Set forth herein are garnet material compositions, e.g., lithium-stuffed garnets and lithium-stuffed garnets doped with alumina, which are suitable for use as electrolytes and catholytes in solid state battery applications. Also set forth herein are lithium-stuffed garnet thin films having fine grains therein. Disclosed herein are novel and inventive methods of making and using lithium-stuffed garnets as catholytes, electrolytes and/or anolytes for all solid state lithium rechargeable batteries. Also disclosed herein are novel electrochemical devices which incorporate these garnet catholytes, electrolytes and/or anolytes. Also set forth herein are methods for preparing novel structures, including dense thin (<50 um) free standing membranes of an ionically conducting material for use as a catholyte, electrolyte, and, or, anolyte, in an electrochemical device, a battery component (positive or negative electrode materials), or a complete solid state electrochemical energy storage device. Also, the methods set forth herein disclose novel sintering techniques, e.g., for heating and/or field assisted (FAST) sintering, for solid state energy storage devices and the components thereof.

An exemplary embodiment of the present disclosure provides a method for manufacturing a transparent ceramic material. The method comprises providing a compact comprising a metal oxide and, during sintering, exposing the compact to a vapor comprising one of or both fluorine ions and lithium ions to form a transparent ceramic material comprising at least 90% of a theoretical transparency.

Set forth herein are processes for making lithium-stuffed garnet oxides (e.g., Li.sub.7La.sub.3Zr.sub.2O.sub.12, also known as LLZO) that have passivated surfaces comprising a fluorinate and/or an oxyfluorinate species. These surfaces resist the formation of oxides, carbonates, hydroxides, peroxides, and organics that spontaneously form on LLZO surfaces under ambient conditions. Also set forth herein are new materials made by these processes.

An oxide ion conductor has a X.sub.3Z.sub.2(TO.sub.4).sub.3 structure, where X is a divalent metal element, Z is a trivalent metal element, and T is a tetravalent metal element, and has a composition expressed by (X.sub.1-xA.sub.x).sub.3(Z.sub.1-yB.sub.y).sub.2(T.sub.1-zC.sub.z).sub.3O.sub.12+δ where the element X is Ca, Fe, Gd, Ba, Sr, Mn, and/or Mg, the element Z is Al, Cr, Fe, Mn, V, Ga, Co, Ni, Ru, Rh, and/or Ir, the element T is Si and/or Ge, an element A is La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and/or Sr, an element B is Zn, Mn, Co, Ru, and/or Rh, and an element C is Si, Al, Ga, and/or Sn, 0≤x≤0.2, 0≤y≤0.2, and 0≤z≤0.2 are satisfied, and δ is a value securing electrical neutrality.

A ceramic powder material containing: a first garnet-type compound containing Li, La, and Zr; and a second garnet-type compound containing Li, La, and Zr and having a composition different from a composition of the first garnet-type compound, in which the first garnet-type compound and the second garnet-type compound are represented by Formula [1] Li.sub.7-(3x+y)M1.sub.xLa.sub.3Zr.sub.2-yM2.sub.yO.sub.12, where M1 is Al or Ga, M2 is Nb or Ta, the first garnet-type compound satisfies 0≤(3x+y)≤0.5, and the second garnet-type compound satisfies 0.5<(3x+y)≤1.5.

Disclosed herein are ceramic materials, such as bismuth substituted garnets, which can have high curie temperatures and high dielectric constants. In certain implementations, indium can be incorporated into the ceramic to improve certain properties and to avoid calcium compensation. The ceramic materials disclosed herein can be particular advantageous for below resonance applications.

Embodiments of synthetic garnet materials having advantageous properties, especially for below resonance frequency applications, are disclosed herein. In particular, embodiments of the synthetic garnet materials can have high Curie temperatures and dielectric constants while maintaining low magnetization. These materials can be incorporated into isolators and circulators, such as for use in telecommunication base stations.

An oxide-based solid electrolyte with a high lithium ion conductance is provided. A lithium ion-conducting garnet type oxide includes Li, La, Ga, Zr, a halogen element, and oxygen. A lithium ion conductivity at room temperature is not lower than 1.0×10.sup.−3 S/cm. A proportion of Ga with respect to 1 mole of the oxide may be not larger than 0.5 moles.

The halogen element may be at least one type selected from the group consisting of Cl, Br, and I, and a proportion of Li with respect to 1 mole of the oxide may be not smaller than 6.1 moles and smaller than 6.5 moles.

A sintered composite ceramic includes a lithium-garnet major phase; and a lithium dendrite growth inhibitor minor phase, such that the lithium dendrite growth inhibitor minor phase comprises lithium tungstate. A method includes sintering a metal oxide component and a garnet component at a temperature in a range of 750° C. to 1500° C. to form a sintered composite ceramic.

A solid composition according to the present disclosure is a solid composition to be used for forming a functional ceramic having a crystal phase, and contains an oxide constituted by a crystal phase different from the crystal phase of the functional ceramic at normal temperature and normal pressure, and an oxoacid compound. The oxoacid compound preferably contains at least one of a nitrate ion and a sulfate ion as an oxoanion. Further, the oxide preferably has a crystal grain size of 10 nm or more and 200 nm or less.