Na3NH2B12H12 as high performance solid electrolyte for all-solid-state Na-ion batteries

He, Lin; Lin, Huaijun; Li, Hai Feng; Filinchuk, Yaroslav; Zhang, Junjun; Liu, Ying; Yang, Mingyang; Hou, Yan; Deng, Yonghong; Li, Haiwen; Shao, Huaiyu; Wang, Liping; Lu, Zhouguang

doi:10.1016/j.jpowsour.2018.06.054

Cited by 37 publications

(30 citation statements)

References 27 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Unlike order‐disorder‐governed dodeca‐ and decaboranes, the cationic mobility in Na 3 BH 4 B 12 H 12 or (Li 0.7 Na 0.3 ) 3 BH 4 B 12 H 12 is not entropically activated, thus requiring no HT phase transition for ionic conduction . Na 3 NH 2 B 12 H 12 was also demonstrated to have a much higher ionic conductivity than its parent compounds . Partial substitution of H in Na 2 B 12 H 12 by I to form Na 2 B 12 H 12‐ x I x resulted in positive effect on ionic conductivity, reaching as high as 0.1 S cm −1 at 87 °C 152b.…”

Section: Complex Hydrides As Solid‐state Electrolytementioning

confidence: 98%

“…Compositing higher boranes with amides, borohydrides, halides, etc., were found effective to enhance their ionic conductivity. Unlike order‐disorder‐governed dodeca‐ and decaboranes, the cationic mobility in Na 3 BH 4 B 12 H 12 or (Li 0.7 Na 0.3 ) 3 BH 4 B 12 H 12 is not entropically activated, thus requiring no HT phase transition for ionic conduction .…”

Section: Complex Hydrides As Solid‐state Electrolytementioning

confidence: 99%

See 1 more Smart Citation

Complex Hydrides for Energy Storage, Conversion, and Utilization

2019

View full text Add to dashboard Cite

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...

show abstract

Section: Complex Hydrides As Solid‐state Electrolytementioning

confidence: 98%

Section: Complex Hydrides As Solid‐state Electrolytementioning

confidence: 99%

Complex Hydrides for Energy Storage, Conversion, and Utilization

2019

View full text Add to dashboard Cite

show abstract

“…6,7 Lithium and sodium hydro-closo-borates ([B n H n ] 2− ) and hydro-closomonocarbaborates ([CB n−1 H n ] − ) show even higher thermal stability and ionic conductivity in their respective HT phases. [8][9][10][11] The HT phase of hydroborates can be stabilized at lower temperatures by ball milling, 12,13 partial dehydrogenation, 14 nano confinement, 15,16 or anion/cation substitution, [17][18][19][20][21][22][23][24][25][26][27] which leads to the increase in the room-temperature ionic conductivity. For instance, Na 4 (B 12 H 12 )(B 10 H 10 ) (also named Na 2 (B 12 H 12 ) 0.5 (B 10 H 10 ) 0.5 in literature), an equimolar mixture of Na 2 B 12 H and Na 2 B 10 H , exhibits a room-temperature ionic conductivity of 10 −3 S cm −1 by stabilizing the HT phase of Na 2 B 10 H 10 .…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Oxidative Stability of Hydroborate-Based Solid-State Electrolytes

Asakura

Duchêne

Kühnel

et al. 2019

ACS Appl. Energy Mater.

107

View full text Add to dashboard Cite

We report a robust methodology based on linear sweep voltammetry to determine experimentally the electrochemical oxidative stability of hydroborate-based solid-state electrolytes for all-solid-state batteries. To accelerate kinetics and improve the sensitivity to decomposition, we explore different solid-state electrolyte/carbon composites and employ a low scan rate of 10 μV s −1. Using LiBH 4 as a model system, we show that proper selection of the conductive carbon and its ratio in the composite are important for an accurate determination of the intrinsic oxidative stability. This method is robust with respect to the choice of the current collector material and the ionic conductivity of the solid-state

show abstract

“…Na 3 BH 4 B 12 H 12 was stable at RT and showed an electrochemical window up to 10 V (versus Na 1 /Na) [60]. This study was followed by the discovery of the high Na 1 cation mobility in Na 3 NH 2 B 12 H 12 , another mixed-anion borane, for which r 5 1.0 Â 10 À4 S/cm, at 372 K. The composition also revealed high electrochemical (10 V versus Na/Na 1 ) and thermal stability (up to 593 K) [61].…”

Section: Borohydridesmentioning

confidence: 94%

“…The Na 3 NH 2 B 12 H 12 complex hydride, obtained from metal amide and higher borane, has been recently employed as SSE in the all-solid-state NIB, with the composite TiS 2 /Na 3 NH 2 B 12 H 12 cathode and the Na anode [61]. The cell was reversibly operated at 535 K and a rate of 0.1C, over 200 cycles.…”

Section: Na-ion Batteriesmentioning

confidence: 99%