Interface-enhanced Li ion conduction in a LiBH<sub>4</sub>–SiO<sub>2</sub> solid electrolyte

Choi, Yong Seok; Lee, Young-Su; Oh, Kyu Hwan; Cho, Young Whan

doi:10.1039/c6cp03563a

Cited by 74 publications

(93 citation statements)

References 49 publications

(75 reference statements)

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“…30,36 Another approach is to increase the ionic conductivity of LiBH 4 by mixing it with oxides or by means of nanoconfinement. [37][38][39][40] As described above, halogenation represents a successful strategy to stabilize the LiBH 4 conducting phase at RT. However, the ionic conductivity alone is not sufficient for designing effective SEs, but it must be flanked by an elevate (electro)chemical compatibility between SE and electrodes.…”

Section: Introductionmentioning

confidence: 99%

Phase Stability and Fast Ion Conductivity in the Hexagonal LiBH₄–LiBr–LiCl Solid Solution

et al. 2019

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This study shows a flexible system that offers promising candidates for Li-based solid state electrolyte. The Brsubstitution for BH 4 stabilizes the hexagonal structure of LiBH 4 at room temperature, whereas Clis soluble only at higher temperatures. Incorporate chloride in hexagonal solid solution lead to increase the energy density of the system. For the first time, a stable hexagonal solid solution of LiBH 4 containing both Cland Br-halide anions has been obtained at room temperature (RT). The LiBH 4 -LiBr-LiCl ternary phase diagram has been determined at RT by X-ray diffraction coupled with a Rietveld refinement. A solubility of up to 30% of Clin the solid solution has been established. The effect of the halogenation on the Li-ion conductivity and electrochemical stability has been investigated by Electrochemical Impedance Spectroscopy and Cyclic Voltammetry. Considering the ternary samples, h-Li(BH 4 ) 0.7 (Br) 0.2 (Cl) 0.1 compositionshowed the highest value for conductivity (1.3 × 10 −5 S/cm at 30 °C), which is about three order of magnitude higher than that for pure LiBH 4 in the orthorhombic structure. The values of Li-ion conductivity at room temperature depend only on the BH 4 content in the solid solution, suggesting that the Br/Cl ratio does not affect the defect formation energy in the structure. The chloride anion substitution in the hexagonal structure increases the activation energy, moving from about 0.45 eV for samples without Clions in the structure, up to about 0.63 eV for h-Li(BH 4 ) 0.6 (Br) 0.2 (Cl) 0.2 compositions, according with the Meyer-Neldel rule. In addition to increasing Li ion conductivity, the halogenation increase also the thermal stability of the system.Unlike for the Li-ion conductivity, Br/Cl ratio influences the electrochemical stability: a wide oxidative window of 4.04 V vs. Li + /Li is reached in the Li-Br system, while further addition of Cl is a trade-off between oxidative stability and weight reduction. The halogenation allow both binary and ternary systems operating below 120 °C, thus suggesting possible applications of these fast ion conductors as solid-state electrolyte in Li-ion batteries. Graphical AbstractKeywords: complex hydride, solid state electrolyte, Li-ion batteries

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Section: Introductionmentioning

confidence: 99%

Phase Stability and Fast Ion Conductivity in the Hexagonal LiBH₄–LiBr–LiCl Solid Solution

et al. 2019

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“…Recent interest in utilizing LiBH 4 as a solid-state electrolyte was established through the work of Orimo [4], who demonstrated that the ionic conductivity of lithium can be greater than 1 mS/cm at temperatures above the orthorhombic to hexagonal phase transition that occurs at 380 K [5]. This work has been expanded to achieve high conductivity in LiBH 4 based solid electrolytes through the addition of Li halide salts [6][7][8], nanoconfinement [9][10][11][12], nanoionic destabilization [13,14], ion substitution [15][16][17][18][19][20][21], and eutectic formation [22].…”

Section: Introductionmentioning

confidence: 99%

Investigation of the Reversible Lithiation of an Oxide Free Aluminum Anode by a LiBH4 Solid State Electrolyte

et al. 2017

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Abstract:In this study, we analyze and compare the physical and electrochemical properties of an all solid-state cell utilizing LiBH 4 as the electrolyte and aluminum as the active anode material. The system was characterized by galvanostatic lithiation/delithiation, cyclic voltammetry (CV), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), Raman spectroscopy, electrochemical impedance spectroscopy (EIS), and scanning electron microscopy (SEM). Constant current cycling demonstrated that the aluminum anode can be reversibly lithiated over multiple cycles utilizing a solid-state electrolyte. An initial capacity of 895 mAh/g was observed and is close to the theoretical capacity of aluminum. Cyclic voltammetry of the cell was consistent with the constant current cycling data and showed that the reversible lithiation/delithiation of aluminum occurs at 0.32 V and 0.38 V (vs. Li + /Li) respectively. XRD of the aluminum anode in the initial and lithiated state clearly showed the formation of a LiAl (1:1) alloy. SEM-EDS was utilized to examine the morphological changes that occur within the electrode during cycling. This work is the first example of reversible lithiation of aluminum in a solid-state cell and further emphasizes the robust nature of the LiBH 4 electrolyte. This demonstrates the possibility of utilizing other high capacity anode materials with a LiBH 4 based solid electrolyte in all-solid-state batteries.

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“…The narrow‐shaped 7 Li NMR (RT) spectrum of MCM41–LiBH 4 ‐91 resembled that of highly conductive hexagonal LiBH 4 . The fast Li + mobility in MCM41–LiBH 4 ‐91 may be mainly attributed to the interface interactions between nano‐LiBH 4 and SiO 2 , which was further proved by Choi et al They compared the ionic conductivities of the melt‐infiltrated porous‐LiBH 4 –MCM41 (MI‐LM) and ball‐milled‐LiBH 4 –fumed‐SiO 2 (BM‐LF) ( Figure a), and the ionic conductivity of the BM‐LF sample rivals that of MI‐LM, reaching 10 −4 S cm −1 . Note that two conspicuous differences exist between the MI‐LM and BM‐LF composites: i) the Brunauer–Emmett–Teller (BET) surface area for porous MCM‐41 (946 m 2 g −1 ) is about threefold that for nonporous fumed silica (362 m 2 g −1 ); and ii) LiBH 4 is nanoconfined in pure porous MCM‐41, but not in fumed silica.…”

Section: Progress Of Borohydride‐based Solid‐state Electrolytes and Amentioning

confidence: 73%

“…Interface Engineering Strategy (“Filler Effect”) : de Jongh and co‐workers studied the ionic conductivity of nanoconfined LiBH 4 in ordered mesoporous silica MCM‐41 scaffolds (4 nm pores) . MCM41–LiBH 4 ‐91 delivered an impressive ionic conductivity of 0.1 mS cm −1 at 313 K, which is 1000 times higher than for bulk LiBH 4 at the same temperature . In comparison with the activation energies of orthorhombic and hexagonal LiBH 4 (0.69 and 0.53 eV), that of the MCM41–LiBH 4 ‐91 composite was reduced to 0.43 eV, illustrating the smaller impact of temperature fluctuations on the ionic conductivity of MCM41–LiBH 4 ‐91.…”

Section: Progress Of Borohydride‐based Solid‐state Electrolytes and Amentioning

confidence: 99%

“…a) Temperature dependence of ionic conductivity for various modified LiBH 4 materials, which include melt‐infiltration LiBH 4 ‐MCM41 (MI‐LM) and ball‐milled LiBH 4 ‐fumed SiO 2 (BM‐LF) . b) Temperature dependence of ionic conductivity for 70 wt% nano‐LiBH 4 –30 wt% SiO 2 , 40 wt% nano‐LiBH 4 –60 wt% SiO 2 , and bulk LiBH 4 measured using a Au blocking electrode.…”

Section: Progress Of Borohydride‐based Solid‐state Electrolytes and Amentioning

confidence: 99%

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Borohydride‐Scaffolded Li/Na/Mg Fast Ionic Conductors for Promising Solid‐State Electrolytes

et al. 2018

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devices and for various types of consumer electronics. All-solid-state rechargeable batteries (ASSBs) utilizing solid-electrolyte separators rather than combustible liquid electrolytes possess the inherent advantages of enhanced safety and stability for state-of-the-art battery technologies. [1] Recently, ASSBs have attracted a resurgence of interest as ideal candidates for the next generation of electrochemicalenergy-storage devices. The superiority of ASSBs could be ascribed to the distinctive attributes of solid-state electrolytes (SSEs), including high Li-ion transference number and safety, and comparable ionic conductivity to their liquid counterparts. [2] The adoption of SSEs could offer new opportunities for the high-temperature electrical-energy-storage market and pave the way for the utilization of high-capacity electrodes, such as Li, Na, and sulfur. [2c,3] In contrast, in conventional batteries employing liquid electrolytes, the highcapacity electrodes may meet with detrimental side reactions, causing problems such as dendrite growth, reactivity, and/ or dissolution in the solvent. [4,5] With the construction of rigid solid electrolyte separators and stable interfaces in ASSBs, dendrite growth can be effectively mitigated, thus improving the safety of the batteries. [4,6] Owing to these benefits, in battery research, the number of studies on fabricating superionic SSEs has grown rapidly. Despite great progress gained these years, issues Borohydride solid-state electrolytes with room-temperature ionic conductivity up to ≈70 mS cm −1 have achieved impressive progress and quickly taken their place among the superionic conductive solid-state electrolytes. Here, the focus is on state-of-the-art developments in borohydride solid-state electrolytes, including their competitive ionic-conductive performance, current limitations for practical applications in solid-state batteries, and the strategies to address their problems. To open, fast Li/Na/Mg ionic conductivity in electrolytes with BH 4 − groups, approaches to engineering borohydrides with enhanced ionic conductivity, and later on the superionic conductivity of polyhedral borohydrides, their correlated conductive kinetics/thermodynamics, and the theoretically predicted high conductive derivatives are discussed. Furthermore, the validity of borohydride pairing with coated oxides, sulfur, organic electrodes, MgH 2 , TiS 2 , Li 4 Ti 5 O 12 , electrode materials, etc., is surveyed in solid-state batteries. From the viewpoint of compatible cathodes, the stable electrochemical windows of borohydride solid-state electrolytes, the electrode/electrolyte interface behavior and battery device design, and the performance optimization of borohydride-based solid-state batteries are also discussed in detail. A comprehensive coverage of emerging trends in borohydride solid-state electrolytes is provided and future maps to promote better performance of borohydride SSEs are sketched out, which will pave the way for their further development in the field of energy stora...

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Interface-enhanced Li ion conduction in a LiBH₄–SiO₂ solid electrolyte

Cited by 74 publications

References 49 publications

Phase Stability and Fast Ion Conductivity in the Hexagonal LiBH₄–LiBr–LiCl Solid Solution

Phase Stability and Fast Ion Conductivity in the Hexagonal LiBH₄–LiBr–LiCl Solid Solution

Investigation of the Reversible Lithiation of an Oxide Free Aluminum Anode by a LiBH4 Solid State Electrolyte

Borohydride‐Scaffolded Li/Na/Mg Fast Ionic Conductors for Promising Solid‐State Electrolytes

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Interface-enhanced Li ion conduction in a LiBH4–SiO2 solid electrolyte

Cited by 74 publications

References 49 publications

Phase Stability and Fast Ion Conductivity in the Hexagonal LiBH4–LiBr–LiCl Solid Solution

Phase Stability and Fast Ion Conductivity in the Hexagonal LiBH4–LiBr–LiCl Solid Solution

Investigation of the Reversible Lithiation of an Oxide Free Aluminum Anode by a LiBH4 Solid State Electrolyte

Borohydride‐Scaffolded Li/Na/Mg Fast Ionic Conductors for Promising Solid‐State Electrolytes

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Resources

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Interface-enhanced Li ion conduction in a LiBH₄–SiO₂ solid electrolyte

Phase Stability and Fast Ion Conductivity in the Hexagonal LiBH₄–LiBr–LiCl Solid Solution

Phase Stability and Fast Ion Conductivity in the Hexagonal LiBH₄–LiBr–LiCl Solid Solution