Li2Ni0.2Co1.8O4 having a spinel framework as a zero-strain positive electrode material for lithium-ion batteries

Ariyoshi, Kingo; Orikasa, Yuki; Kajikawa, Kensuke; Yamada, Yusuke

doi:10.1039/c9ta03191j

Cited by 22 publications

(21 citation statements)

References 45 publications

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“…Thus, by omitting Ni from the LT phase, the materials approach a zero-strain mechanism: 0.05% for LT-LCO and 0.11% for Li2Ni0.2Co1.8O4. 19 This change is the smallest among the lithium insertion materials of spinel structure except for LTO.…”

Section: Analysis Of the Lt-to Ht-lco Phase Transitionmentioning

confidence: 95%

“…[12][13][14] LCO has two polymorphs depending on the synthetic temperature: a layered structure for the high-temperature phase (LiCoO2; HT-LCO) and a spinel-framework structure for the low-temperature phase (Li2Co2O4; LT-LCO). [12][13][14][15][16][17][18][19][20][21][22] LT-LCO has the same chemical formula as that of the HT phase but with a different cationic arrangement. Thus, in LT-LCO, the Co and oxide ions form a spinelframework in which the Li ions fully occupy the vacant octahedral sites to form a reduced (or lithiated) spinel structure.…”

Section: Introductionmentioning

confidence: 99%

“…Thus, in LT-LCO, the Co and oxide ions form a spinelframework in which the Li ions fully occupy the vacant octahedral sites to form a reduced (or lithiated) spinel structure. [14][15][16][17][18][19] The LT-LCO was extensively studied from the late 1990s to the early 2000s, because the LT-LCO having 3D-framework would have superior dimensional stability to HT-phase. However, the electrochemical performance of the LT-LCO could not surpass that of the HT-LCO, owing to difficulties in the synthesis of single-phase LT-LCO.…”

Section: Introductionmentioning

confidence: 99%

“…Thus, the LT phase has a lower electrode potential than the HT phase and presents flat charge-discharge curves in contrast to the sloping voltage profiles presented by the HT phase. 14,18,19 EXPERIMENTAL Synthesis and Structural Characterization of Li2Co2O4. The Li2Co2O4 samples were prepared by a solid-state synthetic method.…”

Section: Introductionmentioning

confidence: 99%

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Reaction Mechanism and Kinetic Analysis of the Solid-State Reaction to Synthesize Single-Phase Li₂Co₂O₄Spinel

2020

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Lithium cobalt oxide has two polymorphs that display different electrochemical properties despite their identical redox reactions: a high-temperature phase having a layered structure (LiCoO2; HT-LCO) and a low-temperature phase with a spinel-framework (Li2Co2O4;LT-LCO). The synthetic conditions of the single-phase LT-LCO were determined by thermogravimetric (TG) analysis performed on the solid-state reaction of Li2CO3 and Co3O4.The results revealed that LCO synthesis was a second order reaction with the activation energy of Ea = 150 kJ mol −1 and preexponential factor of A = 9.2 × 10 7 s −1 . XRD studies indicated that low temperature synthesis below 350 °C is necessary to obtain the single-phase LT phase, because the HT-phase fraction increased with increasing synthesis temperature. Virtually single-phase LT-LCO obtained by calcining at 325 °C for 240 h exhibited zero-strain lithium insertion. These results contribute towards the establishment of a synthetic method for novel materials with reduced spinel structure.

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Section: Analysis Of the Lt-to Ht-lco Phase Transitionmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Reaction Mechanism and Kinetic Analysis of the Solid-State Reaction to Synthesize Single-Phase Li₂Co₂O₄Spinel

2020

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“…Aside from layered materials, zero‐strain spinel phases like LiRh 2 O 4 and low‐temperature LiCoO 2 derivatives may be helpful in controlling internal stress, but the question still remains in the overall performance optimization. [ 107–109 ]…”

Section: Structural Design Of Cathode Electrode Concerning Interfaciamentioning

confidence: 99%

Structure Design of Cathode Electrodes for Solid‐State Batteries: Challenges and Progress

Zhang

Yue²,

Liang

et al. 2020

Small Structures

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Solid‐state lithium batteries have aroused wide interest with the probability to guarantee safety and high energy density at the same time. In the past decade, fruitful endeavors have been devoted to promoting each component of these batteries, including solid electrolyte with high conductivity, dendrite‐free lithium anode, and high‐capacity cathode. However, the currently achieved cell performances are still inconsistent with the original expectations, in which interfaces severely hamper the energy output and cycling stability for practical application. Herein, particular attentions are paid to the interface between cathode and solid electrolyte. The huge resistance caused at this interface can be found throughout the entire life of batteries from preparation to operation. Accordingly, these issues are divided into physical contact, thermal interdiffusion, space‐charge layer, electrochemomechanical breakdown, and undesirable side reactions and further elucidated in detail. Moreover, representative developments concerning the cathode/solid electrolyte interface in terms of compositional and morphological control in cathode, architecture and manufacture design in solid electrolyte, and artificial interphase building are summarized. With these efforts, the emphasis of the fundamental issues and perspectives of interface between cathode and solid electrolyte may eventually contribute to high‐energy long‐cycling solid‐state lithium batteries.

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A New Sodium Calcium Cyclotetravanadate Framework: “Zero‐Strain” during Large‐Capacity Lithium Intercalation

Yang

Liang

Cao

et al. 2021

Adv Funct Materials

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Zero-strain" materials with little lattice strain and volume change during long-term cycling are ideal electrode choices for long-life lithium-ion batteries. However, the very limited "zero-strain" materials explored generally show small capacities (<200 mAh g −1 ), and the origin of "zero-strain" is still unclear. Here, Na 2 Ca(VO 3 ) 4 (NCVO) nanowires are explored as a new anode material capable of keeping single-phase-transition "zero-strain" during large-capacity (381 mAh g −1 ) Li + intercalation. NCVO owns a crystal structure with isolated [V 4 O 12 ] 4− tetracycles separated by large-sized NaO 6 octahedra and CaO 8 square antiprism decahedra, generating large-sized quadrilateral and hexagonal channels (≈3.6 Å). During lithiation, two-electron transfer per vanadium is accomplished, introducing a large amount of Li + into interstitial sites and increasing the size of reduced vanadium ions. The former and latter expansion effects are eliminated by the superior volume-buffering capabilities of the sufficiently large interstitial sites and electrochemical inactive Na-/Ca-based polyhedra, respectively, thus achieving "zero-strain" with the maximum volume variation of only 0.039% and mean strain of only 0.060%. Therefore, the NCVO nanowires exhibit exceptional cyclic stability, as demonstrated by 93.8%/93.2%/94.7% capacity retention over 2000/2000/7000 cycles at 1C/2C/10C. The understanding of the crystal-structural features for "zero-strain" provides a guide for the future designs of "zero-strain" energy-storage materials.

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Li₂Ni_0.2Co_1.8O₄ having a spinel framework as a zero-strain positive electrode material for lithium-ion batteries

Abstract: A zero-strain insertion material of Li2Ni0.2Co1.8O4 having a spinel framework was synthesized and showed very small dimensional change during charge–discharge reaction with large volumetric capacity.

Cited by 22 publications

References 45 publications

Reaction Mechanism and Kinetic Analysis of the Solid-State Reaction to Synthesize Single-Phase Li₂Co₂O₄Spinel

Reaction Mechanism and Kinetic Analysis of the Solid-State Reaction to Synthesize Single-Phase Li₂Co₂O₄Spinel

Structure Design of Cathode Electrodes for Solid‐State Batteries: Challenges and Progress

A New Sodium Calcium Cyclotetravanadate Framework: “Zero‐Strain” during Large‐Capacity Lithium Intercalation

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Li2Ni0.2Co1.8O4 having a spinel framework as a zero-strain positive electrode material for lithium-ion batteries

Abstract: A zero-strain insertion material of Li2Ni0.2Co1.8O4 having a spinel framework was synthesized and showed very small dimensional change during charge–discharge reaction with large volumetric capacity.

Cited by 22 publications

References 45 publications

Reaction Mechanism and Kinetic Analysis of the Solid-State Reaction to Synthesize Single-Phase Li2Co2O4Spinel

Reaction Mechanism and Kinetic Analysis of the Solid-State Reaction to Synthesize Single-Phase Li2Co2O4Spinel

Structure Design of Cathode Electrodes for Solid‐State Batteries: Challenges and Progress

A New Sodium Calcium Cyclotetravanadate Framework: “Zero‐Strain” during Large‐Capacity Lithium Intercalation

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Resources

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Li₂Ni_0.2Co_1.8O₄ having a spinel framework as a zero-strain positive electrode material for lithium-ion batteries

Reaction Mechanism and Kinetic Analysis of the Solid-State Reaction to Synthesize Single-Phase Li₂Co₂O₄Spinel

Reaction Mechanism and Kinetic Analysis of the Solid-State Reaction to Synthesize Single-Phase Li₂Co₂O₄Spinel