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 .
Specification
The objection to the specification has been overcome by the amendment and is withdrawn.
Response to Arguments
Applicant's arguments filed October 28, 2025, have been fully considered but they are not persuasive.
Applicant contends that the Bi of Kintaka is not present as a solid solution in the garnet structure as required by the newly amended claims (p. 7). However, as quoted by Applicant, Kintaka states that the Bi is "likely segregated mainly in the grain boundaries" (emphasis added). After sintering, some portion of the Bi will necessarily migrate into the crystal structure.
Applicant contends that the Wagner and Wang references teach that Bi is uniformly distributed in the crystal structure after formation (pp. 8-10). This is irrelevant, as both references include the Bi with the LLZO precursors. The method of Kintaka involves addition of the Bi after the LLZO structure has been formed.
Claim Interpretation
The limitation “in the vicinity of the grain boundary” in claim 1 is being interpreted as 50 nm or less from the grain boundary toward the grain interior, as defined in [0021] of the instant specification. Note that if claim 1 is amended to explicitly include this definition, claims 14 and 19 would be rejected under 35 USC 112(d) for failure to further limit the parent claim.
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.
Claim(s) 1, 9-11, and 14 is/are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Kintaka (US 2014/0186720 A1).
Regarding claim 1, Kintaka teaches a solid electrolyte ceramic material comprising sintered solid electrolyte particles of Li, La, Bi, and O with a garnet-type crystal structure and a higher Bi concentration near the grain boundaries ([0084]).
The Bi is added to already-formed LLZO particles ([0084]). Some Bi will necessarily dissolve in the crystal structure and can only enter the particles by diffusion. The concentration will therefore necessarily decrease with distance from the grain boundaries, and the region within 50 nm of the grain boundary will necessarily have a higher concentration than the interior of the particles.
Regarding claim 9, the average grain size is 0.5 µm ([0084]), which falls within the range of the instant claim.
Regarding claim 10, the particles also contain Zr ([0084]).
Regarding claim 11, Kintaka teaches that any Bi substituted for Zr will be pentavalent ([0034]). The structure must therefore include at least some pentavalent Bi.
Regarding claim 14, the Bi is added to already-formed LLZO particles ([0084]) and therefore can only enter the particles by diffusion. The concentration will therefore necessarily decrease with distance from the grain boundaries, and the region within 50 nm of the grain boundary will necessarily have a higher concentration than the interior of the particles.
Claim Rejections - 35 USC § 103
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.
Claim(s) 15-19 is/are rejected under 35 U.S.C. 103 as being unpatentable over Kintaka as applied to claim 1 above.
Regarding claim 15, Kintaka teaches that the solid electrolyte is intended for use in a lithium battery such as an electrode/solid electrolyte laminate ([0076]-[0077]), which would necessarily be a solid-state battery. It would have been obvious to one of ordinary skill in the art before the effective filing date of the instant invention to use the electrolyte of Kintaka for its intended purpose.
Regarding claim 16, Kintaka gives an example in which electrode layers are laminated on the solid electrolyte layer, with the electrode layers including lithium-ion active materials ([0062]-[0063]). It would have been obvious to one of ordinary skill in the art before the effective filing date of the instant invention to try any of the configurations listed by Kintaka, including the laminated structure.
Regarding claim 17, the laminated structure is formed of green sheets ([0062]), which will necessarily result in an integrally sintered body.
Regarding claim 18, an electrode/solid electrolyte laminate would necessarily include the solid electrolyte in the solid electrolyte layer.
Regarding claim 19, the Bi is added to already-formed LLZO particles ([0084]) and therefore can only enter the particles by diffusion. The concentration will therefore necessarily decrease with distance from the grain boundaries, and the region within 50 nm of the grain boundary will necessarily have a higher concentration than the interior of the particles.
Claim(s) 3-8 is/are rejected under 35 U.S.C. 103 as being unpatentable over Kintaka as applied to claim 2 above, and further in view of Schwanz et al. (“Ionic conductivity enhacements and low temperature synthesis of Li7La3Zr2O12 garnets by Bi aliovalent substitutions”, arXiv:1902.06831 [cond-mat.mtrl-sci], February 2019).
Regarding claim 3, Kintaka teaches that the Bi may be substituted for Zr (Kintaka [0034]). Schwanz teaches that substituting Bi for Zr improves the garnet phase formation and ionic conductivity (Schwanz Abstract). It would have been obvious to one of ordinary skill in the art before the effective filing date of the instant invention to substitute Bi for Zr in the electrolyte material of Kintaka to improve garnet phase formation and ionic conductivity. Doing so will necessarily result in Bi occupying six-coordinated positions (i.e., the Zr position).
Regarding claims 4-7, modified Kintaka does not teach the claimed Bi molar ratios. Modified Kintaka teaches Zr-Bi substitutions at Bi molar concentrations of 0.05-0.4 (Kintaka Table 3). This gives an interior concentration x2 of 0-0.4 and a grain boundary concentration x1 of 0-2 depending on diffusion during firing/calcination, each of which overlaps the ranges of the instant claims. In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990).
Regarding claim 8, the majority of the Bi remains unintegrated after 3 hours of sintering (Kintaka [0084]), and firing time is typically limited to 10 hours (Kintaka [0055]-[0056] and [0050]). The incorporated Bi in the grain boundary region is therefore expected to be significantly higher than in the interior, including values above 0.01.
Claim(s) 20 is/are rejected under 35 U.S.C. 103 as being unpatentable over Kintaka as applied to claim 1 above, and further in view of Yokoyama (US 2020/0127326 A1).
Regarding claim 20, Kintaka does not teach a porosity of 10% or less. Yokoyama teaches voids in the solid electrolyte increase interface resistance (Yokoyama [0004] and that bulk density should be greater than 70% (Yokoyama [0085]-[0086]), which means porosity should be less than 30%, which overlaps the range of the instant claim. In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990). It would have been obvious to one of ordinary skill in the art before the effective filing date of the instant invention to eliminate as many voids as possible and therefore reduce porosity as much as possible, including to less than 10%, in order to prevent increasing interface resistance.
Claim(s) 1, 9-11, 14, 15, 19, and 20 is/are rejected under 35 U.S.C. 103 as being unpatentable over Yokoyama in view of Schwanz.
Regarding claim 1, Yokoyama teaches a gannet-type solid electrolyte ceramic material comprising sintered solid electrolyte particles of Li, La, Zr, O, and a metal Ma selected from a group including Bi (Yokoyama Abstract and [0003]). Yokoyama teaches that the element Ma that is not incorporated into the electrolyte is deposited at the grain boundary (Yokoyama [0044]). The concentration within 50 nm of the grain boundary is therefore necessarily higher than in the grain interior.
Yokoyama does not teach that Ma must be Bi. Schwanz teaches that substituting Bi for Zr in LLZO electrolytes improves the garnet phase formation and ionic conductivity (Schwanz Abstract). It would have been obvious to one of ordinary skill in the art before the effective filing date of the instant invention to substitute Bi for Zr in the electrolyte material of Yokoyama to improve garnet phase formation and ionic conductivity.
Regarding claim 9, modified Yokoyama teaches a grain size of 0.5-1 µm (Yokoyama [0070]), which falls within the range of the instant claim.
Regarding claim 10, the material of modified Yokoyama also includes Zr (Yokoyama Abstract).
Regarding claim 11, Ma is substituted for Zr (Yokoyama Abstract), so the Bi would necessarily be in pentavalent form.
Regarding claim 14, modified Yokoyama teaches that the element Ma not incorporated into the electrolyte is deposited at the grain boundary (Yokoyama [0044]). The concentration within 50 nm of the grain boundary is therefore necessarily higher than in the grain interior.
Regarding claim 15, modified Yokoyama teaches a solid-state lithium battery formed from the solid electrolyte (Yokoyama claim 5 and [0044]).
Regarding claim 19, Yokoyama teaches that the element Ma that is not incorporated into the electrolyte is deposited at the grain boundary (Yokoyama [0044]). The concentration within 50 nm of the grain boundary is therefore necessarily higher than in the grain interior.
Regarding claim 20, Yokoyama does not teach a porosity of 10% or less. Yokoyama teaches that bulk density should be greater than 70% (Yokoyama [0085]-[0086]), which means porosity should be less than 30%, which overlaps the range of the instant claim. In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990). In addition, Yokoyama teaches that voids in the solid electrolyte increases interface resistance (Yokoyama [0004]). It would have been obvious to one of ordinary skill in the art before the effective filing date of the instant invention to eliminate as many voids as possible and therefore reduce porosity as much as possible, including to less than 10%, in order to prevent increasing interface resistance.
Claim(s) 12 and 13 is/are rejected under 35 U.S.C. 103 as being unpatentable over Yokoyama in view of Schwanz as applied to claim1 above, and further in view of Li et al. (“Rational design of strontium antimony co-doped Li7La3Zr2O12 electrolyte membrane for solid-state lithium batteries”, Journal of Alloys and Compounds 794, pp. 347-357, July 2019).
Regarding claim 12, modified Yokoyama teaches an average composition of Li7-xLa3Zr2−(x+y)MaxMbyO12, where Ma is Bi, Mb is selected from a group including Ta, and 0.5<(x+y)<1.2 (Yokoyama claim 1), and that Ta is the preferred Mb (Yokoyama [0048]).
Modified Yokoyama does not teach that La3 is replaced with La3-zCz. Li teaches that substituting Sr for La in LLZO garnet electrolytes improves densification and ion mobility (Li Abstract). It would have been obvious to one of ordinary skill in the art before the effective filing date of the instant invention to substitute Sr for some of the La in the electrolyte of modified Yokoyama to improve densification and ion mobility. Li teaches a range of 0.02<z<0.2 (Li Table 1), which falls within the range of the instant claim.
This is the equivalent Li7-x+zLa3-zSrz(Zr+Ta)2−xBixO12, or formula 1 of the instant claim for y=0, M=Zr+Ta, C=Sr, a=0, b=4, c=2, and 0.02<z<0.2, each of which falls within the ranges of the instant claim; and 0<x<1.2, which overlaps the range of the instant claim. In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990).
Regarding claim 13, the composition of modified Yokoyama includes Zr.
Conclusion
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
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/J.A.C/ Examiner, Art Unit 1722
/NIKI BAKHTIARI/ Supervisory Patent Examiner, Art Unit 1722