Electrochemical reaction mechanisms under various charge-discharge operating conditions for Li1.2Ni0.13Mn0.54Co0.13O2 in a lithium-ion battery

Konishi, Hiroaki; Hirano, Takuichi; Takamatsu, Daiko; Gunji, Akira; Feng, Xinglei; Furutsuki, Sho; Okumura, Toyoki; Terada, Shohei; Tamura, Kazuhisa

doi:10.1016/j.jssc.2018.03.028

Cited by 10 publications

(19 citation statements)

References 36 publications

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“…Several reasons for the OCV hysteresis in LMR-NCM are discussed in the literature, mainly focusing on reversible transition metal migration 44 and changes of oxygen redox, 45 causing the reentrant Li environment during discharge to be energetically different from that during charge. 4,46 The phenomenon of hysteresis in LMR-NCM is not only observable in the voltage curve, but also in a path dependent cathode resistance [1][2][3] as well as in the SOC dependent hysteresis of LMR-NCM lattice parameters 5,6 and atomic distances. 7 The OCV hysteresis is of particular interest for this study, because it directly reflects the chemical potential, constituting a basic thermodynamic property.…”

Section: Equilibration Time [H]mentioning

confidence: 99%

“…This OCV hysteresis is a material-specific property. The hysteresis does not only affect the voltage profile, but also the cathode resistance, [1][2][3] the Li site occupation 4 as well as the LMR-NCM lattice parameters 5,6 and atomic distances. 7 To gain a better understanding of the thermodynamic processes upon cycling LMR-NCM cathodes, entropy measurements were conducted in this study.…”

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confidence: 99%

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Entropy Measurements of Li-Ion Battery Cells with Li- and Mn-Rich Layered Transition Metal Oxides via Linear Temperature Variation

Friedrich

Pieper

Gasteiger

2021

J. Electrochem. Soc.

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Changes in the partial molar entropy of lithium- and manganese-rich layered transition metal oxides (LMR-NCM) are investigated using a recently established electrochemical measuring protocol, in which the open-circuit voltage (OCV) of a cell is recorded during linear variation of the cell temperature. With this method, the entropy changes of LMR-NCM in half-cells were precisely determined, revealing a path dependence of the entropy during charge and discharge as a function of state of charge, which vanished as a function of OCV. This observation is in line with other hysteresis phenomena observed for LMR-NCM, of which the OCV hysteresis is the most striking one. For a systematic investigation of the entropy changes in LMR-NCM, measurements were conducted during the first activation cycle and in a subsequent cycle. In addition, two LMR-NCM materials with different degrees of overlithiation were contrasted. Contributions from configurational and vibrational entropy are discussed. Our results suggest that the entropy profile during activation exhibits features from the configurational entropy, while during subsequent cycling the vibrational entropy dominates the entropy curve.

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Section: Equilibration Time [H]mentioning

confidence: 99%

mentioning

confidence: 99%

Entropy Measurements of Li-Ion Battery Cells with Li- and Mn-Rich Layered Transition Metal Oxides via Linear Temperature Variation

Friedrich

Pieper

Gasteiger

2021

J. Electrochem. Soc.

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“…It has been reported that the redox of transition metal and oxygen contribute to the discharge reaction for lithium‐rich layer‐structured cathode materials . Our group previously reported that the discharge reaction compensated by the redox of nickel mainly progressed above 3.6 V, and the discharge reaction compensated by the redox of oxygen and manganese mainly progressed below 3.6 V . The reaction compensated by the redox of nickel exhibited a higher rate performance than that compensated by the redox of oxygen and manganese .…”

Section: Resultsmentioning

confidence: 82%

“…For the lithium‐rich nickel‐manganese‐based material, the nickel, manganese, and oxygen contribute to the redox reaction, and the electrochemical performance is affected by the contribution of each element to the redox reaction . Therefore, controlling the contribution of each element to the redox reaction is an important factor in attaining a high electrochemical performance.…”

Section: Resultsmentioning

confidence: 99%

Effect of Lithium/Transition‐Metal Ratio on the Electrochemical Properties of Lithium‐Rich Cathode Materials with Different Nickel/Manganese Ratios for Lithium‐Ion Batteries

2019

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A lithium‐rich nickel‐manganese‐based material (Li1.2Ni0.2Mn0.6O2) exhibited a high discharge capacity at a low C‐rate. However, this material has problems in that it has a poor rate performance, large potential hysteresis, and poor cycle performance. Although increasing the Ni/Mn ratio for Li1.2Ni0.2Mn0.6O2 ameliorated these problems, it decreased the discharge capacity. In this study, the lithium/transition‐metal (Li/TM) ratios for lithium‐rich layer‐structured cathodes with different Ni/Mn ratios were controlled to attain a high discharge capacity, high rate performance, small potential hysteresis, and high cycle performance. For a low‐Ni/Mn‐ratio (Li1.2Ni0.2Mn0.6O2) cathode, a decrease in the Li/TM ratio deteriorated the discharge capacity. Conversely, for cathodes with a high Ni/Mn ratio (Li1.2Ni0.25Mn0.55O2 and Li1.2Ni0.3Mn0.5O2), the decreases in the Li/TM ratios improved the discharge capacity. In addition, for the high‐Ni/Mn‐ratio cathodes, the decrease in the Li/TM ratio from 1.2/0.8 to 1.18/0.82 increased the discharge capacity at a high C‐rate (3 C) from 157 to 183 Ah kg‐1 (Li1.2Ni0.25Mn0.55O2) and from 139 to 156 Ah kg‐1 (Li1.2Ni0.3Mn0.5O2). Furthermore, the decrease in the Li/TM ratio suppressed potential hysteresis and capacity degradation during cycling for the high‐Ni/Mn‐ratio cathodes.

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“…However, the electrochemical reactions of such materials containing multiple metal elements are inherently complicated, and it is thus difficult to precisely determine the redox couples with respect to the electrode potential in Ni-Co-Mn systems. 17 The reaction at spinel LiNi0.5Mn1.5O4 cathodes occurs at a higher voltage than that at spinel LiMn2O4 cathodes. The substitution of metal species contributes to increasing the operating voltage owing to the compact crystal fields imposed by the spinel framework of oxygen linked by tetravalent Mn ions.…”

Section: Introductionmentioning

confidence: 95%

Development of Simultaneous Measurement System for X-ray Absorption Spectra at Two Absorption Edges

et al. 2019

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Dispersive X-ray absorption fine structure (DXAFS) spectroscopy is a versatile measurement technique for analyzing chemical reactions in real time. We have developed a novel time-resolved DXAFS instrument based on two polychromators and a wide-range position-sensitive detector that permits direct observation of the synergistic effects of two elements. This system enables simultaneous acquisition of the X-ray absorption spectra for two different elements without any mechanical movement of the X-ray optics. The developed system was successfully applied to monitor both the synthesis of a Ni-Cu bimetallic catalyst, which revealed that the reduction of Ni occurred at a higher temperature than that of Cu, and the charge-discharge processes of a LixNi0.5Mn1.5O4-based lithium-ion battery, which demonstrated that the redox reactions of Ni and Mn occurred sequentially at specific electrode potentials.

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Electrochemical reaction mechanisms under various charge-discharge operating conditions for Li1.2Ni0.13Mn0.54Co0.13O2 in a lithium-ion battery

Cited by 10 publications

References 36 publications

Entropy Measurements of Li-Ion Battery Cells with Li- and Mn-Rich Layered Transition Metal Oxides via Linear Temperature Variation

Entropy Measurements of Li-Ion Battery Cells with Li- and Mn-Rich Layered Transition Metal Oxides via Linear Temperature Variation

Effect of Lithium/Transition‐Metal Ratio on the Electrochemical Properties of Lithium‐Rich Cathode Materials with Different Nickel/Manganese Ratios for Lithium‐Ion Batteries

Development of Simultaneous Measurement System for X-ray Absorption Spectra at Two Absorption Edges

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