Compatibility assessment of solid ceramic electrolytes and active materials based on thermal dilatation for the development of solid-state batteries

Bertrand, Marc; Rousselot, Steeve; Aymé‐Perrot, David; Dollé, Mickaël

doi:10.1039/d0ma00743a

Cited by 15 publications

(13 citation statements)

References 92 publications

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“…Unfortunately, the heat treatment causes irreversible degradation reactions at the electrolyte–electrode interface resulting in increased interfacial resistances. [ 10–12 ] In contrast, thiophosphate‐based SSEs are rather soft and, thus, provide good interfacial contact to CAMs. Furthermore, they exhibit high ionic conductivities of above 20 mS cm −1 at room temperature [ 3,13 ] making them more attractive for applications in ASSBs.…”

Section: Introductionmentioning

confidence: 99%

A Dry‐Processed Al₂O₃/LiAlO₂ Coating for Stabilizing the Cathode/Electrolyte Interface in High‐Ni NCM‐Based All‐Solid‐State Batteries

Negi

Yusim

Pan

et al. 2021

Adv Materials Inter

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Due to their high theoretical energy densities and superior safety, thiophosphate‐based all‐solid‐state batteries (ASSBs) are considered as promising power source for electric vehicles. However, for large‐scale industrial applications, interfacial degradation between high‐voltage cathode active materials (CAMs) and solid‐state electrolytes (SSEs) needs to be overcome with a simple, cost‐effective solution. Surface coatings, which prevent the direct physical contact between CAM and SSE and in turn stabilize the interface, are considered as promising approach to solve this issue. In this work, an Al2O3/LiAlO2 coating for Li(Ni0.70Co0.15Mn0.15)O2 (NCM) is tested for ASSBs. The coating is obtained from a recently developed dry coating process followed by post‐annealing at 600 °C. Structural characterization reveals that the heat treatment results in the formation of a dense Al2O3/LiAlO2 coating layer. Electrochemical evaluations confirm that the annealing‐induced structural changes are beneficial for ASSB. Cells containing Al2O3/LiAlO2‐coated NCM show a significant improvement of the rate capability and long‐term cycling performance compared to those assembled from Al2O3‐coated and uncoated cathodes. Moreover, electrochemical impedance spectroscopy analysis shows a decreased cell impedance after cycling indicating a reduced interfacial degradation for the Al2O3/LiAlO2‐coated electrode. The results highlight a promising low‐cost and scalable CAM coating process, enabling large‐scale cathode coating for next‐generation ASSBs.

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Section: Introductionmentioning

confidence: 99%

A Dry‐Processed Al₂O₃/LiAlO₂ Coating for Stabilizing the Cathode/Electrolyte Interface in High‐Ni NCM‐Based All‐Solid‐State Batteries

Negi

Yusim

Pan

et al. 2021

Adv Materials Inter

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“…The top-view SEM image of the non-cycled area in Figure c shows thin fractures on the electrode surface only visible with the d-BSE mode due to its element mass-sensitive contrast. These thin fractures are formed during the annealing at high temperatures due to thermal residual stress derived from the mismatch in the thermal expansion coefficient between the Pt layer and the ceramic transition metal oxide and the high density of the deposited electrode layers. The pores or unbonded areas at the LNMO/Pt interface in Figure d are typically found at the interface of ceramic/metal joints when the material is cooled down from the bonding temperature to room temperature .…”

Section: Resultsmentioning

confidence: 99%

Revealing the Role of Electrolyte Salt Decomposition in the Structural Breakdown of LiNi_0.5Mn_1.5O₄

Cazorla Soult,

Pitillas Martinez,

Marcoen

et al. 2023

J. Phys. Chem. C

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Spinel LiNi0.5Mn1.5O4 (LNMO) is one of the most promising cobalt-free high-performance electrodes for boosting energy density in future Li-ion batteries and microbatteries. However, its high operating potential of over 4.7 V vs Li+/Li leads to undesired secondary reactions derived from the oxidative electrolyte decomposition that cause active material dissolution and structural degradation. Even though great effort has been put into understanding the decomposition products in the liquid electrolyte, the effects that the electrolyte decomposition has on the electrode integrity are often overlooked. Sputtered thin film electrodes with simplified geometries and composition are ideal model systems to deconvolute the effects and isolate the influencing factors. The influence of electrolyte salt on the electrochemical performance and chemical stability is analyzed here on thin film LNMO employing spectroscopic and microscopic tools. The negative effects of electrolyte decomposition on cyclability and electrode composition are noticeable when using LiPF6 salt, but the degradation with an LiClO4-based electrolyte was found to be more severe. LiClO4 decomposing in the operating potential range is associated with the generation of Cl compounds that etch the spinel oxide dissolving transition metal, diminishing the available intercalating active material and triggering the electrode breakdown. Acidification of the electrolyte occurs during repeated cycling, and the proton source is attributed to the hydrogen abstraction from the solvent oxidation induced by the high operating voltages. Our results suggest that electrolyte decomposition could trigger significant proton intercalation and surface reconstruction in the electrode, ultimately causing its electrochemical and structural breakdown.

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“…Phase-pure LATP was produced via a hydrothermal process. , TiO 2 (99% Sigma-Aldrich) was first stirred in an aqueous solution containing phosphoric acid (85%) at 160 °C. Then, Al(OH) 3 (Fisher Scientific) and LiOH (98% Sigma-Aldrich) were added after cooling to 80 °C.…”

Section: Methodsmentioning

confidence: 99%

“…Lithium exchange with the SIL is expected to improve ionic conductivity relative to what can be obtained with the ISE alone. The SIL LiG 4 TFSI was chosen due to its similarity with poly(ethylene oxide) (PEO), a commonly used SPE, as tetraethylene glycol dimethyl ether (G4) coordinates to the Li + ion like a crown ether, forming a complex cation [Li(G 4 )] + . − Ceramic powders (LATP, aluminum-doped LLZO, and LSTH) are mixed with a small amount of LiG 4 TFSI (10% by weight) and pressed to form a solid pellet, which is then presented as a solid-state electrolyte. The authors wish to clarify that the tested materials remain in the solid state after the addition of liquid electrolytes and do not have properties similar to those of gel electrolytes.…”

Section: Introductionmentioning

confidence: 99%

NMR Study of Lithium Transport in Liquid–Ceramic Hybrid Solid Composite Electrolytes

Foran

Méry

Bertrand

et al. 2022

ACS Appl. Mater. Interfaces

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Despite their high conductivity, factors such as being fragile enough to face processing issues and interfacial incompatibility with lithium electrodes are some of the main drawbacks hindering the commercialization of inorganic (mainly oxide-based) solid electrolytes for use in all-solid-state lithium batteries. To this end, strategies such as the addition of solid polymer electrolytes have been proposed to improve the electrode−electrolyte interface. Hybrid electrolytes, which are usually composed of ceramic particles dispersed in a polymer, generally have a better affinity with electrodes and higher ionic conductivity than pure inorganic electrolytes. However, a significant downside of this strategy is that differences in lithium transportability between electrolyte layers can result in the formation of a high interfacial energy barrier across the cell. One strategy to ensure sufficient "wetting" of ceramics is to incorporate a liquid electrolyte directly into the solid inorganic electrolyte resulting in the formation of a hybrid liquid−ceramic electrolyte. To this end, liquid−ceramic hybrid electrolytes were prepared by adding LiG 4 TFSI, a solvate ionic liquid (SIL), to garnet, NASICON, and perovskite-type ceramic electrolytes. Although SIL addition resulted in increased ionic conductivity, comparisons between the pure SIL and the hybrid systems revealed that improvements were due to the SIL alone. A thorough investigation of the hybrid systems by solid-state nuclear magnetic resonance (NMR) revealed little to no lithium exchange between the ceramic and the SIL. This confirms that lithium conductivity preferentially occurs through the SIL in these hybrid systems. The primary role of the ceramic is to provide mechanical strength.

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Compatibility assessment of solid ceramic electrolytes and active materials based on thermal dilatation for the development of solid-state batteries

Abstract: Assembling an all ceramic solid-state battery (ACSSB) using inorganic oxide electrolytes is challenging. The battery must have a continuous layered structure with a thin dense electrolyte separator and interfaces between...

Cited by 15 publications

References 92 publications

A Dry‐Processed Al₂O₃/LiAlO₂ Coating for Stabilizing the Cathode/Electrolyte Interface in High‐Ni NCM‐Based All‐Solid‐State Batteries

A Dry‐Processed Al₂O₃/LiAlO₂ Coating for Stabilizing the Cathode/Electrolyte Interface in High‐Ni NCM‐Based All‐Solid‐State Batteries

Revealing the Role of Electrolyte Salt Decomposition in the Structural Breakdown of LiNi_0.5Mn_1.5O₄

NMR Study of Lithium Transport in Liquid–Ceramic Hybrid Solid Composite Electrolytes

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Compatibility assessment of solid ceramic electrolytes and active materials based on thermal dilatation for the development of solid-state batteries

Abstract: Assembling an all ceramic solid-state battery (ACSSB) using inorganic oxide electrolytes is challenging. The battery must have a continuous layered structure with a thin dense electrolyte separator and interfaces between...

Cited by 15 publications

References 92 publications

A Dry‐Processed Al2O3/LiAlO2 Coating for Stabilizing the Cathode/Electrolyte Interface in High‐Ni NCM‐Based All‐Solid‐State Batteries

A Dry‐Processed Al2O3/LiAlO2 Coating for Stabilizing the Cathode/Electrolyte Interface in High‐Ni NCM‐Based All‐Solid‐State Batteries

Revealing the Role of Electrolyte Salt Decomposition in the Structural Breakdown of LiNi0.5Mn1.5O4

NMR Study of Lithium Transport in Liquid–Ceramic Hybrid Solid Composite Electrolytes

Contact Info

Product

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A Dry‐Processed Al₂O₃/LiAlO₂ Coating for Stabilizing the Cathode/Electrolyte Interface in High‐Ni NCM‐Based All‐Solid‐State Batteries

A Dry‐Processed Al₂O₃/LiAlO₂ Coating for Stabilizing the Cathode/Electrolyte Interface in High‐Ni NCM‐Based All‐Solid‐State Batteries

Revealing the Role of Electrolyte Salt Decomposition in the Structural Breakdown of LiNi_0.5Mn_1.5O₄