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

Abstract

Solid-state lithium ion electrolytes of lithium potassium bismuth oxide based compounds are provided which contain an anionic framework capable of conducting lithium ions. Materials 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 provided. Electrodes containing the lithium borate based materials coated on the active material and batteries containing the electrodes are also provided.

Claims

1. A solid-state lithium ion electrolyte, comprising: at least one material selected from the group of compounds of formulae (I), (II), (III) and (IV):
Li.sub.y(M1).sub.x1KBiO.sub.6  (I) wherein 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 metal different from Li selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 13;
Li.sub.yK.sub.1-x2(M2).sub.x2BiO.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 at least one metal different from K selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 13;
Li.sub.yBi.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 at least one metal different from Bi selected from elements of groups 13, 14 and 15; and
Li.sub.yKBiO.sub.6-x4(X).sub.x4  (IV) wherein x4 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 X is at least one element different from 0 selected from elements of groups 15, 16 and 17.

2. The solid state lithium ion electrolyte according to claim 1, wherein the material of formulae (I)-(IV) is of a trigonal crystal structure, an activation energy of the composite is from 0.15 to 0.3 eV, and a lithium ion conductivity is from 0.1 to 13.0 mS/cm at 300K.

3. The solid state lithium ion electrolyte according to claim 1, wherein an X-ray Diffraction (XRD) analysis of the material obtained based on Cu-Kα radiation with wavelength of 1,54184 Å comprises the following peaks which have a relative intensity to the highest intensity peak of at least 10%: TABLE-US-00002 Peak position Relative intensity 17.199 100.000  21.113 94.141 27.345 60.688 27.358 44.251 34.802 23.002 34.812 13.231 37.002 25.393 41.062 65.207 42.963 17.130 42.988 20.950 46.625 18.685 51.702 17.045 53.306 19.779 56.460 12.784 57.987 14.187 60.928 19.272 60.955  11.884.

4. 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 compounds of formulae (I), (II), (III), (IV) and (V):
Li.sub.y(M1).sub.x1KBiO.sub.6  (I) wherein 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 metal different from Li selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 13;
Li.sub.yK.sub.1-x2(M2).sub.x2BiO.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 at least one metal different from K selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 9, 10, 11, 12, and 13;
Li.sub.yKBi.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 at least one metal different from Bi selected from elements of groups 13, 14 and 15;
Li.sub.yKBiO.sub.6-x4(X).sub.x4  (IV) wherein x4 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 X is at least one element different from O selected from elements of groups 15, 16 and 17; and
Li.sub.6KBiO.sub.6  (V).

5. The solid state lithium battery of claim 4, wherein the material of formulae (I)-(V) is of a trigonal crystal structure, an activation energy of the material is from 0.15 to 0.3 eV, and a lithium ion conductivity is from 0.1 to 13 mS/cm at 300K.

6. The solid state lithium battery of claim 5, wherein an XRD analysis of the material obtained based on Cu-Kα radiation with wavelength of 1.54184 Å comprises the following peaks which have a relative intensity to the highest intensity peak of at least 10%: TABLE-US-00003 Peak position Relative intensity 17.199 100.000  21.113 94.141 27.345 60.688 27.358 44.251 34.802 23.002 34.812 13.231 37.002 25.393 41.062 65.207 42.963 17.130 42.988 20.950 46.625 18.685 51.702 17.045 53.306 19.779 56.460 12.784 57.987 14.187 60.928 19.272 60.955  11.884.

7. The solid state lithium battery of claim 4, wherein the battery is a lithium metal battery or a lithium ion battery.

8. An electrode for a solid state lithium battery, comprising: a current collector; an electrode active layer on the current collector; and a coating on the surface of the electrode active layer opposite the current collector; wherein the coating is of a compound of at least one material selected from the group of compounds of formulae (I), (II), (III), (IV) and (V):
Li.sub.y(M1).sub.x1 KBiO.sub.6  (I) wherein 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 metal different from Li selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 13;
Li.sub.yK.sub.1-x2(M2).sub.x2 BiO.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 at least one metal different from K selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, and 13;
Li.sub.yKBi.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 at least one metal different from Bi selected from elements of groups 13, 14 and 15;
Li.sub.yKBiO.sub.6-x4(X).sub.x4  (IV) wherein x4 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 X is at least one element different from O selected from elements of groups 15, 16 and 17; and
Li.sub.6KBiO.sub.6  (V).

9. The electrode for a solid state lithium battery of claim 8, wherein the material of formulae (I)-(V) is of a trigonal crystal structure, an activation energy of the material is from 0.15 to 0.3 eV, and a lithium ion conductivity of the material is from 0.1 to 13.0 mS/cm at 300K.

10. A solid state lithium battery comprising at least one electrode according to claim 8, 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.6KBiO.sub.6.

(2) FIG. 2 shows an Arrhenius plot of Li.sup.+ diffusivity D in Li.sub.6KBiO.sub.6 doped with Sn, Rh or Cr as indicated.

(3) FIG. 3 shows the calculated X-ray Diffraction Analysis for Li.sub.6KBiO.sub.6 obtained based on Cu-Kα radiation with wavelength of 1.54184 Å.

(4) FIG. 4 shows the position (2θ) and relative intensity of the peaks of the X-ray Diffraction Analysis for Li.sub.6KBiO.sub.6.

(5) FIG. 5 shows a schematic diagram of the electrode according to one embodiment.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

(6) 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.

(7) 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. 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.

(8) 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.sup.+ 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.

(9) The inventors are conducting ongoing investigations of new lithium compounds in order to identify materials having the properties which may serve as solid-state electrolytes in solid state lithium batteries. Such materials may also have utility as components of an electrode active material to improve capacity and/or cycling performance. Additionally and/or alternatively, such composite materials may be employed as protective coatings on an electrode active layer. In the course of this ongoing study and effort the inventors have developed and implemented a methodology to identify 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.

(10) 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.

(11) 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 metal sulfide 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 Si with aliovalent cationic species while compensating the charge neutrality with Li vacancy or excess Li. For example, replacing 50% of Si in Li.sub.10Si.sub.2PbO.sub.10 with P results in the formation of Li.sub.9PSiPbO.sub.10.

(12) The diffusivity at 300 K was determined according to equation (I)
D=D.sub.0 exp(−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 (II):
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.

(13) 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.

(14) Thus, selected lithium potassium bismuth 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.

(15) 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:

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

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

(18) 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 be derived from the n×2 matrices.

(19) 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.

(20) Ab initio molecular dynamics (AIMD) simulation was then applied to predict the conductivity of the targeted lithium aluminum borates. The initial structures were statically relaxed and were set to an initial temperature of 100 K. The structures were then heated to targeted temperatures (600-1200 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. Typical examples of the calculated diffusivity as a function of temperature are shown in FIG. 2 for samples of Li.sub.6.5KBi.sub.0.5Sn.sub.0.5O.sub.6, Li.sub.6.335KBi.sub.0.665Sn.sub.0.335O.sub.6, Li.sub.6.165KBi.sub.0.835Sn.sub.0.165O.sub.6, Li.sub.6.165KBi.sub.0.835Rh.sub.0.165O.sub.6 and Li.sub.6.335KBi.sub.0.665Cr.sub.0.335O.sub.6 where doping with Sn, Rh or Cr is shown. The Li.sup.+ diffusivity at different temperatures from 600-1200 K follows an Arrhenius-type relationship.

(21) 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 each of the samples of FIG. 2.

(22) TABLE-US-00001 TABLE 1 Activation energy and room temperature conductivity of doped Li.sub.3Al(BO.sub.3).sub.2 from AIMD simulations. composition E.sub.a (eV) σ (mS/cm) at 300K Li.sub.6.5KBi.sub.0.5Sn.sub.0.5O.sub.6 0.18 11 Li.sub.6.335KBi.sub.0.665Sn.sub.0.335O.sub.6 0.19 8 Li.sub.6.165KBi.sub.0.835 Sn.sub.0.165O.sub.6 0.27 0.33 Li.sub.6.165KBi.sub.0.835Rh.sub.0.165O.sub.6 0.19 7 Li.sub.6.335KBi.sub.0.665Cr.sub.0.335O.sub.6 0.19 13

(23) As indicated, all of the compounds have conductivities above 0.1 mS/cm, thus meeting one of the requirements to be suitable as a solid Li-ion conductor.

(24) Accordingly, the first embodiment provides a solid-state lithium ion electrolyte, comprising: at least one material selected from the group of compounds of formulae (I), (II), (III) and (IV):
Li.sub.y(M1).sub.x1KBiO.sub.6  (I)

(25) wherein 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, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 13;
Li.sub.yK.sub.1-x2(M2).sub.x2BiO.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 at least one element different from K selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16 and 17;
Li.sub.yKBi.sub.1-x3(M3).sub.x3O.sub.6  (III)

(26) 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 Bi selected from elements of groups 13, 14 and 15; and
Li.sub.yKBiO.sub.6-x4(X).sub.x4  (IV)

(27) wherein x4 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 X is at least one element different from O selected from elements of groups 15, 16 and 17.

(28) The materials of formulae (I) to (IV) are doped materials of the compound of formula (V):
Li.sub.6KBiO.sub.6  (V)
wherein at least one of Li, K, Bi and O are aliovalently replaced as described above. The inventors have learned that the resulting doped materials retain the crystal structure of the base compound and have activation energies and conductivity related to the base compound of formula (V). Based on the measurement methods described above the lithium ion (Li.sup.+) conductivity of the solid state lithium ion electrolytes of formulae (I) to (V) is from 0.1 to 13.0 mS/cm at 300K, the activation energy of the composite of formula (IV) is 0.15 to 0.3 eV, and the composite of formula (V) comprises a crystal lattice structure having a trigonal crystal structure.

(29) A calculated X-ray diffraction analysis for Li.sub.6KBiO.sub.6 obtained based on Cu-Kα radiation with wavelength of 1.54184 Å is shown in FIG. 3 and the location (2θ) and relative intensities of the major peaks is shown in FIG. 4.

(30) Synthesis of the materials 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 für Naturforschung B,50,1995, 1061; iv) Journal of Solid State Chemistry 130, 1997, 90; v) Journal of Alloys and Compounds, 645, 2015, 5174; and vi) Z. Naturforsch. 51b, 199652 5. Exemplary methods of synthesis of bismuth metal oxides are described in K. Kumada et al., Mater. Res. Bull., 32, 1003-8 (1997); K. Kumada et al., Solid State Ionics, 122, 183-9(1999); D. E. Cox & A. W. Sleight, Solid State Commun., 19, 969-973 (1976); and O. Knop et al., Can. J. Chem., 58, 2221-4 (1980). Adaptation of these methods to prepare the compounds according to the embodiments disclosed herein is well within the capability of one of ordinary skill in the art.

(31) 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.

(32) 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.

(33) The anode may be any anode structure conventionally employed in a lithium ion battery or lithium metal 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.

(34) 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.

(35) 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.

(36) In a further set of embodiments, electrodes for solid state lithium batteries containing the solid electrolyte composites of formulae (I) to (V) are also provided.

(37) Thus the present disclosure provides 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 a composite compound of at least one composite material selected from the group of compounds of formulae (I), (II), (III), (IV) and (V):
Li.sub.y(M1).sub.x1KBiO.sub.6  (I)

(38) wherein 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, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 13;
Li.sub.yK.sub.1-x2(M2).sub.x2BiO.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 at least one element different from K selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 12, 13, 14, 16 and 17;
Li.sub.yKBi.sub.1-x3(M3).sub.x3O.sub.6  (III)

(39) 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 Bi selected from elements of groups 13, 14 and 15;
Li.sub.yKBiO.sub.6-x4(X).sub.x4  (IV)

(40) wherein x4 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 X is at least one element different from O selected from elements of groups 15, 16 and 17; and
Li.sub.6KBiO.sub.6  (V).

(41) In another embodiment, the present disclosure provides 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 is coated on a surface opposite the current collector with a composition comprising a compound of at least one material selected from the group of compounds of formulae (I), (II), (III), (IV) and (V):
Li.sub.y(M1).sub.x1KBiO.sub.6  (I)

(42) wherein 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, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 13;
Li.sub.yK.sub.1-x2(M2).sub.x2BiO.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 at least one element different from K selected from elements of groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16 and 17;
Li.sub.yKBi.sub.1-x3(M3).sub.x3O.sub.6  (III)

(43) 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 Bi selected from elements of groups 13, 14 and 15;
Li.sub.yKBiO.sub.6-x4(X).sub.x4  (IV)

(44) wherein x4 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 X is at least one element different from O selected from elements of groups 15, 16 and 17; and
Li.sub.6KBiO.sub.6  (V).

(45) In each of these electrode embodiments, the physical properties and other aspects described above for the solid state electrolyte are also applicable.

(46) FIG. 5 shows a schematic drawing of the arrangement of elements in a general electrode according to the embodiment. Component (10) is the current collector. Layer (20) on the current collector is the electrode active material. Surface (4) of the electrode active material which is opposite the side on the current collector is coated with layer (30) of the material according to formulae (I) to (V).

(47) 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 exposed surface of the active material which has been applied onto the current collector. In either embodiment the presence of the lithium ion super conductor on or within the electrode structure may enhance performance of the electrode, for example, by increase of capacity and/or charge/discharge cycling stability and especially when applied as a coating layer, may serve to protect a conventional solid state electrolyte. Further, such coating may serve to improve adhesion of the electrode surface with a solid state electrolyte.

(48) 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 the layer of cathode active material applied to the current collector is coated on a surface opposite the current collector with a layer comprising at least one of the solid electrolyte materials of formulae (I) to (V).

(49) 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 composites of formulae (I) to (V) 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 composites of formulae (I) to (V).

(50) Batteries containing a cathode as described in the above embodiments, 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.

(51) 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.