First principles investigation of electronic structure change and energy transfer by redox in inverse spinel cathodes LiNiVO4 and LiCoVO4

Chen, Zhenlian; Li, Jun; Zhang, Zhiyong

doi:10.1039/c2jm33026a

Cited by 15 publications

(19 citation statements)

References 46 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For instance, the highest occupied O 2 2− ‐π* molecular orbitals may be competing with open TM‐d orbitals for the oxidation and local coordination to charge compensation in the process of delithiation. [ 41 ] Thus, one should identify consistent spectroscopies showing both electronic and vibrational characteristics if the OO dimers truly confined in the bulk, not just one of them. That should be the determining factor to not only the dimer formation but also its lifetime to oxygen release.…”

Section: Electrochemistry Of Lcsomentioning

confidence: 99%

Prospect and Status of Polyanionic Lithium Cobalt Silicates as High Energy‐Density and Safe Cathode Materials for Lithium‐Ion Batteries

Zhang

Chen

et al. 2021

Physica Status Solidi (b)

Self Cite

View full text Add to dashboard Cite

Lithium cobalt silicate Li2CoSiO4 (LCSO) is a promising but challenging high energy‐density cathode for lithium‐ion battery. Herein, recent studies of synthesis–structure–performance of LCSO are reported, in which carbon coating, element doping, and nanostructure designs are incorporated in a two‐step synthesis starting with hydrothermal reaction. The initial performance is significantly improved with respect to previous reports in literature with the charge and discharge capacities now reaching 330 and 220 mAh g−1, respectively. The discharge voltage platform is compatible with the 4 V window of the nonaqueous organic electrolytes and presents no structural‐change‐induced voltage drops. The striking finding from the study of LCSO is the oxygen redox activity amid the second lithium deintercalation process, in which peroxo formation dominates the charge compensation to the high‐voltage lithium capacity. First‐principles modeling reveals an intrinsic and general relation between oxygen redox and cationic disorder in bulk compounds. Thus, LCSO is a new prototype of polyanionic materials with oxygen redox, which is the foundation of high‐capacity Li‐rich cathodes. This review is also aimed to narrate the progresses of LCSO within a broad domain of Li3PO4‐based polyanionic structures that support the development of solid‐state electrolytes for all solid‐state batteries.

show abstract

Section: Electrochemistry Of Lcsomentioning

confidence: 99%

Prospect and Status of Polyanionic Lithium Cobalt Silicates as High Energy‐Density and Safe Cathode Materials for Lithium‐Ion Batteries

Zhang

Chen

et al. 2021

Physica Status Solidi (b)

Self Cite

View full text Add to dashboard Cite

show abstract

“…Experimentally, it has been demonstratedt hat the energy conversion accompanying alkali-ion intercalation can be attributed to the electron redox energy and the Madelungp otential at the alkali-ion sites as relatedt ot he electron and alkali-ion intercalation, respectively. [14,15] For intercalation compounds, the redox reaction depends on the formal valence-state alternation of the active cation and its covalent bonding with the nearest-neighbor anions. [11] The TM is octahedrally coordinated by oxygen in both the layered and spinel crystal structures.…”

Section: Transition-metaloxide Electrodesmentioning

confidence: 99%

“…These valence electrons play a key role in determining the electronic properties of the TMO, and are largely made of TM d‐orbital and oxygen‐ion p‐orbital interactions. Experimentally, it has been demonstrated that the energy conversion accompanying alkali‐ion intercalation can be attributed to the electron redox energy and the Madelung potential at the alkali‐ion sites as related to the electron and alkali‐ion intercalation, respectively . For intercalation compounds, the redox reaction depends on the formal valence‐state alternation of the active cation and its covalent bonding with the nearest‐neighbor anions …”

Section: Alkali‐ion Battery Electrode Chemistrymentioning

confidence: 99%

The Role of Intentionally Introduced Defects on Electrode Materials for Alkali‐Ion Batteries

Uchaker

Cao

2015

Chemistry An Asian Journal

View full text Add to dashboard Cite

Simple defect modification is a powerful means to improve material intercalation capabilities. It has received considerable interest lately as it can directly alter both the chemical and structural characteristics; techniques of note include cationic disordering, amorphization, doping, partial cation reduction, and manipulation of intrinsic defects. Defects can reduce the stress and the electrostatic repulsion between adjacent oxygen layers, which can directly alter the migration energy and diffusion barriers the alkali ion must overcome during intercalation. Complementary to experimental observations, theoretical predictions are paramount to developing a detailed understanding of material-defect chemistry. This focus review aims to demonstrate that the optimized design of stable intercalation compounds could lead to substantial improvements in energy-storage applications by overcoming intrinsic limitations.

show abstract

“…The challenge for these inverse spinel structured cathode materials in lithium ion batteries is their lower initial capacity and drastic capacity loss upon cycles. 7 Numerous efforts have been made in order to overcome these disadvantages including nanofabrication, 8,9 metal ion doping, 10 and surface modifications. 11,12 In particular, surface modification of cathode materials receives major attention due to their advantages such as enhanced structural stability during lithium intercalation, prevention of unwanted interaction of cathode surfaces with electrolytes, and the thermal stability.…”

Section: Introductionmentioning

confidence: 99%

Surface modification and characterization of nanocrystalline LiNi_0.5Co_0.5VO₄with Dy₂O₃by polymeric resin process

Vivekanandhan

Venkateswarlu²,

Satyanarayana

2015

Advanced Device Materials

View full text Add to dashboard Cite

A poly acrylic acid and ethylene glycol mediated polymeric resin process has been demonstrated for the fabrication of functional Dy 2 O 3 layer on the nanocrystalline LiNi 0.5 Co 0.5 VO 4 surfaces. Polymeric resin helps in the uniform distribution as well as the stabilization of Dy 3+ ions on the LiNi 0.5 Co 0.5 VO 4 surfaces. The thermal degradation of Dy 3+ distributed polymeric resin at 500 °C results in the formation of Dy 2 O 3 on the surface of LiNi 0.5 Co 0.5 VO 4 particles, which was confirmed by TG/ DTA and FTIR analysis. Excellent homogeneity of the Dy 2 O 3 layer with a controlled thickness on the surface of LiNi 0.5 Co 0.5 VO 4 has been confirmed by SEM-EDS and TEM analysis.

show abstract

First principles investigation of electronic structure change and energy transfer by redox in inverse spinel cathodes LiNiVO4 and LiCoVO4

Cited by 15 publications

References 46 publications

Prospect and Status of Polyanionic Lithium Cobalt Silicates as High Energy‐Density and Safe Cathode Materials for Lithium‐Ion Batteries

Prospect and Status of Polyanionic Lithium Cobalt Silicates as High Energy‐Density and Safe Cathode Materials for Lithium‐Ion Batteries

The Role of Intentionally Introduced Defects on Electrode Materials for Alkali‐Ion Batteries

Surface modification and characterization of nanocrystalline LiNi_0.5Co_0.5VO₄with Dy₂O₃by polymeric resin process

Contact Info

Product

Resources

About

First principles investigation of electronic structure change and energy transfer by redox in inverse spinel cathodes LiNiVO4 and LiCoVO4

Cited by 15 publications

References 46 publications

Prospect and Status of Polyanionic Lithium Cobalt Silicates as High Energy‐Density and Safe Cathode Materials for Lithium‐Ion Batteries

Prospect and Status of Polyanionic Lithium Cobalt Silicates as High Energy‐Density and Safe Cathode Materials for Lithium‐Ion Batteries

The Role of Intentionally Introduced Defects on Electrode Materials for Alkali‐Ion Batteries

Surface modification and characterization of nanocrystalline LiNi0.5Co0.5VO4with Dy2O3by polymeric resin process

Contact Info

Product

Resources

About

Surface modification and characterization of nanocrystalline LiNi_0.5Co_0.5VO₄with Dy₂O₃by polymeric resin process