An insight into coordination ability of dicyanoimidazolato anions toward lithium in presence of acetonitrile. Crystal structures of novel lithium battery electrolyte salts

Dranka, Maciej; Niedzicki, Leszek; Kasprzyk, Marta; Marcinek, Marek; Wieczorek, W.; Zachara, Janusz

doi:10.1016/j.poly.2012.12.022

Cited by 20 publications

(26 citation statements)

References 24 publications

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“…9 Changes observed in ionic conductivity 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 Increasing the number of solvent donor centers per lithium cation, which can be expressed by an average Li:O molar ratio (see Table 1) leads to the separation of lithium cations and TDI anions. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 11 An alternative to dimeric structural motif is a chain utilizing two diagonally placed nitrogen donor centers.…”

Section: Resultsmentioning

confidence: 99%

Structural Studies of Lithium 4,5-Dicyanoimidazolate–Glyme Solvates. 1. From Isolated Free Ions to Conductive Aggregated Systems

et al. 2015

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In this paper, we present complementary series of crystal structures of lithium salts containing 4,5-dicyanoimidazolato anions substituted with perfluoroalkyl groups. Singlecrystal X-ray analysis of ten adducts with aprotic solvents: glymes -dimethyl ethers of poly(ethylene glycols) -and crown ethers have been performed to correlate their molecular structures and properties with spectroscopic and thermal data. Comprehensive structure analysis of crystalline materials reveals valuable information about coordination ability of substituted 4,5-dicyanoimidazolato anions and provides the basis to develop the model of poly(ethylene oxide) electrolytes and liquid systems. Presented results reveal new aggregation modes at high concentrations of lithium salts involving releasing cations by self-assembly of anionic subnetwork and shed some light on electrochemical performance of TDI anions.

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Section: Resultsmentioning

confidence: 99%

Structural Studies of Lithium 4,5-Dicyanoimidazolate–Glyme Solvates. 1. From Isolated Free Ions to Conductive Aggregated Systems

et al. 2015

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“…Recent success of imidazole-derived lithium salts [13] and stressed as ''tailor made'' salts, notably LiTDI (lithium 4,5-dicyano-2-(trifluoromethyl)imidazole), has encouraged us for lithium battery applications [14]. For exploring the properties of this salt, only a few publications are available [15,16]. In compare with many other lithium salts, LiTDI is fully stable in the presence of moisture [17].…”

Section: Introductionmentioning

confidence: 99%

New solid polymer electrolytes (PEO20–LiTDI–SN) for lithium batteries: structural, thermal and ionic conductivity studies

Polu

Rhee

Kim

2015

J Mater Sci: Mater Electron

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Solid polymer electrolyte films based on Poly(ethylene oxide) (PEO) have been prepared by solution casting technique using acetonitrile as a solvent. Succinonitrile (SN) was used as a plasticizer and lithium 4,5-dicyano-2-(trifluoromethyl)imidazole (LiTDI) as a doping salt. The following techniques such as X-ray diffraction (XRD), differential scanning calorimetry (DSC), thermo gravimetric analysis, AC-impedance analysis and linear sweep voltametry have been employed to characterize the prepared solid polymer electrolyte films. The crystalline and amorphous nature of polymer electrolytes was confirmed by XRD and DSC analysis respectively. The electrolyte film with 30 wt% of SN was thermally stable up to 260°C. The ionic conductivities of polymer electrolyte films were calculated from the AC-impedance analysis. The undoped PEO 20 -LiTDI electrolyte exhibited the ionic conductivity of 9.64 9 10 -7 S cm -1 and this value was increased to 2.83 9 10 -5 S cm -1 when 30 wt% of succinonitrile was added to PEO 20 -LiTDI electrolyte at 23°C. The temperature dependent conductivity obeys Arrhenius behavior and the activation energy decreased to 0.264 eV. The electrochemical stability of the optimum conducting composition is 4.3 V, which make it attractive as electrolyte for Li battery.

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“…Lithium cations adopt distorted tetrahedral geometry and are linked via two bridging dicyanoimidazolato ligands forming characteristic dimeric units with a ten-membered Li(NCCN) 2 Li ring. 32 The central ring is planar with r.m.s. deviations from planarity of 0.012 Å for both 2 and 3.…”

Section: Resultsmentioning

confidence: 99%

Lithium cation conducting TDI anion-based ionic liquids

Niedzicki

Karpierz

Zawadzki

et al. 2014

Phys. Chem. Chem. Phys.

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In this paper we present the synthesis route and electrochemical properties of new class of ionic liquids (ILs) obtained from lithium derivate TDI (4,5-dicyano-2-(trifluoromethyl)imidazolium) anion. ILs synthesized by us were EMImTDI, PMImTDI and BMImTDI, i.e. TDI anion with 1-alkyl-3-methylimidazolium cations, where alkyl meant ethyl, propyl and butyl groups. TDI anion contains fewer fluorine atoms than LiPF6 and thanks to C-F instead of P-F bond, they are less prone to emit fluorine or hydrogen fluoride due to the rise in temperature. Use of IL results in non-flammability, which is making such electrolyte even safer for both application and environment. The thermal stability of synthesized compounds was tested by DSC and TGA and no signal of decomposition was observed up to 250 °C. The LiTDI salt was added to ILs to form complete electrolytes. The structures of tailored ILs with lithium salt were confirmed by X-ray diffraction patterns. The electrolytes showed excellent properties regarding their ionic conductivity (over 3 mS cm(-1) at room temperature after lithium salt addition), lithium cation transference number (over 0.1), low viscosity and broad electrochemical stability window. The ionic conductivity and viscosity measurements of pure ILs are reported for reference.

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An insight into coordination ability of dicyanoimidazolato anions toward lithium in presence of acetonitrile. Crystal structures of novel lithium battery electrolyte salts

Cited by 20 publications

References 24 publications

Structural Studies of Lithium 4,5-Dicyanoimidazolate–Glyme Solvates. 1. From Isolated Free Ions to Conductive Aggregated Systems

Structural Studies of Lithium 4,5-Dicyanoimidazolate–Glyme Solvates. 1. From Isolated Free Ions to Conductive Aggregated Systems

New solid polymer electrolytes (PEO20–LiTDI–SN) for lithium batteries: structural, thermal and ionic conductivity studies

Lithium cation conducting TDI anion-based ionic liquids

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