Hybrid solid electrolytes with excellent electrochemical properties and their applications in all-solid-state cells

Three types of inorganic electrolytes [Li₁₀GeP₂S₁₂ (LGPS), 75Li₂S·24P₂S₅·1P₂O₅ (LPOS), Li_1.5Al_0.5Ge_1.5(PO₄)₃ (LAGP)] with different particle sizes and electrochemical properties are selected as active fillers incorporated into poly(ethylene oxide) (PEO) matrix to fabricate hybrid solid electrolytes. The optimum composition of each filler is found in consideration of ionic conductivity. Their electrochemical characteristics are investigated. The optimal conductivities are 1.60 × 10^?5, 1.18 × 10^?5, and 2.12 × 10^?5 S cm^?1 at room temperature for PEO-1%LGPS, PEO-1%LPOS, and PEO-20%LAGP, respectively. The electrochemical stability windows of these hybrid solid electrolytes are all above 5 V (vs. Li⁺/Li). The results show that these fillers have positive effects on the ionic conductivity, lithium ion transference number, and electrochemical stability. The relationship between the type of filler and electrochemical properties has been investigated. All-solid-state cells LiFePO₄/Li are fabricated and present fascinating electrochemical performance with high capacity retention and good cycling stability. This work provides promising electrolytes prepared by a simple method.     

Comparative study of solid-state reaction and sol-gel process for synthesis of Zr-doped Li<Subscript>0.5</Subscript>La<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript> solid electrolytes

We investigated the synergistic influences of synthesis methods (solid-state reaction vs. sol-gel process) and Zr⁴⁺ doping on the structure and ionic conductivity of perovskite-structured Li_0.5La_0.5TiO₃ (LLTO) solid electrolytes. The lithium-ion conductivity of Li_0.5La_0.5Ti_1???x Zr _x O₃ ceramic specimens was evaluated as a function of x value and compared carefully between those two synthesis methods. Regarding the conductivity, sol-gel process is better for the synthesis of LLTO than solid-state reaction. As a result, the highest grain conductivity is obtained in the sol-gel-derived pure LLTO sample with x?=?0, reaching 1.10?×?10^?3 S?·?cm^?1. Partial substitution of Zr⁴⁺ enlarges the LLTO’s grain aggregate size and increases the total superficial area of aggregates. Consequently, Zr⁴⁺ substitution not only affects the grain (bulk) conductivity, but more importantly, also improves the grain boundary conductivity and the total conductivity. The highest total conductivity is 5.84?×?10^?5 S?·?cm^?1 with x?=?0.04 by sol-gel process.     

Characterization of solid electrolytes prepared from ionic glass and ionic liquid for all-solid-state lithium batteries

Glassy solid electrolytes were prepared by combining the 50Li₂SO₄·50Li₃BO₃ (mol%) ionic glass and the 1-ethyl-3-methyl-imidazolium tetrafluoroborate ([EMI]BF₄) ionic liquid. High-energy ball milling was carried out for the mixture of the inorganic ionic glass and the organic ionic liquid. The ambient temperature conductivity of the glass electrolyte with 10 mol% [EMI]BF₄ was 10⁻⁴ S cm⁻¹, which was three orders of magnitude higher than that of the 50Li₂SO₄·50Li₃BO₃ glass. The addition of [EMI]BF₄ to the ionic glass decreased glass transition temperature (T_g) of the glass and the decrease of T_g is closely related to the enhancement of conductivity of the glass. Morphology and local structure of the glass electrolyte was characterized. The dissolution of an ionic liquid in an ionic glass with Li⁺ ion conductivity is a novel way to developing glass electrolytes for all-solid-state lithium secondary batteries.     

Proton and Li-7 NMR study on the effect of the OH− anion upon the Li+-ion conduction in the solid solution Li5NI2LiOH

From ¹H and ⁷LiNMR relaxation times T₁, T₂ and T_1ρ in Li₅NI₂ and the solid solution Li₅NI₂?0.77LiOH, the diffusive motion of the Li⁺ ion was studied to make clear the role of the OH^? ion in improving the Li⁺ ionic conduction. At temperatures as low as 140 K, each Li⁺ ion jumps among four available positions. Its activation energies are 9.26 and 11.8 kJ mol^?1 for Li₅NI₂ and Li₅NI₂?0.77LiOH, respectively. Diffusive motion was observed in T₂ and T_1ρ above 240 K. The mode of the cation distribution and the diffusion mechanism are not affected by the presence of the OH^? anion. The most noticeable fact is that the OH^? ion is substituted selectively for the N^3? ion that is the nearest neighbour of the Li⁺ ion. This selective substitution increases the concentration of the Li⁺ vacancy most effectively up to 4.2% of the total Li positions. At the same time it diminishes the strong attractive force of the N^3? anion binding the Li⁺ ion to the position, and thus the activation energy. For the diffusion, an anomalously low attempt frequency of 3&#x0303; × 10⁹Hz was obtained from T_1ρ, while the normal value of 4.8 × 10¹²Hz was obtained from the ionic conductivity. The large discrepancy was attributed to the collective nature of the Li⁺ diffusive motion.     

Ionic conductivity of pure and doped Li3N

The ionic conductivity of Li₃N crystals doped with various metal ions (magnesium, copper and aluminum) or hydrogen has been investigated. The metal ions have a negative effect on the conductivity whereas hydrogen increases it. The intrinsic Li⁺ ionic conductivity of pure Li₃N is (2·-4)×10^-4Ω^-1cm^-1 at room temperature with an activation energy of 0.26?0.27 eV. Doping with hydrogen to a maximum level of 0.5?1.0 atom% results in a conductivity of 6×10^-3Ω^-1cm^-1 and an activation energy which has been lowered to 0.20 eV. A model is proposed for the action of hydrogen whereby the Li-N bonds next to an NH^2- group are weakened thereby facilatating the creation of Li⁺ Frenkel defects and the vacancy migration. Hydrogen-doped Li₃N is termed an enhanced intrinsic conductor.     

Li4SiO4-Li3VO4赝二元系和Li4GeO4-Li4SiO4-Li3VO4赝三元系中新的锂离子导体

本文在室温到300℃的温度范围内研究了Li₄SiO₄-Li₃VO₄和Li₄GeO₄-Li₄SiO₄-Li₃VO₄体系中的离子导电性,发现γ_II相固溶体Li_3+xV_1-xSi_xO₄是好的锂离子导体。所研究的成分中Li_3.3V_0.7Si_0.3O₄的离子电导率最高,室温下为1×10^-5Ω^-1·cm^-1,在42—192℃的电导激活能为0.36eV,电子电导率可以忽略,因而这是迄今所发现的最好的锂离子导体之一。粗略确定了Li₄GeO₄-Li₄SiO₄-Li₃VO₄三元系中电导率高的范围,发现在Li_3.5V_0.5Ge_0.5O₄中Si部分取代Ge可以使电导率进一步提高,Li_3.5V_0.5Ge_0.4Si_0.1O₄的室温电导率可达1.3×10^-5Ω^-1·cm^-1,电导激活能为0.40eV。 关键词：     

Temperature dependence of Mn2+ EPR in Sn2P2S6 near the phase transition

The X-band EPR spectrum of Mn²⁺ in Sn₂P₂S₆ was studied in the temperature rangeT=223–363 K. At room temperature the spin-Hamiltonian constants areg=2.00±0.01,B ₂ ⁰ =(163±3)·10^?4 cm^?1,B ₂ ² =(159±3)·10^?4 cm^?1,A=?(75±1)·10^?4 cm^?1. The effect of the invariance in temperature of the resonance magnetic fields in the narrow temperature rangeT=337–340 K and the model of the paramagnetic centre are discussed. According to EPR data a phase transition occurs atT=337 K. This transition from the paraelectric phase to the ferroelectric one is accompanied by a dramatic change in value of the spin-Hamiltonian constantB ₂ ⁰ .     

50 MeV Li3+ ion irradiation effect on structural, electrical, and dielectric properties of PVA-based nanocomposite polymer electrolytes

Nanocomposite polymer electrolyte thin films of polyvinyl alcohol (PVA)-orthophosphoric acid (H₃PO₄)-Al₂O₃ have been prepared by solution cast technique. Films are irradiated with 50 MeV Li³⁺ ions having four different fluences viz. 5?×?10¹⁰, 1?×?10¹¹, 5?×?10¹¹, and 1?×?10¹² ions/cm². The effect of irradiation on polymeric samples has been studied and characterized. X-ray diffraction spectra reveal that percent degree of crystallinity of samples decrease with ion fluences. Glass transition and melting temperatures have been also decreased as observed in differential scanning calorimetry. A possible complexation/interaction has been shown by Fourier transform infrared spectroscopy. Temperature-dependent ionic conductivity shows an Arrhenius behavior before and after glass transition temperature. It is observed that ionic conductivity increases with ion fluences and after a critical fluence, it starts to decrease. Maximum ionic conductivity of ～2.3?×?10^?5 S/cm owing to minimum activation energy of ～0.012 eV has been observed for irradiated electrolyte sample at fluence of 5?×?10¹¹ ions/cm². The dielectric constant and dielectric loss also increase with ion fluences while they decrease with frequency. Transference number of ions shows that the samples are of purely ionic in nature before and after ion irradiation.     

Lithium aluminum nitride,Li3AlN2 as a lithium solid electrolyte

Single phase of Li₃AlN₂ was prepared from the mixture of Li₃N/AlN = 1.2 to 1.5 in molar ratio at 700°C and at 900°C. It crystalizes in the cubic system derived from antifluorite-type structure having the lattice parameter $\text{a = 9.470}\text{A}\text{?}$. It is a pure ionic conductor having conductivity of 5 × 10^?8ω^?1cm^?1 at room temperature and an activation energy of 52 kJ/ mol. Its decomposition voltage was 0.85 V at 104°C. The TiS₂/Li₃AlN₂/Li cell could be discharged at a constant current of 45 μA/cm² at 104°C.     

The determination of Li+ mobility in solid electrolyte Li1.3Al0.1Zn0.1Ti1.8P3O12 in view of ionic diffusivity and conductivity

Nasicon-type solid electrolyte Li_1.3Al_0.1Zn_0.1Ti_1.8P₃O₁₂ was prepared by citric acid-assisted acrylamide polymerisation gel method. X-ray diffraction pattern showed that the introduction of Zn²⁺ in the parent matrix Li_1+x Al _x Ti_2?x P₃O₁₂ made it easier to get high-purity rhombohedral structure (space group $ R\overline 3 C $ ) Li_1.3Al_0.1Zn_0.1Ti_1.8P₃O₁₂ without the evidence of impurity secondary phase. The Li⁺ kinetics were investigated by complex impedance in bulk pellet and ionic conductivity in battery-type composite cathode, respectively. Grain-interior resistance measured by galvanostatic intermittent titration technique, potential step chronoamperometry, and AC impedance spectroscopy at 20 °C varies in the range 1.2–1.95?×?10^?4?S?cm^?1, which is in good agreement with that obtained by complex impedance method 1.5?×?10^?4?S?cm^?1.     

Influence of the annealing technique on the properties of Li ion-conductive Li1.3Al0.3Ti1.7(PO4)3 films

Li_1.3Al_0.3Ti_1.7(PO₄)₃ films were comparatively prepared by rapid thermal annealing (RTA) and conventional furnace annealing(CFA). The phase identification and surface morphology of the prepared films were characterized by X-ray diffraction and scanning electron microscopy. The electrochemical window, ionic conductivity, activation energy, and electronic conductivity were conducted by cyclic voltammetry, electrochemical impedance spectroscopy, and four-probe technique. The results show that the films prepared by RTA and CFA are homogenous and crack-free. The film prepared by RTA shows smaller grains and is denser than the one prepared by CFA. The electrochemical windows of the two films are beyond 2.4 V. The ionic conductivities of the films prepared by RTA and CFA are 2.7?×?10^?6 S cm^?1 and 1.4?×?10^?6 S cm^?1, respectively. The activation energy of the film prepared by RTA is 0.431 eV, which is slightly smaller than the one prepared by CFA. The electronic conductivity of the two films is about 10^?10 S cm^?1.     

ArF excimer laser deposition of wide-band gap solid electrolytes for thin film batteries

High quality solid electrolyte thin films was grown by pulsed laser deposition (PLD) using a high photon energy ArF excimer laser. Various amorphous thin films were successfully deposited on glass substrates from oxide targets; such as Li₃PO₄, LiBO₂, Li₂SiO₃, Li₂CO₃, Li₂SO₄, Li₂ZrO₃, LiAlO₂, Li₂WO₄ and Ohara glass ceramics. The morphology, optical property and ionic conductivity of these films were examined by optical microscope, UV–VIS spectroscopy and impedance analysis. Dramatic improvement of the film morphology was observed by using a high photon energy laser, while the broken film with many droplets was obtained by using lower ones. Ionic conductivity of the films was examined by impedance spectroscopy and dc polarization method. For example, an ionic conductivity of a Li₃PO₄ film was 4.6 × 10^? 6 S cm^? 1 at 25 °C with activation energy of 0.57 eV. Electronic conductivity measurements revealed that most of the films were pure lithium ion conductors, while a Li₂WO₄ film was a mixed conductor.     

Ionic transport in the lithium nitride bromides,Li6NBr3 and Li1 3N4Br

The ionic and electronic conductivities of the lithium nitride bromides Li₆NBr₃ and Li_{1 3}N₄Br have been studied in the temperature range from 50 to 220°C and 120 to 450°C, respectively. Both compounds are practically pure lithium ion conductors with negligible electronic contribution. Li₆NBr₃ has an ionic conductivity Ω of 2 × 10^-6Ω^-1cm^-1 at 100°C and an activation enthalpy for σT of 0.46 eV. Li_{1 3}N₄Br shows a phase transition at about 230°C. The activation enthalpy for σT is 0.73 eV below and 0.47 eV above this temperature. The conductivities at 150 and 300°C were found to be 3.5 × 10^-6 Ω^-1cm^-1 and 1.4 × 10^-3Ω^-1cm^-1, respectively. The crystal structure is hexagonal at room temperature with $\text{a = 7.415 (1)}\text{A}\text{?}$ and $\text{c = 3.865 (1)}\text{A}\text{?}$.     

Bromide ion conductivities of eutectic mixtures of quaternary ammonium bromides possessing long alkyl chains

Several quaternary ammonium bromides possessing long alkyl chains and their mixtures were found to be bromide ion conductors. The ionic conductivities of quaternary ammonium bromides themselves were lower than 10^?9 S cm^?1 at a room temperature. On the other hand, the eutectic mixtures of the quaternary ammonium bromides showed large increase of ionic conductivity. The best bromide ion conductors were found for the eutectic of Q₅, Q₇, Q₈, and Q₁₂: 4×10^?8 S cm^?1 at 30°C, and 6.3×10^?6 S cm^?1 at 50°C. Addition of asymmetric quarternary ammonium bromides had a negative effect on the ionic conductivity. These results were explained by a space filling factor in the solid.     

Lithium ion conductivity of the B-site substitution in Li3xLa0.67−xRE y III Ti1−2yPyO3 system (REIII=Sc3+, Y3+, Nd3+, Sm3+, Eu3+, Yb3+)

The B-site substituted perovskite solid solution systems Li_3xLa_0.67−xRE_yTi_1−2yP_yO₃ (RE=Sc, Y, Nd, Sm, Eu, Yb) have been investigated. Perovskite solid solutions formed in the range of x=0.10, y<0.10 for RE=Sc³⁺, Y³⁺, Yb³⁺, x=0.10, y≤0.05 for RE=Nd³⁺, Sm³⁺, Eu³⁺. Li_0.3La_0.57Nd_0.05Ti_0.9P_0.05O₃ has the highest bulk conductivity of 4.31×10⁻⁴ S·cm⁻¹ and the highest total conductivity of 2.52×10⁻⁴ S·cm⁻¹ at room temperature in all prepared compositions. The compositions have low activation energies of about 24–30 kJ/mol in the temperature ranges of 298–523 K. SEM studies showed that the sample made by solid-state reaction has a sphere-like morphology and a rough particle with particle size of about 50 μm. The research results also indicated that the reaction temperature decreases and the electrochemical stabilities of the titanate-based perovskite-type solid solutions are improved by using RE³⁺ and P⁵⁺ replaced Ti⁴⁺ on B-site in the Li_3xLa_0.67−xTiO₃ parent.     

多晶Li3+xV1-xTxO4(T=Ge,Si)离子导电性能的改善

本文用阻抗谱方法研究了Li_3+xV_1-xT_xO₄(T=Si,Ge)多晶的离子导电性,发现一些工艺条件如成型压强、烧结时间和烧结程序对电导率有很大影响。注意分析了这些影响的物理起因。最佳工艺条件是:在大约8t/cm²压强下成型样品。在1000℃连续烧结5至6天,烧结过程中,应尽量避免温度波动。在此条件下制备的Li_3.5V_0.5Ge_0.5关键词：     

LiF-LiCl-B2O3系统非晶态快离子导体结构的研究

本文通过对¹¹B核磁共振(¹¹B-NMR)、红外光谱等实验方法,研究了LiF-LiCl-B₂O₃三元系统玻璃的结构和离子导电性,着重于F^-离子在玻璃网络中所起的作用,以及F^-,Cl^-和Li⁺离子对导电率的影响。LiF-LiCl-B₂O₃三元系统玻璃,随LiF含量的增加,B由三角体向四面体变化,从而F^-离子进入网络,使玻璃结构由[B₂O₃]三角体层状结构向三维空间延展,形成了含有[BO₃F]基团的三维空间网络,Cl^-离子以游离的离子存在于网络中,起着松散网络的作用,对提高电导率有利,而Li⁺离子作为传导离子,对电导率的贡献是主要的。本系统玻璃的电导率是随LiF,LiCl含量的增加而增大,在300℃时测得电导率σ=6.12×10^-4Ω^-1·cm^-1。 关键词：     

Vibrational,electrical, and structural properties of PVDF–LiBOB solid polymer electrolyte with high electrochemical potential window

Polyvinylidene difluoride (PVDF)–lithium bis(oxalato)borate (LiBOB) solid polymer electrolytes (SPEs) have been prepared by solution casting. The highest ionic conductivity achieved is 3.4610^?3 S cm^?1. Electrochemical potential window of the SPEs is found around 4.7 V. Interaction between PVDF and LiBOB is studied systematically. The changes of C–C, CF₂, and CH₂ vibration modes with an emerging shoulder are analyzed. At higher salt content, this shoulder becomes more prominent peak at the expense of CF₂ vibration mode. This suggests the possible Li⁺?F coordination. Deconvolution of IR spectra region from 1750 to 1850 cm^?1 has been carried out to estimate the relative percentage of free ions and contact ions. The finding is in good agreement with conductivity and XRD results. When more salt is present, the number of free ions percentage increases and the Full width at half-maximum (FWHM) of (110) plane is broadening. The Li⁺?F interaction breaks the folding patterns of polymer chain and enhances amorphousness domain.     

Absorption spectrum of Cs2Mg(SO4)2 · 6H2O:Ni2+ single crystals

The absorption spectrum of Ni²⁺ doped in Cs₂Mg(SO₄)₂ · 6H₂O single crystals has been studied at room and liquid nitrogen temperatures in the range 7000–34000 cm^?1. The observed spectrum is satisfactorily interpreted in terms of cubic ligand field model including spin-orbit coulping. The ligand field parameters evaluated to best fit the observed spectrum are B = 955 cm^?1, C = 3572 cm^?1, Dq = 910 cm^?1 and ξ = 550 cm^?1. The non-ligand field band observed at 77K has been interpreted to be the superposition of vabrational mode of SO₄^2? radical on ₃T_1g(F) band.     

Effect of Li2O on the structure,electrical and dielectric properties of xLi2O·(20−x)CaO·30P2O5·30V2O5·20Fe2O3 glasses

Glasses of the general formula xLi₂O·(20?x)CaO·30P₂O₅·30V₂O₅·20Fe₂O₃ with x=0, 5, 10, 15 and 20 mol% were prepared; IR, density, electrical and dielectric properties have been investigated. Lithia-containing glasses revealed more (P₂O₇)^4?, FeO₆, V–O^? and PO^? groups and mostly have lower densities than those of lithia-free ones. The electrical properties showed random behavior by replacing Li₂O for CaO, which has been assigned to the change of the glass structure. The results of activation energy and frequency-dependent conductivity indicate that the conduction proceeds via electronic and ionic mechanisms, the former being dominant. The mechanism responsible for the electronic conduction is mostly thermally activated hopping of electrons from Fe(II) ions to neighboring Fe(III) sites and/or from V⁴⁺ to V⁵⁺. The dielectric constant (ε′) showed values that depend on the structure of glass according to its content of Li₂O. The (ε′) values are ranging between 3 and 41 at room temperature for 1 kHz, yet at high temperatures, glass with 20 mol Li₂O exhibits values of 110 and 3600 when measurement was carried out in the range 0.1–1 kHz, and at 5 MHz, respectively.