Insights into the electrochemical Li/Na-exchange in layered LiCoO2 cathode material

Heubner, Christian; Matthey, Björn; Lein, Tobias; Wolke, Florian; Liebmann, Tobias; Lämmel, C.; Schneider, Michael; Herrmann, Mathias; Michaelis, Alexander

doi:10.1016/j.ensm.2020.02.012

Cited by 30 publications

(28 citation statements)

References 42 publications

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“…e diameter of the semicircles is equal to the resistance values of the corresponding process. It is observed that the lower specific frequency at the top of semicircles and the higher charge transfers were obtained in sodium half-cell possibly indicating slower kinetic of sodium intercalation compared to lithium intercalation into the same delithiated host [20]. EIS spectrum after sodiation exhibits three semicircles as previously reported on Na y NMC electrode [29].…”

Section: Resultssupporting

confidence: 68%

“…erefore, sodiation in delithiated host with the lowest remained lithium-ions is another way to enhance the electrochemical properties of the sodium cathode. Recent studies have reported the use of a delithiated cathode phase as a sodium intercalation host for Na-ion batteries, including layered oxide, phosphates, and Li-rich cathodes [13,[17][18][19][20]. Previously, we studied the full sodiation into LiNMC synthesized via sol-gel reaction [13].…”

Section: Introductionmentioning

confidence: 99%

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New Sodium Intercalation Cathode Prepared by Sodiation of Delithiated Host LiNi_1/3Mn_1/3Co_1/3O₂

Nguyen

Huynh

et al. 2021

Advances in Materials Science and Engineering

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In this work, the layered structure LiNi1/3Mn1/3Co1/3O2 (LiNMC) served as a host to enable sodium-ion intercalation. LiNMC was initially charged in Li-half-cell at C/25 rate up to 4.5 V to extract maximum of Li+ ions and then discharged at the same rate in Na-half-cell down to 2 V for full sodiation to form NayNMC phase. The electrochemical characteristics of the new sodium phase NayNMC were evaluated by cyclic voltammetry (CV), galvanostatic cycling, and electrochemical impedance spectroscopy (EIS). On the CV curve, the featured peaks of phase transition induced by Na+ intercalation into NayNMC host could be distinguished from the couple peak located at 3.8 V upon the Li+ intercalation into LixNMC. The high uniformity and crystallinity of the NayNMC phase enable delivering a good initial capacity of about 120 mAh g−1 with high rate capability up to 5 C rate. Energy-dispersive X-ray spectroscopy (EDS) confirms the presence of sodium element in the sodiated NayNMC. It was also noticed that the pristine O3-type layered structure remained unchanged after ion exchanging but the lattice parameters increased due to the large size of sodium-ions inserted into the structure.

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Section: Resultssupporting

confidence: 68%

Section: Introductionmentioning

confidence: 99%

New Sodium Intercalation Cathode Prepared by Sodiation of Delithiated Host LiNi_1/3Mn_1/3Co_1/3O₂

Nguyen

Huynh

et al. 2021

Advances in Materials Science and Engineering

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“…Among them, the number of ions in the solution must exceed the number of ions in the material to be replaced several times to be completely exchanged. At present, the Li/Na ion exchange reaction is usually used to prepare LIB cathode materials, which can obtain unique structural characteristics based on the precursor with a layered structure [124] . However, the large difference between the Li + and Na + radii causes drastic changes in the interlayer spacing and structure of the material, which may be accompanied by partial lattice distortion and particle breakage [125] .…”

Section: Ion-exchange Methodsmentioning

confidence: 99%

Multi-dimensional correlation of layered Li-rich Mn-based cathode materials

Yang¹,

Zheng²,

Wei³

et al. 2022

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Lithium-rich manganese-based cathode materials are expected to promote the commercialization of lithium-ion batteries to a new stage by virtue of their ultrahigh specific capacity and energy density advantages. However, they are still restricted by complex phase transitions and electrochemical performance degradation caused by labile anion charge compensation. A deep understanding of the electrochemical properties contained in their intrinsic structures and the key driving factors of structural deterioration during cycling are crucial to guide the preparation and optimization of lithium-rich materials. Considering recent progress, this review introduces the intrinsic properties of Li-rich manganese-based cathode materials from interatomic interactions to particle morphology at multiple scales in the spatial dimension. The charge compensation mechanism and energy band reorganization of the initial charge and discharge, the structural evolution during cycling and the electrochemical reaction kinetics of the materials are analyzed in the temporal dimension. Based on the relationship between structure and electrochemical performance, preparation methods and modification methods are introduced to guide and design cathode materials. Effective characterization methods for studying anion charge compensation behavior are also demonstrated. This review provides important guidance and suggestions for making full use of the high specific capacity in these materials derived from anion redox and the maintaining of its stability.

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Section: Introductionmentioning

confidence: 99%

“…The ion exchange method can exchange alkali ions (Li + or Na + ) to prepare new cathode materials for LIBs or SIBs without destroying the structural framework of the material. [41][42][43][44] Paulsen and Dahn et al prepared a number of P2-O2 ion exchange reactions [45][46][47][48] and made sufficient experiments to investigate the electrochemical properties and structure evolution of O2 materials. The O2-type structure can inhibit the migration of Mn to the Li slab owing to the mutual repulsion between adjacent Mn slab atoms, thereby alleviating the formation of spinel phase and voltage attenuation.…”

Section: Introductionmentioning

confidence: 99%

Highly Reversible Anion Redox of Manganese‐Based Cathode Material Realized by Electrochemical Ion Exchange for Lithium‐Ion Batteries

Yang

Zhong

Feng

et al. 2021

Adv Funct Materials

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Anion energy storage provides the possibility to achieve higher specific capacity in lithium‐ion battery cathode materials, but the problems of capacity attenuation, voltage degradation, and inconsistent redox behavior are still inevitable. In this paper, a novel O2‐type manganese‐based layered cathode material Lix[Li0.2Mn0.8]O2 with a ribbon superlattice structure is prepared by electrochemical ion exchange, which realizes the highly reversible redox of anions and excellent cycle performance. Through low‐voltage pre‐cycling treatment, the specific capacity of the material can reach 230 mAh g−1 without obvious voltage attenuation. During the electrochemical ion exchange, the precursor with P2 structure transforms into Lix[Li0.2Mn0.8]O2 with O2 structure through the slippage and shrink of adjacent slabs, and the special superlattice structure in Mn slab is still retained. Simultaneously, a certain degree of lattice mismatch and reversible distortion of the MnO6 octahedron occur. In addition, the anion redox catalyzes the formation of the solid electrolyte interface, stabilizing the electrode/electrolyte interface and inhibiting the dissolution of Mn. The mechanism of electrochemical ion exchange is systematically studied by comprehensive structural and electrochemical characterization, opening an attractive path for the realization of highly reversible anion redox.

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Insights into the electrochemical Li/Na-exchange in layered LiCoO2 cathode material

Cited by 30 publications

References 42 publications

New Sodium Intercalation Cathode Prepared by Sodiation of Delithiated Host LiNi_1/3Mn_1/3Co_1/3O₂

New Sodium Intercalation Cathode Prepared by Sodiation of Delithiated Host LiNi_1/3Mn_1/3Co_1/3O₂

Multi-dimensional correlation of layered Li-rich Mn-based cathode materials

Highly Reversible Anion Redox of Manganese‐Based Cathode Material Realized by Electrochemical Ion Exchange for Lithium‐Ion Batteries

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Insights into the electrochemical Li/Na-exchange in layered LiCoO2 cathode material

Cited by 30 publications

References 42 publications

New Sodium Intercalation Cathode Prepared by Sodiation of Delithiated Host LiNi1/3Mn1/3Co1/3O2

New Sodium Intercalation Cathode Prepared by Sodiation of Delithiated Host LiNi1/3Mn1/3Co1/3O2

Multi-dimensional correlation of layered Li-rich Mn-based cathode materials

Highly Reversible Anion Redox of Manganese‐Based Cathode Material Realized by Electrochemical Ion Exchange for Lithium‐Ion Batteries

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New Sodium Intercalation Cathode Prepared by Sodiation of Delithiated Host LiNi_1/3Mn_1/3Co_1/3O₂

New Sodium Intercalation Cathode Prepared by Sodiation of Delithiated Host LiNi_1/3Mn_1/3Co_1/3O₂