Applying the HSAB design principle to the 3.5 V-class all-solid-state Li-ion batteries with a chloride electrolyte

Tanibata, Naoto; Takimoto, Shuta; Aizu, Shin; Takeda, Hiromasa; Nakayama, Masanobu

doi:10.1039/d2ta05152d

Cited by 12 publications

(7 citation statements)

References 36 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…However, we revisited LMC as a prospective solid electrolyte, as our calculations indicated it should have high Li‐ion conductivity. The high‐energy mechanochemical method used for LMC synthesis promotes ionic conduction by introducing lattice defects 64,65 and yielded a white powder (Figure 4A), in agreement with the large predicted bandgap (Figure 1C). The absence of the raw material peak and the appearance of the target compound peak in the experimental XRD pattern (Figure 4B) indicated that LMC was obtained as the only phase.…”

Section: Resultssupporting

confidence: 67%

Screening chloride Li‐ion conductors using high‐throughput force‐field molecular dynamics

et al. 2023

Self Cite

View full text Add to dashboard Cite

The realization of high‐energy‐density all‐solid‐state Li‐ion batteries requires materials exhibiting both high Li‐ion conductivity and high deformability, as exemplified by Li3MCl6‐type chlorides. Herein, we optimized the classical force‐field (FF) parameters for 36 Li‐ and Cl‐containing compounds to reproduce the results of high‐precision first‐principles calculations and performed rapid FF molecular dynamics (MD) calculations to determine their Li‐ion conductivities. In addition, shear moduli were evaluated by first‐principles calculations and used as a deformability index. Li4Mn3Cl10 was selected based on its Li‐ion conductivity, stiffness, and thermodynamic stability. In accordance with the low calculated shear modulus (11.7 GPa), the cold‐pressed compact had a high relative density of 98%, which indicated good deformability. The room‐temperature conductivity (3.9 mS cm−1) was similar to that (1.6 mS cm−1) obtained by high‐precision first‐principles MD calculations. The Li‐ion conductivity of synthesized Li4Mn3Cl10 (18 µS cm−1) was relatively rather high compared to those of known chloride materials but much lower than the calculated value, which was ascribed to the fact that calculations were performed for the high‐temperature phase, whereas synthesis yielded the low‐temperature phase. The material screening method greatly increases the speed of material exploration and expands the application possibilities of chloride materials for all‐solid‐state batteries.

show abstract

Section: Resultssupporting

confidence: 67%

Screening chloride Li‐ion conductors using high‐throughput force‐field molecular dynamics

et al. 2023

Self Cite

View full text Add to dashboard Cite

show abstract

“…À . [12] The AOC-LiCl sample shows similar signal around 60-80 ppm compared to the synthesized AlOCl reference. Thus the intense NMR resonances at 75 ppm should be attributed to Figure 2h presents the experimental extended X-ray absorption fine structure (EXAFS) results of AOC-2LiCl, demonstrating the nearest neighbor Al local environment.…”

Section: Resultsmentioning

confidence: 82%

A Universal Self‐Propagating Synthesis of Aluminum‐Based Oxyhalide Solid‐State Electrolytes

Zhang,

Xu,

et al. 2024

Angewandte Chemie

View full text Add to dashboard Cite

Inorganic solid‐state electrolytes (SSEs) play a vital role in high‐energy all‐solid‐state batteries (ASSBs). However, the current method of SSE preparation usually involves high‐energy mechanical ball milling and/or a high‐temperature annealing process, which is not suitable for practical application. Here, a facile strategy is developed to realize the scalable synthesis of cost‐effective aluminum‐based oxyhalide SSEs, which involves a self‐propagating method by the exothermic reaction of the raw materials. This strategy enables the synthesis of various aluminum‐based oxyhalide SSEs with tunable components and high ionic conductivities (over 10‐3 S cm‐1 at 25 °C) for different cations (Li+, Na+, Ag+). It is elucidated that the amorphous matrix, which mainly consists of various oxidized chloroaluminate species that provide numerous sites for smooth ion migration, is actually the key factor for the achieved high conductivities. The application of these aluminum‐based oxyhalide SSEs synthesized by our approach further pushes forward their practical application considering their easy synthesis, low cost, and low weight that ensures high‐energy‐density ASSBs.

show abstract

“…[17,45,46] The excellent interfacial stability between C5Z5 and LCO cathode is thus attributed to both overlapped electrochemical window and inadequate thermodynamic driver. [56,57] Indeed, neither XPS nor EDS elemental analysis detected noticeable interfacial reactions between C5Z5 and LCO, even after prolonged cycling over 650 cycles. For all constituent elements, the XPS peaks were of the same chemical states before and after, as shown in ex situ XPS spectra on the surfaces of the C5Z5, Figure 7c-e.…”

Section: Resultsmentioning

confidence: 94%

A High‐Voltage Solid State Electrolyte Based on Spinel‐Like Chloride Made of Low‐Cost and Abundant Resources

Yu,

Huang,

et al. 2024

Adv Funct Materials

View full text Add to dashboard Cite

Recently, halide solid state electrolytes (SSEs) have received great attention owing to their fast ionic conductivity, high oxidation potential, and good chemical and electrochemical compatibility with high voltage cathode materials. However, most of reported halide SSEs contain rather rare and expensive elements, which hinders their sustainable utilizations in practical batteries. Here in this work, under the guidance of systematic modelling based on the density functional theory (DFT), a low‐cost alternative is developed through optimizing the lattice chemistry in a recently identified spinel‐like chloride Li2CrCl4 into Li5/3Cr1/3Zr1/3Cl4 for remarkably enhanced ionic conductivity and stable electrochemical window with respect to the Li‐anode. This new phase has then been synthesized successfully, delivering an ionic conductivity over 1200 times of that of the pristine phase Li2CrCl4, in addition to a high oxidation potential (up to 4.1 V vs Li/Li+) to enable outstanding interfacial compatibility with high voltage cathodes. Such a high‐voltage and fast Li‐ion conducting solid‐state electrolyte is expected to provide a highly desirable basis toward developing high energy‐density all solid‐state batteries (ASSBs) using economical and Earth‐rich elements.

show abstract

Applying the HSAB design principle to the 3.5 V-class all-solid-state Li-ion batteries with a chloride electrolyte

Abstract: All-solid-state Li-ion batteries are expected to be the next generation of batteries with a high energy density and safety. However, for Li-ion batteries to endure high-voltage operations, the decomposition of...

Cited by 12 publications

References 36 publications

Screening chloride Li‐ion conductors using high‐throughput force‐field molecular dynamics

Screening chloride Li‐ion conductors using high‐throughput force‐field molecular dynamics

A Universal Self‐Propagating Synthesis of Aluminum‐Based Oxyhalide Solid‐State Electrolytes

A High‐Voltage Solid State Electrolyte Based on Spinel‐Like Chloride Made of Low‐Cost and Abundant Resources

Contact Info

Product

Resources

About