Lithium potassium element oxide compounds as Li super-ionic conductor, solid electrolyte and coating layer for lithium metal battery and lithium-ion battery

Abstract

Solid-state lithium ion electrolytes of lithium potassium element oxide based compounds are provided which contain an anionic framework capable of conducting lithium ions. The element atoms are Ir, Sb, I Nb and W. An activation energy of the lithium potassium element oxide compounds is from 0.15 to 0.50 eV and conductivities are from 10.sup.−3 to 22 mS/cm at 300K. Compounds of specific formulae are provided and methods to alter the materials with inclusion of aliovalent ions shown. Lithium batteries containing the composite lithium ion electrolytes are also provided. Electrodes containing the lithium potassium element oxide based materials and batteries with such electrodes are also provided.

Claims

1. A solid-state lithium ion electrolyte, comprising: at least one material selected from the group of materials consisting of compounds of formulae (I) (II), (III) and (IV):
Li.sub.y(M1).sub.x1KMO.sub.6  (I) wherein M is selected from the group consisting of Ir, Sb, I, Nb and W, x1 is a number from greater than 0 to less than 6, y is a value such that charge neutrality of the formula is obtained, and M1 is an aliovalent substitute for Li and is at least one element different from Li selected from elements of groups 1, 2, 13 and transition metals;
Li.sub.yK.sub.1-x2(M2).sub.x2MO.sub.6  (II) wherein x2 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the composite formula is obtained, and M2 is an aliovalent substitute for K and is at least one element different from K selected from elements of groups 1, 2, 3, 4, 5, 6, 7,8, 9, 10, 11, 12 and 13;
Li.sub.yKM.sub.1-x3(M3).sub.x3O.sub.6  (III) wherein x3 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the formula is obtained, and M3 is an aliovalent substitute for M and is at least one element different from M selected from elements of groups 1-13; and
Li.sub.6KMO.sub.6  (IV).

2. The solid state lithium ion electrolyte according to claim 1, wherein a lithium ion (Li.sup.+) conductivity of the solid state lithium ion electrolyte is from 10.sup.−3 to 22 mS/cm at 300K.

3. The solid state lithium ion electrolyte according to claim 1, wherein an activation energy of the material is from 0.15 to 0.50 eV.

4. The solid state lithium ion electrolyte according to claim 1, wherein the material comprises a trigonal structure.

5. The solid state lithium ion electrolyte according to claim 1 wherein the compound is of formula (IVa):
Li.sub.6KIrO.sub.6  (Iva) wherein an X-ray Diffraction Analysis obtained based on Cu-Kα radiation with wavelength of 1.54184 Å, of the material comprises the following peaks having an intensity of 10 or more relative to the peak of highest intensity being 100: TABLE-US-00002 Peak Position Relative Intensity 17.669 100.00 21.686 97.25 28.106 57.45 28.110 40.92 35.777 21.83 35.780 10.33 38.032 23.92 42.224 63.66 44.194 14.00 44.202 17.90 47.955 17.72 53.204 15.27 54.870 18.76 58.117 10.18 58.119 10.57 59.698 13.15 62.771 18.41 62.780 11.22 68.715 10.15

6. The solid state lithium ion electrolyte according to claim 1 wherein the compound is of formula (IVb):
Li.sub.6KNbO.sub.6  (IVb) wherein an X-ray Diffraction Analysis obtained based on Cu-Kα radiation with wavelength of 1.54184 Å, of the material comprises the following peaks having an intensity of 10 or more relative to the peak of highest intensity being 100: TABLE-US-00003 Peak Position Relative Intensity 17.255 98.935 21.364 69.654 27.292 100.0 27.591 49.651 34.918 24.734 37.452 17.457 41.301 67.781 43.519 15.403 47.145 12.810 51.432 10.900 52.133 13.685 53.492 20.157 60.921 28.242 67.568 11.551

7. The solid state lithium ion electrolyte according to claim 1 wherein the compound is of formula (IVc):
Li.sub.6KSbO.sub.6  (IVc) wherein an X-ray Diffraction Analysis obtained based on Cu-Kα radiation with wavelength of 1.54184 Å, of the material comprises the following peaks having an intensity of 10 or more relative to the peak of highest intensity being 100: TABLE-US-00004 Peak Position Relative Intensity 17.279 82.727 21.291 100.0 27.410 66.749 27.549 38.662 34.967 13.175 37.322 16.748 41.303 42.265 43.366 14.012 61.139 11.808

8. The solid state lithium ion electrolyte according to claim 1 wherein the compound is of formula (IVd):
Li.sub.6KIO.sub.6  (IVd) wherein an X-ray Diffraction Analysis obtained based on Cu-Kα radiation with wavelength of 1.54184 Å, of the material comprises the following peaks having an intensity of 10 or more relative to the peak of highest intensity being 100: TABLE-US-00005 Peak Position Relative Intensity 16.968 100.0 20.834 79.733 26.967 56.304 26.990 33.974 34.322 16.507 36.501 21.599 40.492 70.471 42.399 19.989 50.970 12.874 52.538 13.645 60.022 14.777

9. The solid state lithium ion electrolyte according to claim 1 wherein the compound is of formula (IVe):
Li.sub.6KWO.sub.6  (IVe) wherein an X-ray Diffraction Analysis obtained based on Cu-Kα radiation with wavelength of 1.54184 Å, of the material comprises the following peaks having an intensity of 10 or more relative to the peak of highest intensity being 100: TABLE-US-00006 Peak Position Relative Intensity 17.152 100.0 17.368 97.436 17.369 97.455 21.215 94.95 21.287 97.823 21.288 97.834 27.365 60.072 27.408 42.143 27.700 57.895 27.798 39.479 34.704 22.886 35.152 21.284 35.153 21.283 37.228 24.666 37.229 24.67 37.358 23.317 41.033 34.473 41.189 33.605 41.734 31.553 41.735 31.559 43.205 19.707 43.357 18.248 43.358 18.241 53.324 11.123 54.235 10.91 56.563 10.221 57.425 10.257 67.043 10.577 67.297 10.609 67.299 10.61

10. A solid state lithium battery, comprising: an anode; a cathode; and a solid state lithium ion electrolyte located between the anode and the cathode; wherein the solid state lithium ion electrolyte comprises at least one material selected from the group of materials consisting compounds of formulae (I), (II)(III) and (IV):
Li.sub.y(M1).sub.x1KMO.sub.6  (I) wherein M is selected from the group consisting of Ir, Sb, I, Nb and W, x1 is a number from greater than 0 to less than 6, y is a value such that charge neutrality of the formula is obtained, and M1 is an aliovalent substitute for Li and is at least one element different from Li selected from elements of groups 1, 2, 13 and transition metals;
Li.sub.yK.sub.1-x2(M2).sub.x2MO.sub.6  (II) wherein x2 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the composite formula is obtained, and M2 is an aliovalent substitute for K and is at least one element different from K selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 13;
Li.sub.yKM.sub.1-x3(M3).sub.x3O.sub.6  (III) wherein x3 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the formula is obtained, and M3 is an aliovalent substitute for M and is at least one element different from M selected from elements of groups 1-13; and
Li.sub.6KMO.sub.6  (IV).

11. The solid state lithium ion battery according to claim 6, wherein the battery is a lithium metal battery or a lithium ion battery.

12. An electrode for a solid state lithium battery, comprising: a current collector; and an electrode active layer on the current collector; wherein the electrode active layer comprises at least one compound selected from the group consisting of compounds of formulae (I), (II), (III) and (IV):
Li.sub.y(M1).sub.x1KMO.sub.6  (I) wherein M is selected from the group consisting of Ir, Sb, I, Nb and W, x1 is a number from greater than 0 to less than 6, y is a value such that charge neutrality of the formula is obtained, and M1 is an aliovalent substitute for Li and is at least one element different from Li selected from elements of groups 1, 2, 13 and transition metals;
Li.sub.yK.sub.1-x2(M2).sub.x2MO.sub.6  (II) wherein x2 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the composite formula is obtained, and M2 is an aliovalent substitute for K and is at least one element different from K selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 13;
Li.sub.yKM.sub.1-x3(M3).sub.x3O.sub.6  (III) wherein x3 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the formula is obtained, and M3 is an aliovalent substitute for M and is at least one element different from M selected from elements of groups 1-13; and
Li.sub.6KMO.sub.6  (V).

13. An electrode for a solid state lithium battery, comprising: a current collector; an electrode active layer on the current collector; and a coating layer on the electrode active layer; wherein the coating layer on the electrode active layer comprises at least one compound selected from the group consisting of compounds of formulae (I), (II), (I) and (IV):
Li.sub.y(M1).sub.x1KMO.sub.6  (I) wherein M is selected from the group consisting of r, Sb, I, Nb and W, x1 is a number from greater than 0 to less than 6, y is a value such that charge neutrality of the formula is obtained, and M1 is an aliovalent substitute for Li and is at least one element different from Li selected from elements of groups 1, 2, 13 and transition metals;
Li.sub.yK.sub.1-x2(M2).sub.x2MO.sub.6  (II) wherein x2 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the composite formula is obtained, and M2 is an aliovalent substitute for K and is at least one element different from K selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 13;
Li.sub.yKM.sub.1-x3(M3).sub.x3O.sub.6  (III) wherein x3 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the formula is obtained, and M3 is an aliovalent substitute for M and is at least one element different from M selected from elements of groups 1-13; and
Li.sub.6KMO.sub.6  (IV).

14. A solid state lithium battery comprising the electrode of claim 12, wherein the solid state lithium battery is a lithium ion battery or a lithium metal battery.

15. A solid state lithium battery comprising the electrode of claim 13, wherein the solid state lithium battery is a lithium ion battery or a lithium metal battery.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows the crystal structure of Li.sub.6KIrO.sub.6.

(2) FIG. 2 shows a calculated XRD analysis for Li.sub.6KIrO.sub.6 obtained based on Cu-Kα radiation with wavelength of 1.54184 Å.

(3) FIG. 3 shows a Table listing the major peaks and relative intensities for the XRD analysis of FIG. 2.

(4) FIG. 4 shows the crystal structure of Li.sub.6KNbO.sub.6.

(5) FIG. 5 shows a calculated XRD analysis for Li.sub.6KNbO.sub.6 obtained based on Cu-Kα radiation with wavelength of 1.54184 Å.

(6) FIG. 6 shows a Table listing the major peaks and relative intensities for the XRD analysis of FIG. 5.

(7) FIG. 7 shows the crystal structure of Li.sub.6KSbO.sub.6.

(8) FIG. 8 shows a calculated XRD analysis for Li.sub.6KSbO.sub.6 obtained based on Cu-Kα radiation with wavelength of 1.54184 Å.

(9) FIG. 9 shows a Table listing the major peaks and relative intensities for the XRD analysis of FIG. 8.

(10) FIG. 10 shows the crystal structure of Li.sub.6KIO.sub.6.

(11) FIG. 11 shows a calculated XRD analysis for Li.sub.6KIO.sub.6 obtained based on Cu-Kα radiation with wavelength of 1.54184 Å.

(12) FIG. 12 shows a Table listing the major peaks and relative intensities for the XRD analysis of FIG. 11.

(13) FIG. 13 shows the crystal structure of Li.sub.6KWO.sub.6.

(14) FIG. 14 shows a calculated XRD analysis for Li.sub.6KWO.sub.6 obtained based on Cu-Kα radiation with wavelength of 1.54184 Å.

(15) FIG. 15 shows a Table listing the major peaks and relative intensities for the XRD analysis of FIG. 14.

(16) FIG. 16 shows an Arrhenius plot of Li.sub.7IrO.sub.6 from AIMD simulations.

(17) FIG. 17 shows an Arrhenius plot of Li.sub.7.33Sn.sub.0.33Ir.sub.0.67O.sub.6 from AIMD simulations.

(18) FIG. 18 shows an Arrhenius plot of Li.sub.6.17KNb.sub.0.83Zro.sub.0.17O12 from AIMD simulations.

(19) FIG. 19 shows shows an Arrhenius plot of Li.sub.6.33KNb.sub.0.67Sn.sub.0.33O12 from AIMD simulations.

(20) FIG. 20 shows shows an Arrhenius plot of Li.sub.6.5KNb.sub.0.5Zr.sub.0.5O12 from AIMD simulations.

(21) FIG. 21 shows shows an Arrhenius plot of Li.sub.6.67KNb.sub.0.33Zr.sub.0.67O.sub.12 from AIMD simulations.

(22) FIG. 22 shows shows an Arrhenius plot of Li.sub.6.33KSb.sub.0.67Sn.sub.0.33O.sub.12 from AIMD simulations.

(23) FIG. 23 shows an Arrhenius plot of Li.sub.6.33KI.sub.0.67Sn.sub.0.33O.sub.12 from AIMD simulations.

(24) FIG. 24 shows an Arrhenius plot of Li.sub.6.33KW.sub.0.67Sn.sub.0.33O.sub.12 from AIMD simulations.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

(25) Throughout this description, the terms “electrochemical cell” and “battery” may be employed interchangeably unless the context of the description clearly distinguishes an electrochemical cell from a battery. Further the terms “solid-state electrolyte” and “solid-state ion conductor” may be employed interchangeably unless explicitly specified differently.

(26) In the chemical formulae provided the term “less than” indicates less than the full value of the number stated. Thus, “less than” may mean a value up to 0.9 of the expressed number.

(27) For example, if the number indicated is 3, a number less than 3 may be 2.7. The term greater than 0 may mean a positive amount being present, such amount may be as little as 0.01.

(28) Structural characteristics of effective Li.sup.+ conducting crystal lattices have been described by Ceder et al. (Nature Materials, 14, 2015, 1026-1031) in regard to known Li ion conductors Li.sub.10GeP.sub.2S.sub.12 and Li.sub.7P.sub.3S.sub.11, where the sulfur sublattice of both materials was shown to very closely match a bcc lattice structure. Further, Li.sup.+ ion hopping across adjacent tetrahedral coordinated Li.sup.+ lattice sites was indicated to offer a path of lowest activation energy.

(29) The inventors are conducting ongoing investigations of new lithium composite compounds in order to identify materials having the properties which may serve as solid-state electrolytes in solid state lithium batteries. In the course of this ongoing study and effort the inventors have developed and implemented a methodology to identify composite materials which have chemical and structural properties which have been determined by the inventors as indicators of lithium ion conductance suitable to be a solid state electrolyte for a lithium-ion battery.

(30) To qualify as solid state electrolyte in practical applications, the material must meet several certain criteria. First, it should exhibit desirable Li-ion conductivity, usually no less than 10.sup.−6 S/cm at room temperature. Second, the material should have good stability against chemical, electrochemical and thermal degradation. Third, the material should have low grain boundary resistance for usage in all solid-state battery. Fourth, the synthesis of the material should be easy and the cost should not be high.

(31) A criterion of this methodology requires that to qualify as solid state electrolyte in practical application, the material must exhibit desirable Li-ion conductivity, usually no less than 10.sup.−6 S/cm at room temperature. Thus, ab initio molecular dynamics simulation studies were applied to calculate the diffusivity of Li ion in the lattice structures of selected lithium potassium tantalate materials. In order to accelerate the simulation, the calculation was performed at high temperatures and the effect of excess Li or Li vacancy was considered. In order to create excess Li or Li vacancy, aliovalent replacement of cation or anions may be evaluated. Thus, Li vacancy was created by, for example, partially substituting K or Ta with aliovalent cationic species while compensating the charge neutrality with Li vacancy or excess Li.

(32) The diffusivity at 300 K was determined according to equation (I)
D=D.sub.0exp(−E.sub.a/k.sub.bT)  equation (I)
where D.sub.0, E.sub.a and k.sub.b are the pre-exponential factor, activation energy and Boltzmann constant, respectively. The conductivity is related with the calculated diffusivity according to equation (TT):
σ=D.sub.300ρe.sup.2/k.sub.bT  equation (II)
where ρ is the volumetric density of Li ion and e is the unit charge.

(33) The anionic lattice of Li-ion conductors has been shown to match certain lattice types (see Nature Materials, 14, 2015, 2016). Therefore, in the anionic lattice of the potential Li.sup.+ ion conductor is compared to the anionic lattice of Li.sup.+ ion conductor known to have high conductivity.

(34) Thus, selected lithium potassium iridium oxide compounds were compared to Li-containing compounds reported in the inorganic crystal structure database (FIZ Karlsruhe ICSD—https://icsd.fiz-karlsruhe.de) and evaluated in comparison according to an anionic lattice matching method developed by the inventors for this purpose and described in copending U.S. application Ser. No. 15/597,651, filed May 17, 2017, to match the lattice of these compounds to known Li-ion conductors.

(35) According to the anionic lattice matching method described in copending U.S. application Ser. No. 15/597,651, an atomic coordinate set for the compound lattice structure may be converted to a coordinate set for only the anion lattice. The anions of the lattice are substituted with the anion of the comparison material and the obtained unit cell rescaled. The x-ray diffraction data for modified anion-only lattice may be simulated and an n×2 matrix generated from the simulated diffraction data. Quantitative structural similarity values can be derived from the n×2 matrices.

(36) The purpose of anionic lattice matching is to further identify compounds with greatest potential to exhibit high Li.sup.+ conductivity. From this work, the compounds described in the embodiments which follow were determined to be potentially suitable as solid-state Li.sup.+ conductors.

(37) Ab initio molecular dynamics (AIMD) simulation was then applied to predict the conductivity of the targeted lithium potassium tantalates. The initial structures were statically relaxed and were set to an initial temperature of 100 K. The structures were then heated to targeted temperatures (750-1150 K) at a constant rate by velocity scaling over a time period of 2 ps. The total time of AIMD simulations were in the range of 200 to 400 ps. The Li.sup.+ diffusivity at different temperatures from 750-1150 K follows an Arrhenius-type relationship.

(38) During the course of investigation the inventors have identified compounds based on aliovalent substitution of Li.sub.6KIrO.sub.6 as having properties which make them of great interest as lithium ion conductors. The chemical compositions of interest were further evaluated for structural stability based on an analysis of compositional phase diagrams which were constructed using the pynatgen computation package to evaluate the phase equilibria of a given phase of the studied composition. The phase equilibria of a given solid electrolyte was determined by constructing the convex energy hull of all relevant phases in the compositional phase diagram. The phase equilibria at the composition C corresponding to the energy minimum E.sub.eq(C) were identified by comparing the energy of all relevant phases in its compositional space. The phase stability of the investigated phase was evaluated using the decomposition energy ΔE.sub.D of a given phase to its phase equilibria according to Eq. III.
ΔE.sub.D(phase)=E.sub.eq(C)−E(phase)  (Eq. III).

(39) ΔE.sub.D is the negative of the value of the energy above the hull. Compounds having a ΔE.sub.D of −50 or less were considered to be of sufficent stability to warrant study via AIMD calculations. The method of this analysis is described by Mo et al. (First Principles Study on Electrochemical and Chemical Stability of the Solid Electrolyte-Electrode Interfaces in All-Solid-State Li-ion Batteries to be published in Journal of Materials Chemistry A) the disclosure of which is incorporated herein by reference.

(40) Elements suitable for aliovalent substitution may be selected by an ionic substitution probability determined by the method as described by Hautier et al. (Inorg. Chem. 2011, 50, 656-663) wherein candidate dopants may be selected by an ionic substitution probabilistic model, constructed upon data mining of all known inorganic crystal materials. Dopants which could potentially create vacancies or interstitials within the particular materials were included. The structures with dopants that were not energetically favorable would be screened and excluded during phase stability calculations. The configurations of the sublattices, dopants, and vacancies or interstitials were determined by the computation methods described herein. Such methods have been described for example, in the following reports:

(41) Bai et al., ACS Appl. Energy Mater. 2018, 1, 1626-1634; and

(42) He et al., Phys. Chem. Chem. Phys., 2015. 17, 18035.

(43) Applying equation (I) above the diffusivity at 300 K was determined and then the conductivity may be determined using the link between conductivity and diffusivity of equation (II). Table 1 shows the activation energy and room temperature conductivity determined for a series of compounds studied. Arrhenius plots of Li′ diffusivity are shown for each of these materials in FIGS. 4 to 20. The determined activation energies and lithium ion conductivities of these materials identifies them as materials suitable as solid state electrolyte and Li ion conductors according to the present disclosure.

(44) TABLE-US-00001 TABLE 1 Activation energy and room temperature conductivity of doped Li.sub.6KTaO.sub.6 from AIMD simulations. Composition Ea (eV) σ@300K (mS/cm) Li7IrO6 (Li substituted K) 0.34 0.35 Li7.33Sn0.33Ir0.67O6 0.30 1.92 Li6.17KNb0.83Zr0.17O12 0.29 0.34 Li6.33KNb0.67Sn0.33O12 0.27 1.05 Li6.5KNb0.5Zr0.5O12 0.17 16.43 Li6.67KNb0.33Zr0.67O12 0.22 4.84 Li6.33KSb0.67Sn0.33O12 0.16 21.12 Li6.33KI0.67Sn0.33O12 0.23 2.77 Li6.33KW0.67Sn0.33O12 0.49 0.001

(45) Accordingly, in one embodiment the present disclosure provides a solid-state lithium ion electrolyte, comprising: at least one material selected from the group of materials consisting of compounds of formulae (I), (II) and (III):
Li.sub.y(M1).sub.x1KMO.sub.6  (1)

(46) wherein M is selected from the group consisting of Ir, Sb, T, Nb and W, x1 is a number from greater than 0 to less than 6, y is a value such that charge neutrality of the formula is obtained, and M1 is at least one element different from Li selected from elements of groups 1, 2, 13 and transition metals;
Li.sub.yK.sub.1-x2(M2).sub.x2MO.sub.6  (II)

(47) wherein x2 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the composite formula is obtained, and M2 is at least one element different from K selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 13;
Li.sub.yKM.sub.1-x3(M3).sub.x3O.sub.6  (III)

(48) wherein x3 is a number from greater than 0 to less than 1, y is a value such that charge neutrality of the formula is obtained, and M3 is at least one element different from M selected from elements of groups 1-13.

(49) The compounds of formulae (I) to (III) are doped materials of the compound of general formula (IV):
Li.sub.6KMO.sub.6  (IV)
wherein at least one of Li, K and M are aliovalently replaced as described above. The compound of formula (IV) and the materials of formulae (I), (II) and (III) comprise a crystal lattice having a trigonal structure.

(50) The crystal structure of Li.sub.6KIrO.sub.6 is shown in FIG. 1. A calculated X-ray diffraction analysis obtained based on Cu-Kα radiation with wavelength of 1.54184 Å for Li.sub.6KIrO.sub.6 is shown in FIG. 2 and a Table showing the major peak positions (2θ) is shown in FIG. 3.

(51) The crystal structure of Li.sub.6KNbO.sub.6 is shown in FIG. 4. A calculated X-ray diffraction analysis obtained based on Cu-Kα radiation with wavelength of 1.54184 Å for Li.sub.6KNbO.sub.6 is shown in FIG. 5 and a Table showing the major peak positions (2θ) is shown in FIG. 6.

(52) The crystal structure of Li.sub.6KSbO.sub.6 is shown in FIG. 7. A calculated X-ray diffraction analysis obtained based on Cu-Kα radiation with wavelength of 1.54184 Å for Li.sub.6KSbO.sub.6 is shown in FIG. 8 and a Table showing the major peak positions (2θ) is shown in FIG. 9.

(53) The crystal structure of Li.sub.6KIO.sub.6 is shown in FIG. 10. A calculated X-ray diffraction analysis obtained based on Cu-Kα radiation with wavelength of 1.54184 Å for Li.sub.6KIO.sub.6 is shown in FIG. 11 and a Table showing the major peak positions (2θ) is shown in FIG. 12.

(54) The crystal structure of Li.sub.6KWO.sub.6 is shown in FIG. 13. A calculated X-ray diffraction analysis obtained based on Cu-Kα radiation with wavelength of 1.54184 Å for Li.sub.6KWO.sub.6 is shown in FIG. 14 and a Table showing the major peak positions (2θ) is shown in FIG. 15.

(55) The inventors have learned that the resulting doped materials according to formulae (I) to (I-III) retain the crystal structure of the base compounds (I-IV) and have activation energies and conductivity related to the base compounds. Based on the measurement methods described above the lithium ion (Li+) conductivity of the composite materials of formulae (I), (II), (III) and (IV) may be from 10.sup.−3 to 22 mS/cm at 300K, preferably from 0.1 to 22.0 mS/cm at 300K and most preferably from 1.0 to 22 mS/cm at 300K. The activation energy of the the materials of formulae (I), (II), (III) and (IV) may be from 0.15 to 0.50 eV, preferably from 0.25 eV to 0.40 eV.

(56) Synthesis of the compounds of the embodiments described above may be achieved by solid state reaction between stoichiometric amounts of selected precursor materials. Exemplary methods of solid state synthesis are described for example in each of the following papers: i) Monatshefte für Chemie, 100, 295-303, 1969; ii) Journal of Solid State Chemistry, 128, 1997, 241; iii) Zeitschrift furNaturforschung B,50,1995, 1061; iv) Journal of Solid State Chemistry 130, 1997, 90; v) Journal of Alloys and Compounds, 645, 2015, S174; vi) Z. Naturforsch. 51b, 199652 5; and vii) Weppner et al. (U.S. Pat. No. 8,092,941). Adaptation of these methods to prepare the composite compounds according to the embodiments disclosed herein is well within the capability of one of ordinary skill in the art.

(57) In further embodiments, the present application includes solid state lithium ion batteries containing the solid-state electrolytes described above. Solid-state batteries of these embodiments including metal-metal solid-state batteries may have higher charge/discharge rate capability and higher power density than classical batteries and may have the potential to provide high power and energy density.

(58) Thus, in further embodiments, solid-state batteries comprising: an anode; a cathode; and a solid state lithium ion electrolyte according to the embodiments described above, located between the anode and the cathode are provided.

(59) The anode may be any anode structure conventionally employed in a lithium ion battery. Generally such materials are capable of insertion and extraction of Li.sup.+ ions. Example anode active materials may include graphite, hard carbon, lithium titanate (LTO), a tin/cobalt alloy and silicon/carbon composites. In one aspect the anode may comprise a current collector and a coating of a lithium ion active material on the current collector. Standard current collector materials include but are not limited to aluminum, copper, nickel, stainless steel, carbon, carbon paper and carbon cloth. In an aspect advantageously arranged with the solid-state lithium ion conductive materials described in the first and second embodiments, the anode may be lithium metal or a lithium metal alloy, optionally coated on a current collector. In one aspect, the anode may be a sheet of lithium metal serving both as active material and current collector.

(60) The cathode structure may be any conventionally employed in lithium ion batteries, including but not limited to composite lithium metal oxides such as, for example, lithium cobalt oxide (LiCoO.sub.2), lithium manganese oxide (LiMn.sub.2O.sub.4), lithium iron phosphate (LiFePO.sub.4) and lithium nickel manganese cobalt oxide. Other active cathode materials may also include elemental sulfur and metal sulfide composites. The cathode may also include a current collector such as copper, aluminum and stainless steel.

(61) In one aspect, the active cathode material may be a transition metal, preferably, silver or copper. A cathode based on such transition metal may not include a current collector.

(62) In a further set of embodiments, electrodes containing the solid electrolyte materials of formulae (I) -(IV) are also disclosed. Thus in the preparation of the electrode the active material as described above may be physically mixed with the solid electrolyte material before application to the current collector or the solid electrolyte material may be applied as a coating layer on the applied active material. In either embodiment the presence of the lithium ion super conductor on or within the the electrode structure may enhance performance of the electrode and especially when applied as a coating layer, may serve to protect a conventional solid state electrolyte.

(63) Thus, an embodiment of the present disclosure includes a cathode comprising a current collector and a layer of cathode active material applied to the current collector wherein at least one of the following components is present: i) the cathode active material applied to the current collector is a physical mixture containing at least one of the solid electrolyte materials of formulae (I) -(IV) as described above; and ii) the layer of cathode active material applied to the current collector is coated with a layer comprising at least one of the solid electrolyte materials of formulae (I) -(IV). Cathodes having both elements i) and ii) are also included in the present disclosure.

(64) In related embodiments the present disclosure includes an anode comprising a current collector and a layer of anode active material applied to the current collector wherein at least one of the following components is present: i) the anode active material applied to the current collector is a physical mixture containing at least one of the solid electrolyte materials of formulae (I) -(IV) as described above; and ii) the layer of anode active material applied to the current collector is coated with a layer comprising at least one of the solid electrolyte materials of formulae (I) -(IV).

(65) Batteries containing a cathode as described in the above embodiment, an anode described in the above embodiment or containing both an anode and cathode according to the above embodiments are also embodiments of the present disclosure.

(66) The above description is presented to enable a person skilled in the art to make and use the invention, and is provided in the context of a particular application and its requirements. Various modifications to the preferred embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments and applications without departing from the spirit and scope of the invention. Thus, this invention is not intended to be limited to the embodiments shown, but is to be accorded the widest scope consistent with the principles and features disclosed herein. In this regard, certain embodiments within the invention may not show every benefit of the invention, considered broadly.