High performance sputtered LiCoO2 thin films obtained at a moderate annealing treatment combined to a bias effect

Tintignac, S.; Baddour‐Hadjean, R.; Pereira-Ramos, J.P.; Salot, Raphaël

doi:10.1016/j.electacta.2011.11.033

Cited by 66 publications

(62 citation statements)

References 47 publications

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“…This result is in close agreement with other studies. 7,8,15,52,53 A more detailed analysis in the high wavenumber region shows two bands: one around 585 cm -1 correspondent to ν(CoO 6 ) and another in 540 cm -1 for δ(O−Co−O). It is also observed one shoulder located around 630-660 cm -1 assigned as overtone vibration.…”

Section: Resultsmentioning

confidence: 99%

“…[1][2][3][4][5][6][7][8] This system has interesting electrochemical features that allows a wide use as cathodes of lithium ion batteries. 2,4 The investigation of the structural aspects of the material is a crucial issue to better understand the electrochemical properties of the LiCoO 2 compound.…”

Section: Introductionmentioning

confidence: 99%

“…Therefore, several authors usually classify these structures as LT-LiCoO 2 and HT-LiCoO 2 , respectively . 1,2,7,8,[18][19][20][21][22][23][24] The rhombohedral phase is characterized by a structure with alternating layers of cobalt and lithium cations intercalated with oxygen anions. 22 The lithium and cobalt(III) ions are arranged in intercalated layers ( Figure 1a).…”

Section: Introductionmentioning

confidence: 99%

“…2,4 The investigation of the structural aspects of the material is a crucial issue to better understand the electrochemical properties of the LiCoO 2 compound. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] For example, the nature of the crystal, its size and shape, are directly related with its electrochemical characteristics. 2 The LiCoO 2 synthesized at low temperatures (LT), below 500 °C, presents a cubic spinel structure ( ), while the synthesis at high temperatures (HT) (above 500 °C), generates the rhombohedral structure with stratified layers ( ).…”

mentioning

confidence: 99%

“…Experimental studies report that the HT-LiCoO 2 phase has two bands observed around 487 (A 1g ) and 597 (E g ) cm -1 in the Raman spectra, while the LT-LiCoO 2 has four bands at 449, 484, 590 and 605 cm -1 (modes A 1g , E g and 2F 2g ). 7,8,15,52,53 In this work, the FTIR spectra were divided into two parts, as shown in Figure 2: the region of low wavenumber, which contains a defined band at 297 cm -1…”

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Synthesis and Characterization of LiCoO2 from Different Precursors by Sol‑Gel Method

Freitas

Siqueira

Costa

et al. 2017

J. Braz. Chem. Soc.

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Lithium cobalt oxide, LiCoO 2 , widely used as cathode in lithium ion batteries was synthesized and their structural and electronic properties investigated. The crystalline powders were prepared by the sol-gel method with four complexing agents: citric acid, glycine, starch and gelatin. These syntheses were compared with the blank test (without complexing agent). The X-ray diffraction and vibrational spectroscopy allowed the identification of the rhombohedral phase LiCoO 2 ( ) as the only or principal crystalline component in all samples. A small fraction of a second phase of cubic spinel Co 3 O 4 was observed in the samples of starch, gelatin and the blank test. The Rietveld refinements showed small structural variations, indicating reduced influence of the complexing agents on the synthesis. The theoretical HOMO-LUMO (highest occupied molecular orbital-lowest unoccupied molecular orbital) gap values are in agreement to those estimated by diffuse reflectance spectroscopy (DRS). The scanning electron microscopy (SEM) showed morphological pattern regardless of the complexing agent used, showing an alternative method.Keywords: LiCoO 2 , sol-gel method, XRD, Rietveld refinement, lithium ion batteries, DFT IntroductionLithium cobalt oxide, LiCoO 2 , has been the focus of many studies regarding their structural and electronic properties. [1][2][3][4][5][6][7][8] This system has interesting electrochemical features that allows a wide use as cathodes of lithium ion batteries. 2,4 The investigation of the structural aspects of the material is a crucial issue to better understand the electrochemical properties of the LiCoO 2 compound. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] For example, the nature of the crystal, its size and shape, are directly related with its electrochemical characteristics. 2 The LiCoO 2 synthesized at low temperatures (LT), below 500 °C, presents a cubic spinel structure ( ), while the synthesis at high temperatures (HT) (above 500 °C), generates the rhombohedral structure with stratified layers ( ). Therefore, several authors usually classify these structures as LT-LiCoO 2 and HT-LiCoO 2 , respectively . 1,2,7,8,[18][19][20][21][22][23][24] The rhombohedral phase is characterized by a structure with alternating layers of cobalt and lithium cations intercalated with oxygen anions. 22 The lithium and cobalt(III) ions are arranged in intercalated layers (Figure 1a). The cobalt(III) ion is located at the octahedral sites, forming a strong bond with the neighboring oxygen anion to constitute the Co−O layers (Figure 1b). Finally, the lithium layers are intercalated between the CoO 2 plans. 1,3,4 The octahedral sites of these layers are occupied by lithium and cobalt(III) ions alternately that forms a sequential stacking with oxygen ion layers in a close packing of the ABCABC type ( Figure 1c). 4,5 This specific stacking arrangement leads to an environment equivalent for all ions, allowing the maximum charge delocalization and the minimal system energy. 1,3,4 The degree of crystal orde...

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Synthesis and Characterization of LiCoO2 from Different Precursors by Sol‑Gel Method

Freitas

Siqueira

Costa

et al. 2017

J. Braz. Chem. Soc.

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Electrochemical Lithium Insertion into TiO₂ Anatase ALD Thin Films for Li‐Ion Microbatteries: An Atomic‐Scale Picture Provided by Raman Spectroscopy

Bhatia

Hallot

Leviel

et al. 2023

Adv Materials Inter

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Such applications have created a high demand for Li-ion microbatteries with high energy density. Up to now, the vast majority of commercial microbatteries use transition metal oxides active materials at the cathode side, e.g. LiCoO 2 , [2] V 2 O 5 , [3] LiMn 1.5 Ni 0.5 O 4 , [4] or phosphate-based materials such as LiFePO 4 , [5] or LiMnPO 4 . [6] At the anode side, Li-metal is commonly used due to its interesting characteristics such as low molecular weight which leads to a high specific capacity of 3828 mAh g −1 and high reducing character (E Li + /Li = −3.05 V vs standard hydrogen electrode (SHE)). However, the Li metal reactivity toward the air and the humidity imposes several constraints, especially battery encapsulation to protect the lithium against the environment. Furthermore, the low melting point of lithium (181 °C) excludes or makes difficult specific assembling processes used to integrate the components directly on the electronic circuit, for instance, the solder-reflow process involving a temperature peak at 260 °C. Therefore, further development of thin film anode materials plays a crucial part in the development of Li-ion microbatteries. [7] Electrochemical lithium (de)intercalation in an atomic layer deposited (ALD) TiO 2 anatase thin film deposited on a planar Si /Al 2 O 3 /Pt substrate is investigated by Raman spectroscopy. An initial discharge capacity of 63 µAh cm −2 µm −1 (0.5 Li + mole −1 ) is reached at C/10 rate, which increases up to 77 µAh cm −2 µm −1 upon further cycles. An excellent capacity retention is achieved over at least 100 cycles, showing the good adherence of the ALD thin film. Raman spectra of Li x TiO 2 (0 ≤ x ≤ 0.5) thin film electrodes point to the nucleation of the orthorhombic lithiated titanate (LT) Li 0.5 TiO 2 phase from x = 0.1. This LT phase coexists with tetragonal TiO 2 in the 0.1 ≤ x ≤ 0.4 composition domain to be pure for x = 0.5. A fully reversible transformation from orthorhombic LT to tetragonal TiO 2 is observed upon the charge. The high quality of the Raman spectra allows identifying for the first time 12 modes in the 100-800 cm −1 region for the electrochemically formed LT phase. Furthermore, an appropriate Raman spectra analysis allows a reliable and quantitative determination of the thin film composition during discharge and charge. These results illustrate Raman spectroscopy is a powerful probe to scrutinize the Li insertion/extraction mechanism in TiO 2 thin films.

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Physical Vapor Deposition in Solid‐State Battery Development: From Materials to Devices

et al. 2021

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This review discusses the contribution of physical vapor deposition (PVD) processes to the development of electrochemical energy storage systems with emphasis on solid‐state batteries. A brief overview of different PVD technologies and details highlighting the utility of PVD for the fabrication and characterization of individual battery materials are provided. In this context, the key methods that have been developed for the fabrication of solid electrolytes and active electrode materials with well‐defined properties are described, and demonstrations of how these techniques facilitate the in‐depth understanding of fundamental material properties and interfacial phenomena as well as the development of new materials are provided. Beyond the discussion of single components and interfaces, the progress on the device scale is also presented. State‐of‐the‐art solid‐state batteries, both academic and commercial types, are assessed in view of energy and power density as well as long‐term stability. Finally, recent efforts to improve the power and energy density through the development of 3D‐structured cells and the investigation of bulk cells are discussed.

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High performance sputtered LiCoO2 thin films obtained at a moderate annealing treatment combined to a bias effect

Cited by 66 publications

References 47 publications

Synthesis and Characterization of LiCoO2 from Different Precursors by Sol‑Gel Method

Synthesis and Characterization of LiCoO2 from Different Precursors by Sol‑Gel Method

Electrochemical Lithium Insertion into TiO₂ Anatase ALD Thin Films for Li‐Ion Microbatteries: An Atomic‐Scale Picture Provided by Raman Spectroscopy

Physical Vapor Deposition in Solid‐State Battery Development: From Materials to Devices

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High performance sputtered LiCoO2 thin films obtained at a moderate annealing treatment combined to a bias effect

Cited by 66 publications

References 47 publications

Synthesis and Characterization of LiCoO2 from Different Precursors by Sol‑Gel Method

Synthesis and Characterization of LiCoO2 from Different Precursors by Sol‑Gel Method

Electrochemical Lithium Insertion into TiO2 Anatase ALD Thin Films for Li‐Ion Microbatteries: An Atomic‐Scale Picture Provided by Raman Spectroscopy

Physical Vapor Deposition in Solid‐State Battery Development: From Materials to Devices

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Electrochemical Lithium Insertion into TiO₂ Anatase ALD Thin Films for Li‐Ion Microbatteries: An Atomic‐Scale Picture Provided by Raman Spectroscopy