Probing and suppressing voltage fade of Li-rich Li1.2Ni0.13Co0.13Mn0.54O2 cathode material for lithium-ion battery

Zou, Wei; Xia, Fanjie; Song, Jian-Ping; Wu, Liang; Chen, Liang-Dan; Chen, Hao; Liu, Yang; Dong, Wenyi; Wu, Sijia; Hu, Zhi‐Yi; Liu, Jing; Wang, Hong‐En; Chen, Lihua; Liu, Yu; Peng, Dong‐Liang; Su, Bao‐Lian

doi:10.1016/j.electacta.2019.06.119

Cited by 44 publications

(9 citation statements)

References 47 publications

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“…Generally, it is believed that oxygen loss and TM ions migration are the main culprits that cause the decay of the layered LLOs to the spinel structure (LiMn 2 O 4 ). , As shown in Figure , at a state of high delithiation, a large number of Li vacancies and some oxygen vacancies appear in PLLO and TM ions will migrate into the Li octahedron in the Li layer through the tetrahedron and are pinned here permanently, thereby forming the LiMn 2 O 4 . In the doped LLOs, CBLLO, the process of phase transition is inhibited.…”

Section: Resultsmentioning

confidence: 99%

Dual-Site Doping Strategy for Enhancing the Structural Stability of Lithium-Rich Layered Oxides

Tang

Duan

Xie

et al. 2021

ACS Appl. Mater. Interfaces

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Lithium-rich layered oxide (LLO) cathode materials are considered to be one of the most promising next-generation candidates of cathode materials for lithium-ion batteries due to their high specific capacity. However, some inherent defects of LLOs hinder their practical application due to the oxygen loss and structure collapse resulting from intrinsic anion and cation redox reactions, such as poor cycle stability, sluggish Li+ kinetics, and voltage decay. Herein, we put forward a facile synergistic strategy to respond to these shortcomings of LLOs via dual-site doping with cerium (Ce) and boron (B) ions. The doped Ce ions occupy the octahedral sites, which not only enlarge the cell volume but also stabilize the layered framework and introduce abundant oxygen vacancies for LLOs, while B ions occupy the tetrahedral sites in the lattice, which block the migration path of transition metal (TM) ions and reduce the oxygen loss using the strong B–O bond. Based on this dual-site doping effect, after 100 cycles at 1 C, the dual-site doped materials exhibit excellent structural stability with a capacity retention of 91.15% (vs 75.12%) and also greatly suppress the voltage decay in LLOs with a voltage retention of 93.60% (vs 87.83%).

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Section: Resultsmentioning

confidence: 99%

Dual-Site Doping Strategy for Enhancing the Structural Stability of Lithium-Rich Layered Oxides

Tang

Duan

Xie

et al. 2021

ACS Appl. Mater. Interfaces

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“…In LRLO the probability of the occurrence of repeated vicinal LiTM 6 motifs is neither null nor unitary, thus leading to an intermediate lattice where rhombohedral symmetries coexist with limited monoclinic features [23,40] . The achievement of a well‐ordered layered structure is confirmed by the splitting of the (006)/(102) and (108)/(110) pair of peaks, [32,41,42] indexed by the rhombohedral structure. No phase impurity is detected by diffraction in all samples, indicating the high purity of the synthesized materials, either undoped or Fe‐doped.…”

Section: Resultsmentioning

confidence: 99%

Understanding the Impact of Fe‐Doping on the Structure and Battery Performance of a Co‐Free Li‐Rich Layered Cathodes

et al. 2023

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A series of Co‐free Li‐rich layered oxides, Li1.24Mn0.62‐xNi0.14FexO2 (x=0, 0.01, 0.02 and 0.03) has been synthetized by a self‐combustion reaction. Fe doping affects either lattice structure and bonding as shown by the changes in the size of unit cell calculated from diffraction patterns and in the vibrational frequencies observed in Raman spectra. The electrochemical performance has been evaluated in a lithium cell by galvanostatic cycling: Doped samples show better capacity retention and minor decreases in the specific capacity (i. e., Li1.24Mn0.60Ni0.14Fe0.02O2 can supply a specific capacity of 235 mAhg−1 with 94 % of capacity retention after 150 cycles). These positive effects originated by alterations in the point defectivity (Ni3+ concentration, anionic and cationic vacancies), changes in the transport properties, as showed by Cyclic Voltammetry; as well as an improved structural resilience compared to the un‐doped material in postmortem analyses.

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Section: Electrochemical Characterizationmentioning

confidence: 94%

“…For both samples, the oxidation peak at about 3.2 V is related to the oxidation of Mn 3+ to Mn 4+ , while the oxidation peak at around 3.8 V is attributed to the oxidation of Ni 2+ to Ni 3+ and Ni 4+ and the oxidation of Co 3+ to Co 4+ . [7,[16][17][18] Similarly, for the discharge process, the reduction peak between 3.6 V and 3.8 V vs. Li + /Li results from the Ni 4+ /Ni 2+ redox The lowering of the (integrated) intensity of the reduction peak associated with the Ni 4+ /Ni 2+ redox couple upon increasing cycle number and the simultaneous increase of the (integrated) peak intensity of the reduction peak attributed to the Mn 4+ /Mn 2+ redox couple strongly indicates the transformation from the initial layered structure to a (disordered) spinel-type structure [7,16,17,20]. The increase of the Mn 4+ /Mn 3+ reduction peak goes along with the increase in (integrated) peak intensity of the oxidation peak associated with the Mn 3+ /Mn 4+ redox couple.…”

Section: Electrochemical Characterizationmentioning

confidence: 99%

The Influence of Synthesis Method on the Local Structure and Electrochemical Properties of Li-Rich/Mn-Rich NMC Cathode Materials for Li-Ion Batteries

et al. 2022

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Electrochemical energy storage plays a vital role in combating global climate change. Nowadays lithium-ion battery technology remains the most prominent technology for rechargeable batteries. A key performance-limiting factor of lithium-ion batteries is the active material of the positive electrode (cathode). Lithium- and manganese-rich nickel manganese cobalt oxide (LMR-NMC) cathode materials for Li-ion batteries are extensively investigated due to their high specific discharge capacities (>280 mAh/g). However, these materials are prone to severe capacity and voltage fade, which deteriorates the electrochemical performance. Capacity and voltage fade are strongly correlated with the particle morphology and nano- and microstructure of LMR-NMCs. By selecting an adequate synthesis strategy, the particle morphology and structure can be controlled, as such steering the electrochemical properties. In this manuscript we comparatively assessed the morphology and nanostructure of LMR-NMC (Li1.2Ni0.13Mn0.54Co0.13O2) prepared via an environmentally friendly aqueous solution-gel and co-precipitation route, respectively. The solution-gel (SG) synthesized material shows a Ni-enriched spinel-type surface layer at the {200} facets, which, based on our post-mortem high-angle annual dark-field scanning transmission electron microscopy and selected-area electron diffraction analysis, could partly explain the retarded voltage fade compared to the co-precipitation (CP) synthesized material. In addition, deviations in voltage fade and capacity fade (the latter being larger for the SG material) could also be correlated with the different particle morphology obtained for both materials.

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Probing and suppressing voltage fade of Li-rich Li1.2Ni0.13Co0.13Mn0.54O2 cathode material for lithium-ion battery

Cited by 44 publications

References 47 publications

Dual-Site Doping Strategy for Enhancing the Structural Stability of Lithium-Rich Layered Oxides

Dual-Site Doping Strategy for Enhancing the Structural Stability of Lithium-Rich Layered Oxides

Understanding the Impact of Fe‐Doping on the Structure and Battery Performance of a Co‐Free Li‐Rich Layered Cathodes

The Influence of Synthesis Method on the Local Structure and Electrochemical Properties of Li-Rich/Mn-Rich NMC Cathode Materials for Li-Ion Batteries

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