Mechanochemically Prepared Li2S–P2S5–LiBH4 Solid Electrolytes with an Argyrodite Structure

Sakuda, Atsushi; Yamauchi, Akihiro; Yubuchi, So; Kitamura, Naoto; Idemoto, Yasushi; Hayashi, Akitoshi; Tatsumisago, Masahiro

doi:10.1021/acsomega.8b00377

Cited by 44 publications

(47 citation statements)

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“…(100 − x )(0.75Li 2 S‐0.25P 2 S 5 )‐ x LiBH 4 ( x ≤ 33) was synthesized through mechanical milling technique, where the electrolyte at x = 33 showed a Li + conductivity of 1.6 × 10 −3 S cm −1 at room temperature . When x = 50, the sample formed a crystalline phase of Li 6 PS 5 ·BH 4 and exhibited an even higher Li + conductivity of 1.8 × 10 −3 S cm −1 at room temperature . The favorable ionic conductivity of borohydride–sulfide combination might originate from the large anionic frameworks with high polarizability.…”

Section: Complex Hydrides As Solid‐state Electrolytementioning

confidence: 98%

Complex Hydrides for Energy Storage, Conversion, and Utilization

2019

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functionalities and exhibit great potentials for the applications in the energy transfer chain (Figure 1).In chemistry, a hydride is a compound having negatively charged hydrogen anion. [2] Nowadays, however, hydrogenous compounds having hydrogen bonded to metals or nonmetal in ionic, metallic or covalent manner are collectively referred as hydrides. [3] Complex hydride is such a class of compound having a general formula of M(XH n ) m , where M is usually a metal cation and X is a metal or nonmetal element which sets up covalent or ionocovalent bonding with H. [4] The M[XH n ] m is H-rich and can decompose selectively to H 2 allowing complex hydrides of light-weight elements potential hydrogen storage media. As a matter of fact, since the pioneering work of Ti-catalyzed NaAlH 4 in 1997, [5] extensive investigations on hydrogen storage over alanates, [6] amide-hydride composites, [7] borohydrides, [8] amidoboranes [9] as well as metallorganic hydrides [10] were carried out and tremendous progress has been made (Figure 2). [1,4a] The break and setup of XH bonding would be endergonic and exergonic, respectively. The energy input and output in hydrogen desorption and reabsorption over a complex hydride depends strongly on its thermodynamic stability, which also offers an opportunity of using complex hydrides as thermal energy storage materials to cope up with the intermittent, fluctuating and unstable supply of renewable energies. Owning to their exclusive advantages of diversity, high energy densities and tunability, complex hydrides have been actively pursued for this application since year 2000. [11] Solid electrolytes with fast conduction of Li, Na, or Mg ions are highly demanded for all-solid-state batteries with high energy density and safety. Coincidentally, complex hydrides are composed of those cations and a relatively large sized [XH n ] anion. The coordination flexibility of the large anion with alkali or alkaline earth cation would create some favorable structural features, such as defects and/or low-barrier diffusion channels, to facilitate cation migration within the lattice of complex hydrides. [12] Starting from the finding of high Li-ion conduction in the high-temperature-phase LiBH 4 , [13] a variety of complex hydrides has been developed, some of which show superior ion conductivity to their nonhydride peers. [14] Hydrogen storage over complex hydride would undergo dihydrogen dissociation into surface H atoms followed by H Functional materials are the key enabling factor in the development of clean energy technologies. Materials of particular interest, which are reviewed herein, are a class of hydrogenous compound having the general formula of M(XH n ) m , where M is usually a metal cation and X can be Al, B, C, N, O, transition metal (TM), or a mixture of them, which sets up an iono-covalent or covalent bonding with H. M(XH n ) m is generally termed as a complex hydride by the hydrogen storage community. The rich chemistry between H and B/C/N/O/Al/TM allows complex hydrides of diverse compo...

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Section: Complex Hydrides As Solid‐state Electrolytementioning

confidence: 98%

Complex Hydrides for Energy Storage, Conversion, and Utilization

2019

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“…18 Recent efforts have led to a variety of materials such as Li6PS5X ( = Cl, Br, and I), Li10MP2S12 ( = Ge and Sn), Li7P3S11, the Li2S-P2S5 glasses and many more fast ionic conductors, enabling the concept of all-solid-state battery (ASSB) to be realistic and comparable to the conventional Li-ion batteries. [19][20][21][22][23][24][25][26][27][28][29][30] The studies on all-solid-state Li-S batteries have become prominent after Hayashi et al reported operational all-solid-state Li-S batteries, employing mechanically alloyed Li2S-P2S5 glass-ceramic electrolyte. [31][32][33][34][35] In the early stage, a significant improvement in the performance has been achieved by processing the cathode composites via ball-milling, which was attributed to the intimate contact of the cathode components.…”

Section: Introductionmentioning

confidence: 99%

Observation of Chemomechanical Failure and the Influence of Cutoff Potentials in All-Solid-State Li–S Batteries

et al. 2019

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potentials in all-solid-state Li-S batteries. ChemRxiv. Preprint.Owing to a remarkably high theoretical energy density, the lithium-sulfur (Li-S) battery has attracted significant attention as a candidate for next-generation batteries. While employing solid electrolytes can provide a new avenue for high capacity Li-S cells, all-solid-state batteries have unique failure mechanisms such as chemo-mechanical failure due to the volume changes of active materials. In this study, we investigate all-solid-state Li-S model cells with differently processed cathode composites and elucidate a typical failure mechanism stemming from irreversible Li 2 S formation in the cathode composites. Reducing the particle size is key to minimizing the influence of volume changes and a capacity of over 1000 mAh g sulfur -1 is achieved by ball-milling of the cathode composites. In addition, the long-term stability of the ball-milled cathode is investigated by varying upper and lower cut-off potentials for cycling, which results in unveiling the significantly detrimental role of the lower cut-off potential. Preventing a deep-discharge leads to a reversible capacity of 800 mAh g sulfur -1 over 50 cycles in the optimized cell. This work highlights the importance of mitigating chemo-mechanical failure using microstructural engineering as well as the influence of the cut-off potentials in all-solid-state Li-S batteries. File list (2)download file view on ChemRxiv revised manuscript.pdf (3.56 MiB) download file view on ChemRxiv Supporting Information.pdf (3.38 MiB)

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“…Surprisingly, while the conductivity of Li6PS5I5/6(BH4)1/6 was ameliorated, that of Li6PS5Br5/6(BH4)1/6 was reduced compared to the pure halide argyrodite, which can be explained by the local geometry constraints of the Li diffusion pathway. The conductivity of the Li6PS5BH4 synthesized by mechanochemical reaction is as high as 1.9 × 10−3 S cm−1 at RT [100]. The combination of the borohydride with sulphide and thio-sulphate compounds was also found to be appealing, resulting in a high ionic conductivity, a good electrochemical stability and compatibility with many electrode materials [101,102].…”

Section: Argyrodite Structure Materialsmentioning

confidence: 99%

A Review of the MSCA ITN ECOSTORE—Novel Complex Metal Hydrides for Efficient and Compact Storage of Renewable Energy as Hydrogen and Electricity

et al. 2020

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Hydrogen as an energy carrier is very versatile in energy storage applications. Developments in novel, sustainable technologies towards a CO2-free society are needed and the exploration of all-solid-state batteries (ASSBs) as well as solid-state hydrogen storage applications based on metal hydrides can provide solutions for such technologies. However, there are still many technical challenges for both hydrogen storage material and ASSBs related to designing low-cost materials with low-environmental impact. The current materials considered for all-solid-state batteries should have high conductivities for Na+, Mg2+ and Ca2+, while Al3+-based compounds are often marginalised due to the lack of suitable electrode and electrolyte materials. In hydrogen storage materials, the sluggish kinetic behaviour of solid-state hydride materials is one of the key constraints that limit their practical uses. Therefore, it is necessary to overcome the kinetic issues of hydride materials before discussing and considering them on the system level. This review summarizes the achievements of the Marie Skłodowska-Curie Actions (MSCA) innovative training network (ITN) ECOSTORE, the aim of which was the investigation of different aspects of (complex) metal hydride materials. Advances in battery and hydrogen storage materials for the efficient and compact storage of renewable energy production are discussed.

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Mechanochemically Prepared Li₂S–P₂S₅–LiBH₄ Solid Electrolytes with an Argyrodite Structure

Abstract: Solid electrolytes with compositions of (100 – x )(0.75Li 2 S·0.25P 2 S 5 )· x LiBH 4 (mol %, 0 ≤ x ≤ 100) were mechanochemically prepared from the 75Li 2 S·25P 2 S 5 (mol %) glass and LiBH 4 crystal. The samples with x ≥ 43 have crystalli… Show more

Cited by 44 publications

References 32 publications

Complex Hydrides for Energy Storage, Conversion, and Utilization

Complex Hydrides for Energy Storage, Conversion, and Utilization

Observation of Chemomechanical Failure and the Influence of Cutoff Potentials in All-Solid-State Li–S Batteries

A Review of the MSCA ITN ECOSTORE—Novel Complex Metal Hydrides for Efficient and Compact Storage of Renewable Energy as Hydrogen and Electricity

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