DETAILED ACTION
Application 18/272,504, “SOLID ELECTROLYTE LAYER AND ALL-SOLID-STATE BATTERY”, was filed with the USPTO on 7/14/2023 and has a foreign priority document of JP2021-020431 filed on 2/12/2021.
This office action is in response to communication filed on 7/14/2023.
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 .
Priority
Acknowledgment is made of applicant’s claim for foreign priority under 35 U.S.C. 119 (a)-(d). The certified copy has been filed in parent Application No. 18/272,504, filed on 7/14/2023.
Information Disclosure Statement
The information disclosure statements (IDS) submitted on 7/14/2023, 8/19/2024, 5/19/2025 and 10/24/2025 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 § 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.
(a)(2) the claimed invention was described in a patent issued under section 151, or in an application for patent published or deemed published under section 122(b), in which the patent or application, as the case may be, names another inventor and was effectively filed before the effective filing date of the claimed invention.
Claims 1 and 4 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by ITO et al. (WO 2013/100000 A1, see machine translation for citation).
Regarding Claim 1, ITO et al. teaches a solid electrolyte layer (13, Fig. 1) comprising:
a first compound (first component, [0013], [0019]) represented by LiaM2(PO4)3 . . . (1) (LixMy(PO4)3, where x is a numerical value in the range of 1 ≤ x ≤ 2 and y is 1 ≤ y ≤ 2, [0019]; when x=1.2, y=2, M=Al, Ti, first component example is Li1.2Al0.2Ti1.8(PO4)3, [0020]); and
a second compound (second component [0013], [0040]) represented by M′P2O7 . . . (2) (Mm(P2O7)n, where m and n are integers of 1 or more, [0040], M selected from Ca, Ba, Sr, [0038]; when M=Ca, m=2, n=1, second component is Ca2P2O7),
wherein, in the first compound, a satisfies 0.9≤ a≤ 1.4 (a = 1.2 in Li1.2Al0.2Ti1.8(PO4)3, [0020]), M is one or more elements selected from the group consisting of Zr, Ti, Ge, Al, Hf, Ca, Ba, Sr, Sc, Y and In (Ti, Ge, Al and Zr, [0019]),
in the second compound, M′ is one or more elements selected from the group consisting of Zr, Ti, Ge, Al, Hf, Ca, Ba, Sr, Sc, Y and In (Ca, Ba, Sr, [0038]), and
an abundance ratio of the second compound (Mm(P2O7)n , [0040]; when M=Ca, m=2, n=1, second component is Ca2P2O7) is 0.5 volume % or more and less than 10 volume % (volume %* is 1.3 volume % or more and less than 4.9 volume %; “2 parts by mole or more and 8 parts by mole or less”, see [0023]).
*Note: volume % = ((mole % × molecular weight) ÷ density; taking first component Li1.2Al0.2Ti1.8(PO4)3 and second component Ca2P2O7:
Molecular weight Li1.2Al0.2Ti1.8(PO4)3 of is 357.73 g/mol, density1 is 2.83 g/cm3; molecular weight of Ca2P2O7 is 254.10 g/ mol, density2 is 3.09 g/cm3.
When Ca2P2O7 is 2 mole and Li1.2Al0.2Ti1.8(PO4)3 is 100 mole, volume % of Ca2P2O7 is (2 X 254.10 / 3.09) / (100 X 357.73 / 2.83 + 2 X 254.10 / 3.09) = 1.3%;
When Ca2P2O7 is 8 mole and Li1.2Al0.2Ti1.8(PO4)3 is 100 mole, volume % of Ca2P2O7 is (8 X 254.10 / 3.09) / (100 X 357.73 / 2.83 + 8 X 254.10 / 3.09) = 4.9%.
1Mohammed Isah Kimpa et al.; Physical characterization and electrical conductivity of Li1.2Ti1.8Al0.2(PO4)3 and Li1.2Ta0.9Al1.1(PO4)3 NASICON material; International Journal of Integrated Engineering, Vol. 10 No. 9 (2018) p. 108
2CRC Handbook of Chemistry and Physics 106th Edition, CRC Press; table “Physical Constants of Inorganic Compounds”, row 622, calcium pyrophosphate.
Regarding Claim 4, ITO et al. teaches an all-solid-state battery (10, Fig. 1) comprising:
the solid electrolyte layer (13, Fig. 1) comprising:
a first compound (first component, [0013], [0019]) represented by LiaM2(PO4)3 . . . (1) (LixMy(PO4)3, where x is a numerical value in the range of 1 ≤ x ≤ 2 and y is 1 ≤ y ≤ 2, [0019]; when x=1.2, y=2, M=Al, Ti, first component example is Li1.2Al0.2Ti1.8(PO4)3, [0020]); and
a second compound (second component [0013], [0040]) represented by M′P2O7 . . . (2) (Mm(P2O7)n, where m and n are integers of 1 or more, [0040], M selected from Ca, Ba, Sr, [0038]; when M=Ca, m=2, n=1, second component is Ca2P2O7),
wherein, in the first compound, a satisfies 0.9≤ a≤ 1.4 (a = 1.2 in Li1.2Al0.2Ti1.8(PO4)3, [0020]), M is one or more elements selected from the group consisting of Zr, Ti, Ge, Al, Hf, Ca, Ba, Sr, Sc, Y and In (Ti, Ge, Al and Zr, [0019]),
in the second compound, M′ is one or more elements selected from the group consisting of Zr, Ti, Ge, Al, Hf, Ca, Ba, Sr, Sc, Y and In (Ca, Ba, Sr, [0038]), and
an abundance ratio of the second compound (Mm(P2O7)n , [0040]; when M=Ca, m=2, n=1, second component is Ca2P2O7) is 0.5 volume % or more and less than 10 volume % (volume %* is 1.3 volume % or more and less than 4.9 volume %; “2 parts by mole or more and 8 parts by mole or less”, see [0023]).
*Note: volume % = ((mole % × molecular weight) ÷ density; taking first component Li1.2Al0.2Ti1.8(PO4)3 and second component Ca2P2O7:
Molecular weight Li1.2Al0.2Ti1.8(PO4)3 of is 357.73 g/mol, density1 is 2.83 g/cm3; molecular weight of Ca2P2O7 is 254.10 g/ mol, density2 is 3.09 g/cm3.
When Ca2P2O7 is 2 mole and Li1.2Al0.2Ti1.8(PO4)3 is 100 mole, volume % of Ca2P2O7 is (2 X 254.10 / 3.09) / (100 X 357.73 / 2.83 + 2 X 254.10 / 3.09) = 1.3%;
When Ca2P2O7 is 8 mole and Li1.2Al0.2Ti1.8(PO4)3 is 100 mole, volume % of Ca2P2O7 is (8 X 254.10 / 3.09) / (100 X 357.73 / 2.83 + 8 X 254.10 / 3.09) = 4.9%.
1Mohammed Isah Kimpa et al.; Physical characterization and electrical conductivity of Li1.2Ti1.8Al0.2(PO4)3 and Li1.2Ta0.9Al1.1(PO4)3 NASICON material; International Journal of Integrated Engineering, Vol. 10 No. 9 (2018) p. 108
2CRC Handbook of Chemistry and Physics 106th Edition, CRC Press; table “Physical Constants of Inorganic Compounds”, row 622, calcium pyrophosphate;
a positive electrode (11, Fig. 1); and
a negative electrode (12, Fig. 1), the positive electrode and the negative electrode sandwiching the solid electrolyte layer (Fig. 1).
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 (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 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 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 2-3 are rejected under 35 U.S.C. 103 as being unpatentable over ITO et al. (WO 2013/100000 A1, see machine translation for citation) in view of LAINE et al. (US 2021/0028444 A1).
Regarding Claim 2, ITO et al. does not teach wherein an average grain diameter Da of the first compound and an average grain diameter Db of the second compound satisfy 0.1≤Da/Db≤20.0.
LAINE et al. teaches wherein an average grain diameter (average grain sizes (AGSs), [0360]) Da of the first compound (MZPCe0.2 (Mg0.5Ce0.2Zr1.8(PO4)3), see [0360], [0369]) and an average grain diameter (average grain sizes (AGSs), [0360]) Db of the second compound (ZrP2O7, [0360]) satisfy 0.1≤Da/Db≤20.0 (Da/Db = 2.25 or 3.25; AGS of MZPCe0.2 is 550 ± 100 nm, AGS of ZrP2O7 is 200 nm; see [0360]).
It would have been obvious to one of ordinary skill in the art before the effective filling date of the claimed invention to modify the solid electrolyte layer taught by ITO et al. such that Da/Db is equal to either 2.25 or 3.25 as taught by LAINE et al. so that the films fracture in an intra-granular mode and show a flat fracture surface (see LAINE et al. [0359]).
Regarding Claim 3, ITO et al. does not teach wherein the average grain diameter Db of the second compound satisfies 0.01 μm≤Db≤10 μm.
LAINE et al. teaches wherein the average grain diameter Db (average grain sizes (AGSs), [0360]) of the second compound (ZrP2O7, [0360]) satisfies 0.01 μm≤Db≤10 μm (200 nm, 0.2 µm, [0360]).
It would have been obvious to one of ordinary skill in the art before the effective filling date of the claimed invention to modify the solid electrolyte layer taught by ITO et al. such that the average grain diameter Db of the second compound satisfies 200 nm/0.2 µm as taught by LAINE et al. because small grain size is, thus, an essential prerequisite for high-performance ionic conductors (see LAINE et al. [0361]).
Relevant or Related Art
The prior art made of record and not replied upon is considered pertinent to application’s disclosure, though not necessarily pertinent to applicant’s invention as claimed.
(TAISUKE) JP 2023/060591 A: first compound: LiZr2(PO4)3, Li1.3Al0.3Ti1.7(PO4)3; second compound: ZrP2O7, TiP2O7
(Tanaka) US 2023/0046253 A1: one compound: LixM2(PO4)z
(Kang) US 2014/0162136 A1: first compound: Li1+xAlxTi2−x(PO4)3, (0≦x≦0.5); second compound: TiP2O7
Conclusion
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/NING CHEN/Examiner, Art Unit 1723 /TIFFANY LEGETTE/Supervisory Patent Examiner, Art Unit 1723