Potential hysteresis between charge and discharge reactions in Li1.2Ni0.13Mn0.54Co0.13O2 for lithium ion batteries

Abstract The mechanism responsible for the large potential hysteresis between charge and discharge reactions in Li 1.2 Ni 0.13 Mn 0.54 Co 0.13 O 2 was investigated. The relationship between open circuit potential and the oxidation state of each transition metal during charge-discharge processes was evaluated. The results indicated that the electrochemical reaction in Li 1.2 Ni 0.13 Mn 0.54 Co 0.13 O 2 , which can be expressed as 0.5Li 2 MnO 3 −0.5LiNi 0.33 Mn 0.33 Co 0.33 O 2 , was composed of two kinds of reactions such as LiNi 0.33 Mn 0.33 Co 0.33 O 2 -like and Li 2 MnO 3 -like reactions. For the LiNi 0.33 Mn 0.33 Co 0.33 O 2 -like reaction, nickel and cobalt contributed to the redox reaction. The electrochemical reaction progressed within a potential range of 3.6–4.6 V, both during charge and discharge processes; thereby, there was little potential hysteresis between charge and discharge processes. For Li 2 MnO 3 -like reaction, manganese and oxygen contributed to the redox reaction. The reaction that occurred within a potential range of 3.6–4.6 V in a charge process mainly progressed within a potential range of 3.6–2.5 V during the discharge process, which indicated that there was large potential hysteresis between charge and discharge processes in the Li 2 MnO 3 -like reaction. Therefore, the large hysteresis of reaction potential between charge and discharge processes in the Li 2 MnO 3 -like reaction was mainly related to that in the 0.5Li 2 MnO 3 −0.5LiNi 0.33 Mn 0.33 Co 0.33 O 2 .

[1]  B. Hwang,et al.  Direct in situ observation of Li2O evolution on Li-rich high-capacity cathode material, Li[Ni(x)Li((1-2x)/3)Mn((2-x)/3)]O2 (0 ≤ x ≤ 0.5). , 2014, Journal of the American Chemical Society.

[2]  Kevin G. Gallagher,et al.  Correlating hysteresis and voltage fade in lithium- and manganese-rich layered transition-metal oxide electrodes , 2013 .

[3]  Y. Okamoto.  Ambivalent Effect of Oxygen Vacancies on Li2MnO3: A First-Principles Study , 2011 .

[4]  Chaolun Gan,et al.  Origin of the irreversible plateau (4.5V) of Li[Li0.182Ni0.182Co0.091Mn0.545]O2 layered material , 2005 .

[5]  I. Nakai,et al.  In Situ Transmission X‐Ray Absorption Fine Structure Analysis of the Li Deintercalation Process in Li ( Ni0.5Co0.5 ) O 2 , 1999 .

[6]  M. Balasubramanian,et al.  In Situ X‐Ray Absorption Studies of a High‐Rate LiNi0.85Co0.15 O 2 Cathode Material , 2000 .

[7]  C. Ghanty,et al.  Electrochemical characteristics of xLi2MnO3-(1-x)Li(Mn0.375Ni0.375Co0.25)O2 (0.0 ≤ x ≤ 1.0) composite cathodes: Effect of particle and Li2MnO3 domain size , 2014 .

[8]  H. Kageyama,et al.  Investigation on lithium de-intercalation mechanism for Li1−yNi1/3Mn1/3Co1/3O2 , 2005 .

[9]  C. Delmas,et al.  Thermal Stability of Lithium Nickel Oxide Derivatives. Part II: LixNi0.70Co0.15Al0.15O2 and LixNi0.90Mn0.10O2 (x = 0.50 and 0.30). Comparison with LixNi1.02O2 and LixNi0.89Al0.16O2 , 2003 .

[10]  Jun Liu,et al.  Carbon-coated high capacity layered Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathodes , 2010 .

[11]  Tsutomu Ohzuku,et al.  High-capacity lithium insertion materials of lithium nickel manganese oxides for advanced lithium-ion batteries: toward rechargeable capacity more than 300 mA h g−1 , 2011 .

[12]  Debasish Mohanty,et al.  Structural transformation of a lithium-rich Li1.2Co0.1Mn0.55Ni0.15O2 cathode during high voltage cycling resolved by in situ X-ray diffraction , 2013 .

[13]  Xiao‐Qing Yang,et al.  In situ X-ray absorption and diffraction studies of carbon coated LiFe1/4Mn1/4Co1/4Ni1/4PO4 cathode during first charge , 2009 .

[14]  Tsuyoshi Sasaki,et al.  Capacity-Fading Mechanisms of LiNiO2-Based Lithium-Ion Batteries I. Analysis by Electrochemical and Spectroscopic Examination , 2009 .

[15]  Christopher S. Johnson,et al.  Anomalous capacity and cycling stability of xLi2MnO3 · (1 − x)LiMO2 electrodes (M = Mn, Ni, Co) in lithium batteries at 50 °C , 2007 .

[16]  Yuichi Sato,et al.  In situ X-ray absorption spectroscopic study of Li-rich layered cathode material Li[Ni0.17Li0.2Co0.07Mn0.56]O2 , 2011 .

[17]  Michael M. Thackeray,et al.  Enhancing the rate capability of high capacity xLi2MnO3 · (1 -x)LiMO2 (M = Mn, Ni, Co) electrodes by Li-Ni-PO4 treatment , 2009 .

[18]  Xiao‐Qing Yang,et al.  Time-Resolved XRD Study on the Thermal Decomposition of Li[sub 1−x]Ni[sub 0.8]Co[sub 0.15]Al[sub 0.05]O[sub 2] Cathode Materials for Li-Ion Batteries , 2005 .

[19]  Ki-Soo Lee,et al.  Structural and Electrochemical Properties of Layered Li [ Ni1 − 2x Co x Mn x ] O2 ( x = 0.1 – 0.3 ) Positive Electrode Materials for Li-Ion Batteries , 2007 .

[20]  C. Delmas,et al.  Reversible Oxygen Participation to the Redox Processes Revealed for Li1.20Mn0.54Co0.13Ni0.13O2 , 2013 .

[21]  J. Tarascon,et al.  The intriguing question of anionic redox in high-energy density cathodes for Li-ion batteries , 2016 .

[22]  A. Busnaina,et al.  Mitigation of Layered to Spinel Conversion of a Li-Rich Layered Metal Oxide Cathode Material for Li-Ion Batteries , 2014 .

[23]  In Situ X-Ray Spectroscopy and Imaging of Battery Materials , 2011 .

[24]  D. Takamatsu,et al.  Evaluation of Stability of Charged Lithium-rich Layer-structured Cathode Material at Elevated Temperature , 2015 .

[25]  John T. Vaughey,et al.  The significance of the Li2MnO3 component in ‘composite’ xLi2MnO3 · (1 − x)LiMn0.5Ni0.5O2 electrodes , 2004 .

[26]  K. Edström,et al.  Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen. , 2016, Nature chemistry.

[27]  John T. Vaughey,et al.  Advances in manganese-oxide ‘composite’ electrodes for lithium-ion batteries , 2005 .

[28]  Rahul Malik,et al.  The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials. , 2016, Nature chemistry.

[29]  M. Yoshikawa,et al.  Evaluation of thermal stability in Li0.2NixMn(1−x)/2Co(1−x)/2O2 (x = 1/3, 0.6, and 0.8) through X-ray absorption fine structure , 2014 .

[30]  Shinichi Komaba,et al.  Detailed studies of a high-capacity electrode material for rechargeable batteries, Li2MnO3-LiCo(1/3)Ni(1/3)Mn(1/3)O2. , 2011, Journal of the American Chemical Society.

[31]  Daniel P. Abraham,et al.  Long-Range and Local Structure in the Layered Oxide Li1.2Co0.4Mn0.4O2 , 2011 .

[32]  François Weill,et al.  Different oxygen redox participation for bulk and surface: A possible global explanation for the cycling mechanism of Li1.20Mn0.54Co0.13Ni0.13O2 , 2013 .

[33]  K. Amine,et al.  Nanoscale Phase Separation, Cation Ordering, and Surface Chemistry in Pristine Li1.2Ni0.2Mn0.6O2 for Li-Ion Batteries , 2013 .

[34]  Lijun Wu,et al.  Combining In Situ Synchrotron X‐Ray Diffraction and Absorption Techniques with Transmission Electron Microscopy to Study the Origin of Thermal Instability in Overcharged Cathode Materials for Lithium‐Ion Batteries , 2013 .

[35]  Hiroshi Nakamura,et al.  Electrochemical Activities in Li2MnO3 , 2009 .

[36]  I. Nakai,et al.  Effect of the elevated temperature on the local structure of lithium manganese oxide studied by in situ XAFS analysis , 1999 .

[37]  N. Kitamura,et al.  Composition dependence of average and local structure of xLi(Li1/3Mn2/3)O2–(1 − x)Li(Mn1/3Ni1/3Co1/3)O2 active cathode material for Li ion batteries , 2014 .

[38]  M. Yoshikawa,et al.  Thermal stability of Li1−yNixMn(1−x)/2Co(1−x)/2O2 layer-structured cathode materials used in Li-Ion batteries , 2011 .

[39]  D. Takamatsu,et al.  Effect of Composition of Transition Metals on Stability of Charged Li-rich Layer-structured Cathodes, Li1.2Ni0.2-xMn0.6-xCo2xO2 (x=0, 0.033, and 0.067), at High Temperatures , 2015 .

[40]  Jaephil Cho,et al.  Effect of Preparation Methods of LiNi1 − x Co x O 2 Cathode Materials on Their Chemical Structure and Electrode Performance , 1999 .

[41]  G. Ceder,et al.  Electrochemical Activity of Li in the Transition-Metal Sites of O3 Li [ Li ( 1 − 2x ) / 3Mn ( 2 − x ) / 3Ni x ] O 2 , 2004 .

[42]  Xiaoliang Feng,et al.  Origin of hysteresis between charge and discharge processes in lithium-rich layer-structured cathode material for lithium-ion battery , 2015 .

[43]  Kevin G. Gallagher,et al.  Examining Hysteresis in Composite xLi2MnO3·(1−x)LiMO2 Cathode Structures , 2013 .

[44]  B. Sheldon,et al.  The impact of oxygen vacancies on lithium vacancy formation and diffusion in Li2-xMnO3-δ , 2015 .

[45]  Y. Ukyo,et al.  Direct observation of reversible oxygen anion redox reaction in Li-rich manganese oxide, Li2MnO3, studied by soft X-ray absorption spectroscopy , 2016 .

[46]  Yuichi Sato,et al.  Direct observation of the partial formation of a framework structure for Li-rich layered cathode mat , 2011 .