase transitions in Li2MnO3electrodes at various states-of-charge.Electrochim Acta 2014;123:395-404.
[30]Mohanty D,Li J,Abraham DP,et al.Unraveling the voltage-fade mechanism in high-energy-density lithium-ion batteries:origin of the tetrahedral cations for spinel conversion.Chem Mater 2014;26:6272-80.
[31]Juhás P,Davis T,Farrow CL,et al.PDFgetX3:a rapid and highly automatable program for processing powder diffraction data into total scattering pair distribution functions.J Appl Crystallogr 2013;46:560-6.
[32]Phillips PJ,Iddir H,Abraham DP,et al.Direct observation of the structural and electronic changes of Li2MnO3during electron irradiation.Appl Phys Lett2014;105:113905.
[2]Whittingham MS.Ultimate limits to intercalation reactions for lithium batteries.Chem Rev 2014;114:11414-43.
[3]Goodenough JB,Kim Y.Challenges for rechargeable batteries.J Power Sources2011;196:6688-94.
[4]Cho E,Kim K,Jung C,et al.Overview of the oxygen behavior in the degradation of Li2MnO3cathode material.J Phys Chem C 2017;121:21118-27.
[5]Yu H,Kim H,Wang Y,et al.High-energy‘‘composite”layered manganese-rich cathode materials via controlling Li2MnO3phase activation for lithium-ion batteries.Phys Chem Chem Phys 2012;14:6584-95.
[6]Manthiram A,Knight JC,Myung ST,et al.Nickel-rich and lithium-rich layered oxide cathodes:progress and perspectives.Adv Energy Mater2016;6:1501010.
[7]Yu H,So YG,Kuwabara A,et al.Crystalline grain interior configuration affects lithium migration kinetics in Li-rich layered oxide.Nano Lett2016;16:2907-15.
[8]Hy S,Liu H,Zhang M,et al.Performance and design considerations for lithium excess layered oxide positive electrode materials for lithium ion batteries.Energy Environ Sci 2016;9:1931-54.
[9]Zheng J,Myeong S,Cho W,et al.Li-and Mn-rich cathode materials:challenges to commercialization.Adv Energy Mater 2017;7:1601284.
[10]Zhang XD,Shi JL,Liang JY,et al.Suppressing surface lattice oxygen release of Li-rich cathode materials via heterostructured spinel Li4Mn5O12coating.Adv Mater 2018;30:1801751.
[11]Nayak PK,Grinblat J,Levi M,et al.Al doping for mitigating the capacity fading and voltage decay of layered Li and Mn-rich cathodes for Li-ion batteries.Adv Energy Mater 2016;6:1502398.
[12]Zubair M,Wang B,Li G,et al.Electrochemical kinetics and cycle stability improvement with Nb doping for lithium-rich layered oxides.ACS Appl Energy Mater 2018;2:503-12.
[13]Wang R,He X,He L,et al.Atomic structure of Li2MnO3after partial delithiation and re-lithiation.Adv Energy Mater 2013;3:1358-67.
[14]Croy JR,Park JS,Dogan F,et al.First-cycle evolution of local structure in electrochemically activated Li2MnO3.Chem Mater 2014;26:7091-8.
[15]Oishi M,Yamanaka K,Watanabe I,et al.Direct observation of reversible oxygen anion redox reaction in Li-rich manganese oxide,Li2MnO3,studied by soft X-ray absorption spectroscopy.J Mater Chem A 2016;4:9293-302.
[16]Yan P,Xiao L,Zheng J,et al.Probing the degradation mechanism of Li2MnO3cathode for Li-ion batteries.Chem Mater 2015;27:975-82.
[17]Kan Y,Hu Y,Lin CK,et al.Migration of Mn cations in delithiated lithium manganese oxides.Phys Chem Chem Phys 2014;16:20697-702.
[18]Egami T,Billinge S.Underneath the Bragg Peaks.2nd ed.Pergamon;2012.
[19]Matsunaga T,Komatsu H,Shimoda K,et al.Dependence of structural defects in Li2MnO3on synthesis Temperature.Chem Mater 2016;28:4143-50.
[20]Seo DH,Lee J,Urban A,et al.The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials.Nat Chem 2016;8:692-7.
[21]Luo K,Roberts MR,Hao R,et al.Charge-compensation in 3d-transition-metaloxide intercalation cathodes through the generation of localized electron holes on oxygen.Nat Chem 2016;8:684-91.
[22]Luo K,Roberts MR,Guerrini N,et al.Anion redox chemistry in the cobalt free3d transition metal oxide intercalation electrode Li[Li0.2Ni0.2Mn0.6]O2.J Am Chem Soc 2016;138:11211-8.
[23]Robertson AD,Bruce PG.Mechanism of electrochemical activity in Li2MnO3.Chem Mater 2003;15:1984-92.
[24]Shimoda K,Oishi M,Matsunaga T,et al.Direct observation of layered-to-spinel phase transformation in Li2MnO3and the spinel structure stabilised after the activation process.J Mater Chem A 2017;5:6695-707.
[25]Tran N,Croguennec L,Ménétrier M,et al.Mechanisms associated with the‘‘plateau”observed at high voltage for the overlithiated Li1.12(Ni0.425Mn0.425Co0.15)0.88O2system.Chem Mater 2008;20:4815-25.
[26]Yu H,So Y-G,Ren Y,et al.Temperature-sensitive structure evolution of lithium-manganese-rich layered oxides for lithium-ion batteries.J Am Chem Soc 2018;140:15279-89.
[27]Kondracki?,Kulka A,Milewska A,et al.In-situ structural studies of manganese spinel-based cathode materials.Electrochim Acta 2017;227:294-302.
[28]Phillips PJ,Bare?o J,Li Y,et al.On the localized nature of the structural transformations of Li2MnO3following electrochemical cycling.Adv Energy Mater 2015;5:1501252.
[29]Amalraj SF,Burlaka L,Julien CM,et al.Phase transitions in Li2MnO3electrodes at various states-of-charge.Electrochim Acta 2014;123:395-404.
[30]Mohanty D,Li J,Abraham DP,et al.Unraveling the voltage-fade mechanism in high-energy-density lithium-ion batteries:origin of the tetrahedral cations for spinel conversion.Chem Mater 2014;26:6272-80.
[31]Juhás P,Davis T,Farrow CL,et al.PDFgetX3:a rapid and highly automatable program for processing powder diffraction data into total scattering pair distribution functions.J Appl Crystallogr 2013;46:560-6.
[32]Phillips PJ,Iddir H,Abraham DP,et al.Direct observation of the structural and electronic changes of Li2MnO3during electron irradiation.Appl Phys Lett2014;105:113905.
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