Characteristics of molybdenum oxide and chromium oxide cathodes in primary and secondary organic electrolyte lithium batteries I. Morphology,structure and their changes during discharge and cycling

Rechargeable positive electrodes for ambient temperature Li-batteries are mainly based on the same general principle: reversible topotactic Li⁺-intercalation into transition metal chalcogenide host lattices, yielding ternary phases Li_nMCh_x. After an intercalation/deintercalation cycle the original host lattice may be retained practically unchanged if the structure of the host matrix is determined by strong covalent bonds and if the concentration of intercalated ions was small. On the other hand, high concentration of unsolvated Li⁺ ions in fairly ionic oxide host lattices such as MoO₃, Cr₂O₅ or Cr₃O₈ (CrO_x) cause significant irreversible structural and also morphological changes of the host matrix. Moreover, ternary oxides Li_nMO_x prepared at room temperature are non-equilibrium phases — their structural parameters and transport properties vary with conditions of preparation, ageing time etc., and elevated temperature finally causes a complete and irreversible breakdown of their original structure. Prolonged cycling of crystalline large particle size MoO₃ leaves quasi-amorphous powders which, however, are still usable for rechargeable cathodes. Failure of Li_nMoO₃ and Li_nCrO_x electrodes is due to recrystallization via solution, forming e.g. Li₂MoO₄ from Li_nMoO₃. To obtain a better understanding of the limitations of MoO₃ and CrO_x cathodes under practical operation conditions changes in structure and morphology during electrochemical and chemical lithiation and after electrochemical cycling were followed by X-ray diffraction and SEM micrographs; supplementary results were obtained by electrochemical methods and by thermal analysis. Electronically conducting preparations of “hexagonal MoO₃” (which is a hydrated MoO₃ modification) were also characterized with respect to their discharge behaviour and reversibility in organic Li⁺-electrolytes ? their “sloping” discharge characteristics disqualify them for practical applications.     

Lithium intercalation in MoO3: A comparison between crystalline and disordered phases

We report properties of lithium-intercalated MoO₃ crystalline and thin-film which are potential cathode materials for high energy density batteries. Discharge and charge reactions of MoO₃ electrodes in a non-aqueous Li⁺-electrolyte have been studied. The kinetically accessible discharge range amounts to 0x1.5 for Li insertion in Li _x MoO₃. Transport parameters such as the Li⁺ chemical diffusion coefficient, thermodynamic factor and ionic conductivity are investigated during the Li⁺ insertion process and discussed with respect to the crystallinity of the cathode material.     

Improved luminescence of Y2MoO6:Eu3+ by doping Li+ ions for light-emitting diode applications

The photoluminescence (PL) property of Y₂MoO₆:Eu³⁺ doped with Li⁺ is investigated in this paper. The red luminescence of Eu³⁺ in Y₂MoO₆ lattice has greatly enhanced by codoping monovalent alkali metal ions Li⁺ into the lattice. The drastic increase in the luminescence intensity of Y_2?xLi_xMoO₆:Eu³⁺ originates from the reason that the Li⁺ ions may serve as a self-promoter for better crystallization to reduce the defect or as a lubricant for the complete incorporation of the Eu³⁺ ions into the Y₂MoO₆ host.     

Structural evolution of the MoO3(010) surface during lithium intercalation

Atomic force microscopy (AFM) has been used to characterize the structural evolution of the MoO₃(010) surface during the initial stage of Li⁺ intercalation. Lithiation was observed in situ using model cells comprised of a single crystal MoO₃ cathode, a dilute propylene carbonate (PC)-based electrolyte, and an Li metal anode. The insertion of Li⁺ into MoO₃ results in the topotactic nucleation and growth of acicular Li_xMoO₃ (x0.25) precipitates at the (010) surface. Because the interlayer spacing of Li_xMoO₃ (d=7.88 Å) is greater than that of MoO₃ (d=b/2=6.93 Å), the Li_xMoO₃ precipitates expand out of the (010) surface as they grow into the MoO₃ crystal along 010. The local strain associated with this expansion causes the Li_xMoO₃ precipitates to crack parallel to the MoO₃001 and 010 axes once their height exceeds approximately 20 nm. With continued Li⁺ intercalation, cracking becomes more prominent, and the (010) surface begins to fragment and disintegrate. Anisotropies in Li⁺ ion uptake and the influence of surface morphology on Li_xMoO₃ precipitation and crack propagation are described.     

Non-stoichiometric molybdenum oxides as cathodes for lithium cells. part v. thermodynamic,kinetic and structural aspects of the behaviour of Mo8O23 and Mo18O52

A deeper insight in the electrochemical behaviour of Li cells based on two non-stoichiometric Mo oxides, Mo₈O₂₃ and Mo₁₈O₅₂, was obtained by determining the OCV's, the diffusion coefficients and the variations of lattice parameters as a function of depth of discharge. The first material is a monoclinic framework-structured compound endowed with large channels which provide easy paths for Li⁺. Occupation of sites in the cavities of this structure produces at first a shrinkage of the unit cell, followed by a moderate re-expansion. Mo₁₈O₅₂ is a triclinic step-layered material which markedly expands upon Li⁺ intercalation. Li⁺ diffuses in it relatively slowly for x<1, i.e. before increasing the interlayer distance, and for x>0.4 due to coulombic repulsion between Li⁺ ions.     

7Li NMR study on Li+ ionic diffusion and phase transition in LixCoO2

The temperature dependence of the spin-lattice relaxation time, T₁ and the line width of the ⁷Li nucleus were measured in delithiated Li_xCoO₂ (x = 0.6, 0.8, 1.0). Two different relaxation behaviors were observed in the temperature dependence of T₁^− 1 in a x = 0.8 sample. These would have arisen from inequivalent Li sites in two coexisting phases; an original hexagonal (HEX-I) and a modified hexagonal (HEX-II) phase in the x = 0.8 sample. We analyzed using a phenomenological non Debye-type relaxation model. Motional narrowing in the line width was observed in each sample, the result revealing that Li⁺ ions begin to move at low temperature in samples with less Li content. It was found that the activation energy associating with Li⁺ ion hopping in the HEX-II phase is smaller than that in the HEX-I phase. These results show that the HEX-II phase produced in the Li deintercalation process would be suitable for Li⁺ ionic diffusion in multi-phase Li_xCoO₂, and it is expected that this would enable fast ionic diffusion. Li⁺ ionic diffusion related to phase transition is discussed from ⁷Li NMR results.     

Thermodynamic study of lithium insertion in V6O13 and Li1+xV3O8

The enthalpies of Li⁺ insertion into two V oxides of interest as cathodes for secondary Li batteries, i.e. V₆O₁₃ and Li_1+xV₃O₈ have been directly measured by solution calorimetry. By comparing the integral molar enthalpies ΔH⁰/x with the corresponding ΔG⁰/x values, ΔS⁰/x higher than expected have been found for Li_1+xV₃O₈. This has been correlated to a reorganization of its distorted structure induced by the initial Li⁺ insertion. Two other cathode materials, having the same variation of the potential with Li⁺ content, i.e. MoO₃ and (Mo_0.3V_0.7)₂O₅, show even higher ΔS⁰/x values. The entropic values stemming from structural reorganizations add to the configurational entropies of inserted ions in determining the initial profile of E as a function of Li⁺.     

Synthesis and redox behavior of a new polyanion compound, Li2Co2(MoO4)3, as 4 V class positive electrode material for lithium batteries

A new material, Li₂Co₂(MoO₄)₃, belonging to NASICON type polyanion family was synthesized by means of a low temperature soft-combustion method using glycine as a soft combustion fuel. The annealed product, Li₂Co₂(MoO₄)₃, was found to exhibit a single phase structure as confirmed by XRD and crystallized in an orthorhombic structure (space group Pnma) with lattice parametersa=5.086(1) Å,b=10.484(2) Å and c=17.606(2) Å. The electronic state of each element present in the new material was confirmed by X-ray photoelectron spectroscopic (XPS) analysis. The stoichiometry of the synthesized product was determined by the metal analysis using inductively coupled plasma (ICP-AES) technique. The microstructural analysis by means of SEM revealed cylindrical fiber-like grains. Electrochemistry of the new material was demonstrated by extraction/insertion process of Li⁺ in lithium batteries. Galvanostatic charge/discharge profiles revealed a reversible discharge capacity of ～ 55 mAh/g over the potential window of 4.9 - 1.5 V.     

Solid solutions Li1+xV3O8 as cathodes for high rate secondary Li batteries

Following a preliminary investigation, Li/Li_1+xV₃O₈ cells have been examined. Using samples of low x content, up to 3 eq Li⁺ could be accepted both chemically and electrochemically by one mole of active material. Li⁺ is accomodated in the tetrahedral sites existing between the (V₃O₈)^(1+x)- layers. Li⁺ jumping from site to site is fast and permits high rate capabilities: at 10 mA/cm², 1.1 eq Li⁺ per mole could still be inserted. The structure does not show irreversible alterations upon extended lithiation, allowing long cycle lives to be achieved. Kinetic constraints limit the recovery of the full capacity of the first discharge at medium-high rates, but the second-discharge capacity declines slowly with cycle number.     

Transport and equilibrium characteristics of γ-lithium vanadium bronze

The diffusion coefficient of Li⁺ in the γ-lithium vanadium bronze (Li_1+xV₃O₈) has been measured with the long-pulse galvanostatic technique. Values ranging from 1.7×10⁻⁷ cm²s⁻¹, at x=0.3, to 2.2×10⁻⁸ cm²s⁻¹, at x= 1.4, have been measured. The thermodynamic factors, d ln a/d ln c, determined from the OCV/x curve and from voltage relaxation after the current pulse, have a mean value of ∼15. The pseudo two-phase region observed in the OCV/x curve at high Li⁺ concentrations seems attributable to ordering of Li⁺ in specific sites and to alteration of the unit cell. This process is reversible as shown by X-ray diffractometry. Finally, from OCV/t plots at different x, the partial molar entropy of Li⁺ was determined. The values, on account of the large dE(x)/dt measured, are higher than those found for V₆O₁₃ or TiS₂.     

7Li and 51V NMR study on Li+ ionic diffusion in lithium intercalated LixV2O5

Li_xV₂O₅ (0.4 < x < 1.4) prepared by solid-state reaction were studied by ⁷Li and ⁵¹V NMR spectroscopy. ⁷Li NMR spectra showed a narrowing of the line width in relation to Li⁺ionic diffusion. Analysis of Li_xV₂O₅ using a Debye-type relaxation model showed a low activation energy ∼0.07 eV in the sample of x = 0.4 below room temperature, and revealed a Li⁺ionic diffusion with larger activation energy ∼0.5 eV above 450 K in lithium-rich samples. The latter is ascribed to the existence of a multi-phase system comprising stable ɛ- and γ-phases, resulting from complicated phase transitions at high temperature. These shapes and shifts enable the classification of the β-, ɛ-, δ-, and γ-phases. The ionic diffusion of Li⁺ ions is discussed in relation to the complicated phase transitions.     

NMR study on an Li+-ion diffusion in the solid solution Li4−x(PO4)x(SiO4)1−x with the Li4SiO4-type structure

Diffusive motion of an Li⁺ion in the solid solution Li_4?x(PO₄)_x(SiO₄)_1?x (0 ≦ x ≦ 0.35) was studied by ⁷Li pulsed nmr between ? 70 and 440°C. Activation energies for an Li⁺ ion diffusion decreased monotonically with increasing x in the composition. These values are smaller than those reported from the measurement of ionic conductivity. Discrepency seems to result from the local nature of an Li⁺ diffusion observed by nmr contrary to the long-range one in the ionic conduction.     

Lithium mobility in the layered oxide Li1−xCoO2

The Li⁺-ion chemical diffusion coefficient in the layered oxide Li_0.65CoO₂ has been measured to be $\text{D}\text{?}\text{= 5 × 10}{}^{\mathrm{?12}}$ m² s^?1 by three independent techniques: (1) from the Warburg prefactor, (2) from the transition frequency for semi-infinite to finite diffusion lengths in steady-state ac-impedence measurements and (3) from a modified Tubandt method that uses ac-impedance data to distinguish interfacial and surface-layer resistances from the bulk resistance of the sample. This value and a small increase in D? with (1 ? x) in Li_1?xCoO₂, 0.45 < (1 ? x) < 0.80, compare favorably with the $\text{D}\text{?}\text{= 5}\text{to}\text{7 × 10}{}^{-12}\text{m}{}^2\text{s}{}^{-1}$ obtained by Honders for this system with pulse techniques. A qualitative discussion is presented as to why this composition dependence and why D? for this system is a factor of five larger than that for Li⁺-ion diffusion in Li_xTiS₂.     

Structural and electrochemical effects of cobalt doping on lithium manganese oxide spinel

Pure LiMn₂O₄ and lithium manganese oxide spinels with partial replacement of manganese by cobalt up to 20 mole%, LiCo_xMn_2−xO₄, were prepared. The effect of extended cycling on the crystal structure was investigated. A capacity decrease with increasing cobalt content was observed in the potential range about 4100 mV vs. Li/Li⁺. Cycling behavior is significantly improved, compared to LiMn₂O₄. LiCo_xMn_2−xO₄ is discharged in a single phase reaction in the upper potential range around 4100 mV vs. Li/Li⁺, whereas pure LiMn₂O₄ shows a two phase behavior. LiMn₂O₄ shows a significant broadening of peaks in plots of differential capacity and change in shape of the voltage profile upon extended cycling. LiCo_xMn_2−xO₄ shows neither broadening nor change. Voltage profiles and plots of the differential capacity differ significantly compared to spinels with lithium substitution, Li_1+xMn_2−xO₄. In contrast to Li_1+xMn_2-xO₄, LiCo_xMn_2-xO₄ is discharged in a two step process in the range of 0 ≤ × ≤ 0,5. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Ionic conductivity and crystal structure for the Li3−2xCr2−xTax(PO4)3 system

The monoclinic phase (P2₁/n) was formed for 0≤x≤0.6 and the NASICON-type rhombohedral phase (R3̄c) was obtained for the region 0.8≤x≤1.2 in the Li_3−2xCr_2−xTa_x(PO₄)₃ system. The activation energy for Li⁺ migration was ca. 0.45 eV for the monoclinic structure and ca. 0.36 eV for the rhombohedral structure. The maximum conductivity of 8.4×10⁻⁶ S cm⁻¹ at 298 K was obtained for x=0.8 of the Li_3−2xCr_2−xTa_x(PO₄)₃ system. The conductivity of LiCrTa(PO₄)₃ was enhanced about three to five times by the addition of the lithium salt due to the improvement of the sinterablity. The maximum conductivity was 2.4×10⁻⁵ S cm⁻¹ at 298 K for LiCrTa(PO₄)₃–0.2Li₃BO₃.     

NMR study of Li+-ion diffusion in the solid solution Li3+x(P1−x,Six)O4> with the γII-Li3PO4 structure

Diffusive motion of a Li⁺ ion in the solid solution of Li₃+x(P₁?x, Si_x)O₄ (0?x?0.4) with the γ_II-Li₃PO₄ structure was studied by the measurement of the ⁷Li spin-lattice relaxation time. The observed motion was a local motion instead of a long-range one. In comparison with the previous study on the solid solution of Li₄?x(P_x, Si₁?x)O₄ with the Li₄SiO₄ structure, it is noticeable that the activation energy is low and almost independent of the composition and that the attempt frequency is smaller in this phase. These characteristics were attributed to the availability of a large interstitial void in the γ_II-Li₃PO₄ structure. The low values of activation energy for the Li⁺ ionic conduction may be explained on the same basis.     

Motional narrowing in the electron-spin-resonance-spectrum of pentavalent vanadium-compounds

The activation energy of the hopping frequency of the vanadium-3d ¹-electron is derived from the temperature dependence of the ESR linewidth in the following semiconducting, pentavalent vanadium-compounds: Na_xV₂O₅, Li_xV₂O₅ (x <0.02), V₂O₅ weakly doped with WO₃ or MoO₃ (E _a ≈0.07 eV). In V₂MoO₈, vanadium-3d ₁-electrons are responsible for the electronic conductivity, too.     

Synthesis and electrochemical performances of Li4Ti4.95Al0.05O12/C as anode material for lithium-ion batteries

Spinel compounds Li₄Ti_5−xAl_xO₁₂/C (x=0, 0.05) were synthesized via solid state reaction in an Ar atmosphere, and the electrochemical properties were investigated by means of electronic conductivity, cyclic voltammetry, and charge-discharge tests at different discharge voltage ranges (0-2.5 V and 1-2.5 V). The results indicated that Al³⁺ doping of the compound did not affect the spinel structure but considerably improved the initial capacity and cycling performance, implying the spinel structure of Li₄Ti₅O₁₂ was more stable when Ti⁴⁺ was substituted by Al³⁺, and Al³⁺ doping was beneficial to the reversible intercalation and deintercalation of Li⁺. Al³⁺ doping improved the reversible capacity and cycling performance effectively especially when it was discharged to 0 V.     

Preparation of Sm3+–Eu3+ coactivating red-emitting phosphors and improvement of their luminescent properties by charge compensation

By charge compensating, a series of red-emitting phosphors Ca_0.54Sr_0.16Ca_0.54Sr_0.31Eu_0.08Sm_0.02(MoO₄)_0.6(WO₄)_0.4 were synthesized. Two approaches to charge compensation were used: (a) 2Ca²⁺/Sr²⁺→Eu ³⁺/Sm³⁺+M ⁺, where M⁺ is a monovalent cation like Li⁺, Na⁺ or K⁺; (b) Ca²⁺/Sr²⁺→Eu ³⁺/Sm³⁺+N ^?, where N⁺ is a monovalent anion like F^?, Cl^?, Br^?, or I^?. One red LED was made by combining the phosphor and 390–405 nm emitting LED chip under 20 mA forward-bias current, the color purity, chromaticity coordinates and the luminous intensity of which were 99.5%, x=0.66, y=0.33, 5600 mcd, respectively.     

Electrical conductivity and dynamics of quasi-solidified lithium-ion conducting ionic liquid at oxide particle surfaces

Lithium ion conducting solid-state composites consisting of lithium ion conducting ionic liquid, lithium bis(trifluoromethanesulfonyl)amide (Li-TFSA) dissolved 1-ethyl-3-methyl imidazolium bis(trifluoromethylsulfonyl)amide (EMI-TFSA), denoted by [yMLi⁺][EMI⁺][TFSA⁻] in this study, and various oxide particles such as SiO₂, Al₂O₃, TiO₂ (anatase and rutile) and 3YSZ are synthesized via a liquid route for the molar concentration of lithium, y, to be 1. The composite consists of SiO₂ and the ionic liquid with y = 0.2 was also prepared. The ionic liquid are quasi-solidified at the above oxide particle surfaces when x is below 40 for y = 1 and x is below 30 for y = 0.2, corresponding to the confinable thickness of the ionic liquid at the oxides' surfaces to be approximately 5-10 nm regardless of the oxide compositions. The electrical conductivities of x vol.%[yMLi⁺][EMI⁺][TFSA^-]-SiO₂, Al₂O₃, TiO₂s or 3YSZ composites are evaluated by ac impedance measurements. The quasi-solid-state composites exhibited liquid-like high apparent conductivity, e.g. 10^− 3.3-10^− 2.0 S cm^− 1 in the temperature range of 323-538 K for SiO₂-ionic liquid composites with y = 1. The self-diffusion coefficients of the constituent species of x vol.% [yMLi⁺][EMI⁺][TFSA⁻] (x is below 40, y = 0.2 and 1) − SiO₂ are evaluated by the Pulse Gradient Spin Echo (PGSE)-NMR technique in the temperature range of 298-348 K. By the quasi-solidification of the ionic liquid at SiO₂ particle surfaces, the absolute values of the diffusion coefficients of all constituent species decreased. The SiO₂ surfaces work to promote ionization of ion pair, [EMI⁺][TFSA⁻], while significant influence on the solvation coordination, [Li(TFSA)_n + 1]ⁿ⁻, was not observed. The apparent transport numbers of Li-containing species both in the bulk and the quasi-solidified ionic liquid showed similar values with each other, which was evaluated to be in the range of 0.010-0.017 for y = 0.2 and 0.051-0.093 for y = 1 in the abovementioned temperature range.