LITHIUM-STUFFED GARNET ELECTROLYTES WITH SECONDARY PHASE INCLUSIONS
DETAILED ACTION
Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Information Disclosure Statement
The information disclosure statements (IDS) submitted on 6/5/2024, 1/28/2025, and 6/9/2025 are in compliance with the provisions of 37 CFR 1.97. Accordingly, the information disclosure statements are being considered by the examiner.
Claim Rejections - 35 USC § 112
The following is a quotation of the first paragraph of 35 U.S.C. 112(a):
(a) IN GENERAL.—The specification shall contain a written description of the invention, and of the manner and process of making and using it, in such full, clear, concise, and exact terms as to enable any person skilled in the art to which it pertains, or with which it is most nearly connected, to make and use the same, and shall set forth the best mode contemplated by the inventor or joint inventor of carrying out the invention.
The following is a quotation of the first paragraph of pre-AIA 35 U.S.C. 112:
The specification shall contain a written description of the invention, and of the manner and process of making and using it, in such full, clear, concise, and exact terms as to enable any person skilled in the art to which it pertains, or with which it is most nearly connected, to make and use the same, and shall set forth the best mode contemplated by the inventor of carrying out his invention.
Claims 100-122 are rejected under 35 U.S.C. 112(a) or 35 U.S.C. 112 (pre-AIA ), first paragraph, as failing to comply with the written description requirement. The claim(s) contains subject matter which was not described in the specification in such a way as to reasonably convey to one skilled in the relevant art that the inventor or a joint inventor, or for applications subject to pre-AIA 35 U.S.C. 112, the inventor(s), at the time the application was filed, had possession of the claimed invention.
Claims 100 and 115 disclose chemical formula LiALaBM’CM”DZrEOF wherein 4<A<8.5, 1.5<B<4, 0<C≤2,0<D<2; 0<E<2, 10<F<13.
However, there is no disclosure in the specification for 0<C≤2,0<D<2, and 0<E<2. While paragraph 000191 discloses 0<C<2.5, 0<D<2, and 0<e<2, these are for different elements.
Claims 101-114 and 116-122 are also rejected under 35 USC 112(a) for being dependent on claims 100 and 115.
Claim Rejections - 35 USC § 102
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of the appropriate paragraphs of 35 U.S.C. 102 that form the basis for the rejections under this section made in this Office action:
A person shall be entitled to a patent unless –
(a)(1) the claimed invention was patented, described in a printed publication, or in public use, on sale, or otherwise available to the public before the effective filing date of the claimed invention.
Claims 121-122 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Xu et al. (J. Power Sources, 302, (2016), 291-297).
Regarding claim 121, Xu et al. teach a powder (Section 2 discloses synthesizing a garnet powder.) comprising:
a primary phase selected from cubic lithium-stuffed garnet (Section 3.1 discloses a cubic-phased lithium garnet.); and a secondary phase comprising tetragonal phase garnet (Section 3.1 discloses tetragonal phase garnets.).
Regarding claim 122, Xu et al. teach the powder of claim 121, wherein the secondary phase comprises further comprises LixAlyOz wherein 1≤x≤5, 1≤y≤5, and 2≤z≤8, LixZryOz wherein 2≤x≤8, 0≤y≤1, and 1≤z≤6, or a combination thereof (Fig. 1 shows multiple phases comprised of LiLaO2, La2Zr2O7, Li6Zr2O7, and Li5AlO4.).
Claim Rejections - 35 USC § 103
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
The text of those sections of Title 35, U.S. Code not included in this action can be found in a prior Office action.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
Claims 100-105, 107-110, 112-122 are rejected under 35 U.S.C. 103 as being unpatentable over Holme et al. (US 2015/0099190 A1) and Djenadic et al. (Solid State Ionics, 263, (2014), 49-56), and further in view of Xu et al. (J. Power Sources, 302, (2016), 291-297).
Regarding claims 100, 105, 107-110, 112, and 113, Holme et al. teach a bilayer (Paragraph 0041, fig. 35 disclose a garnet film bilayer.) comprising:
a metal foil or metal powder bonded to one side of a sintered lithium-stuffed garnet thin film (Paragraph 0245 discloses wherein the garnet is optionally bonded to a current collector (CC) film comprising a metal or metal powder on at least one side of the film. Further, paragraph 0212 discloses the current collector film is a substrate. In certain examples, the substrate is a polymer, a metal foil, or a metal powder. In some of these examples, the substrate is a metal foil. In some examples, the substrate is a metal powder. In some of these examples, the metal is selected from Ni, Cu, Al, steel, alloys, or combinations thereof.);
wherein the sintered lithium-stuffed garnet thin film includes:
a primary cubic phase lithium-stuffed garnet characterized by the chemical formula LiALaBM’CM”DZrEOF wherein 4<A<8.5, 1.5<B<4, 0<C≤2,0<D<2; 0<E<2, 10<F<13, and M’ and M" are each, independently in each instance selected from the group consisting of Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, and Ta (Paragraph 0092 discloses a lithium stuffed garnet having a garnet crystal structure which is inherently cubic. The formula comprises: LiALaBM’CM”DZrEOF, 4<A<8.5, 1.5<B<4, 0≤C≤2, 0≤D≤2, 0≤E≤2, 10<F<13, M' and M'' are each, independently in each instance selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta.).
However, they do not teach a secondary phase inclusion; wherein: the primary cubic phase lithium-stuffed garnet is present in the sintered lithium- stuffed garnet thin film at about 70-99.9 vol % with respect to the volume of the sintered lithium-stuffed garnet thin film; and the secondary phase inclusion is present in the sintered lithium-stuffed garnet thin film at about 0.1-30 vol% with respect to the volume of the sintered lithium-stuffed garnet thin film,
wherein the secondary phase inclusion includes at least two materials selected from the groups consisting of: (i) tetragonal phase garnet; LiaZrbOc, wherein 1≤a≤8,1≤b≤2, and 1≤c≤7, and wherein subscripts a, b, and c are selected so that LiaZrbOc is charge neutral; LigAlhOi, wherein 1≤g≤5, 1≤h≤5, and 2≤i≤8, and wherein subscripts g, h, i are selected so that LigAlhOi is charge neutral; and (ii) La2Zr2O7; La2O3; LaAlO3; La2(Li0.5Al0.5)O4; LiLaO2; LiZr2O3;and combinations thereof.
Djenadic et al. teach a multiphase thin film solid-state electrolyte (Introduction) comprising: a primary cubic phase lithium-stuffed garnet (Abstract discloses Li7-3xLa3Zr2AlxO12, x=0-0.25); a secondary phase inclusion in the primary cubic phase lithium-stuffed garnet (Fig. 2, table 2); wherein: the primary cubic phase lithium-stuffed garnet is present in the multiphase thin film solid-state electrolyte at about 70-99.9 vol % with respect to the volume of the multiphase thin film electrolyte; and the secondary phase inclusion is present in the multiphase thin film solid-state electrolyte at about 30-0.1 vol% with respect to the volume of the multiphase thin film electrolyte(Table 2 discloses 97.9 wt% of Li7L3Zr2O12 (LLZO) and 1.3 wt.% of La2Zr2O7 (LZO). The densities of LLZO and LZO are 4.99 and 5.88 g/cm3 respectively. As such, the vol % for each compound will be 98.9 vol% LLZO and 1.11 vol.% LZO.).
Therefore, it would have been obvious to one of ordinary skill in the art to modify Holme with Djenadic in order to increase conductivity.
However, Neither Holme nor Djenadic teach wherein the secondary phase inclusion includes at least two materials selected from the groups consisting of: (i) tetragonal phase garnet; LiaZrbOc, wherein 1≤a≤8,1≤b≤2, and 1≤c≤7, and wherein subscripts a, b, and c are selected so that LiaZrbOc is charge neutral; LigAlhOi, wherein 1≤g≤5, 1≤h≤5, and 2≤i≤8, and wherein subscripts g, h, i are selected so that LigAlhOi is charge neutral; and (ii) La2Zr2O7; La2O3; LaAlO3; La2(Li0.5Al0.5)O4; LiLaO2; LiZr2O3;and combinations thereof.
Xu et al. teach synthesis of Li7La3Zr2O12 (LLZO) doped with Al (Abstract). The LLZO material synthesized can have multiple phases comprised of LiLaO2, La2Zr2O7, Li6Zr2O7, and Li5AlO4.
Therefore, it would have been obvious to modify Holme and Djenadic with Xu in order to improve stability and ionic conductivity.
Regarding claim 101, the combination of Holme, Djenadic, and Xu et al. teach the bilayer of claim 100. Further, Holme et al. teach wherein the sintered lithium-stuffed garnet thin film thickness is less than 50 µm and greater than 10 nm (Paragraph 0228 discloses the sintered lithium-stuffed garnet thin film has a thickness from 10-60 nm. Paragraph 0229 discloses the sintered lithium-stuffed garnet thin film has a thickness from 11-60 µm. Paragraph 0231 discloses the sintered lithium-stuffed garnet thin film has a thickness from 100 nm to 5 µm.);
Regarding claim 102, the combination of Holme, Djenadic, and Xu et al. teach the bilayer of claim 100. Further, Holme et al. teach wherein the thin film solid-state electrolyte has an area of at least 25 cm2 (Paragraph 0260).
Regarding claim 103, the combination of Holme, Djenadic, and Xu et al. teach the bilayer of claim 100. Further, Holme et al. teach wherein the primary cubic phase lithium-stuffed garnet grain size d50 is from about 0.5µm-10µm (Paragraph 0204 discloses 10nm-10µm.).
Regarding claim 104, the combination of Holme, Djenadic, and Xu et al. teach the bilayer of claim 100. Further, Djenadic et al. teach wherein the secondary phase inclusion d50 grain size is less than 10 µm (Section 3.1 and table 1 disclose 1 nm.).
Therefore, it would have been obvious to one of ordinary skill in the art to modify Holme with Djenadic in order to increase conductivity.
Regarding claim 114, the combination of Holme, Djenadic, and Xu et al. teach the bilayer of claim 100. Further, Holme et al. where the multiphase thin film solid-state electrolyte has a total porosity of less than 5 vol% as determined by SEM. (Paragraph 0206)
Regarding claims 115, 117-120, Holme et al. teach a process of making a composition (Abstract; claim 39.)
wherein the composition comprises:
a primary cubic phase lithium-stuffed garnet characterized by the chemical formula LiALaBM’CM”DZrEOF wherein 4<A<8.5, 1.5<B<4, 0<C≤2,0<D<2; 0<E<2, 10<F<13, and M’ and M" are each, independently in each instance selected from the group consisting of Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, and Ta (Paragraph 0092 discloses a lithium stuffed garnet having a garnet crystal structure which is inherently cubic. The formula comprises: LiALaBM’CM”DZrEOF, 4<A<8.5, 1.5<B<4, 0≤C≤2, 0≤D≤2, 0≤E≤2, 10<F<13, M' and M'' are each, independently in each instance selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta.).
However, they do not teach a secondary phase inclusion; wherein: the primary cubic phase lithium-stuffed garnet is present in the sintered lithium- stuffed garnet thin film at about 70-99.9 vol % with respect to the volume of the sintered lithium-stuffed garnet thin film; and the secondary phase inclusion is present in the sintered lithium-stuffed garnet thin film at about 0.1-30 vol% with respect to the volume of the sintered lithium-stuffed garnet thin film,
wherein the secondary phase inclusion includes at least two materials selected from the groups consisting of: (i) tetragonal phase garnet; LiaZrbOc, wherein 1≤a≤8,1≤b≤2, and 1≤c≤7, and wherein subscripts a, b, and c are selected so that LiaZrbOc is charge neutral; LigAlhOi, wherein 1≤g≤5, 1≤h≤5, and 2≤i≤8, and wherein subscripts g, h, i are selected so that LigAlhOi is charge neutral; and (ii) La2Zr2O7; La2O3; LaAlO3; La2(Li0.5Al0.5)O4; LiLaO2; LiZr2O3;and combinations thereof;
the process comprising the following steps:(a) providing a mixture of lithium-stuffed garnet chemical precursors to the mixture, wherein an amount of Al in the mixture exceeds the solubility limit of Al in the primary cubic phase lithium-stuffed garnet; and (b) calcining the mixture by heating it to at least 800 °C.
Djenadic et al. teach a multiphase thin film solid-state electrolyte (Introduction) comprising: a primary cubic phase lithium-stuffed garnet (Abstract discloses Li7-3xLa3Zr2AlxO12, x=0-0.25); a secondary phase inclusion in the primary cubic phase lithium-stuffed garnet (Fig. 2, table 2); wherein: the primary cubic phase lithium-stuffed garnet is present in the multiphase thin film solid-state electrolyte at about 70-99.9 vol % with respect to the volume of the multiphase thin film electrolyte; and the secondary phase inclusion is present in the multiphase thin film solid-state electrolyte at about 30-0.1 vol% with respect to the volume of the multiphase thin film electrolyte(Table 2 discloses 97.9 wt% of Li7L3Zr2O12 (LLZO) and 1.3 wt.% of La2Zr2O7 (LZO). The densities of LLZO and LZO are 4.99 and 5.88 g/cm3 respectively. As such, the vol % for each compound will be 98.9 vol% LLZO and 1.11 vol.% LZO.).
the process comprising the following steps:(a) providing a mixture of lithium-stuffed garnet chemical precursors to the mixture, wherein an amount of Al in the mixture exceeds the solubility limit of Al in the primary cubic phase lithium-stuffed garnet (Section 2.1); and (b) calcining the mixture by heating it to at least 800 °C (Section 2.1 discloses 900 °C.).
Therefore, it would have been obvious to one of ordinary skill in the art to modify Holme with Djenadic in order to increase conductivity.
However, Neither Holme nor Djenadic teach wherein the secondary phase inclusion includes at least two materials selected from the groups consisting of: (i) tetragonal phase garnet; LiaZrbOc, wherein 1≤a≤8,1≤b≤2, and 1≤c≤7, and wherein subscripts a, b, and c are selected so that LiaZrbOc is charge neutral; LigAlhOi, wherein 1≤g≤5, 1≤h≤5, and 2≤i≤8, and wherein subscripts g, h, i are selected so that LigAlhOi is charge neutral; and (ii) La2Zr2O7; La2O3; LaAlO3; La2(Li0.5Al0.5)O4; LiLaO2; LiZr2O3;and combinations thereof.
Xu et al. teach synthesis of Li7La3Zr2O12 (LLZO) doped with Al (Abstract). The LLZO material synthesized can have multiple phases comprised of LiLaO2, La2Zr2O7, Li6Zr2O7, and Li5AlO4.
Therefore, it would have been obvious to modify Holme and Djenadic with Xu in order to improve stability and ionic conductivity.
Regarding claim 116, the combination of Holme, Djenadic, and Xu et al. teach the process of claim 115. Further, Holme et al. teach wherein the lithium-stuffed garnet chemical precursors are selected from: lithium hydroxide, lithium oxide, zirconium oxide, zirconium nitrate, zirconium acetate, lanthanum oxide, lanthanum nitrate, lanthanum acetate, aluminum oxide, aluminum, aluminum nitrate, aluminum nitrate nonahydrate, aluminum (oxy) hydroxide, gallium oxide, corundum, niobium oxide, tantalum oxide, and combinations thereof (Paragraph 0094 discloses lithium hydroxide, lithium oxide, zirconium oxide, lanthanum oxide, aluminum oxide, aluminum nitrate, aluminum nitrate nonahydrate, niobium oxide, tantalum oxide.).
Conclusion
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Daniel S. Gatewood, Ph.D.
Primary Examiner
Art Unit 1729
/DANIEL S GATEWOOD, Ph. D/Primary Examiner, Art Unit 1729 May 28th, 2026
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