DETAILED ACTION
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 submitted on December 20, 2024 and June 11, 2026 have been considered by the examiner.
Claim Objections
Claim 1 is objected to because of the following informalities. Lines 7-8 of the claim include the limitation: “a temperature of from 400 to 850 ∘C”.
The degree symbol should appear in its standard position and each number should be followed by its unit.
The limitation should be edited to read” “a temperature of from 400 °C to 850 °C”.
Claim 12 is objected to because of the following informalities. Line 1 of the claim includes the limitation: “wherein heat treating step”.
The word “the” should be added after the word “wherein” to amend the limitation to read: “wherein the heat treating step”.
Appropriate correction is required.
Claim Rejections - 35 USC § 112(b)
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claim 11 is rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
Claim 11 recites the limitations "the La precursor" on line 2. There is insufficient antecedent basis for this limitation in the claim.
Claim 13 is rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
Claim 13 recites the limitations "the Zr precursor" and “the La precursor” on line 2. There is insufficient antecedent basis for this limitation in the claim.
Claim 14 is rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
Claim 14 recites the limitations "the Zr precursor" (line 2) and “the La precursor” (line 3) on line 2. There is insufficient antecedent basis for this limitation in the claim.
Claim Rejections - 35 USC § 112(d)
The following is a quotation of 35 U.S.C. 112(d):
(d) REFERENCE IN DEPENDENT FORMS.—Subject to subsection (e), a claim in dependent form shall contain a reference to a claim previously set forth and then specify a further limitation of the subject matter claimed. A claim in dependent form shall be construed to incorporate by reference all the limitations of the claim to which it refers.
The following is a quotation of pre-AIA 35 U.S.C. 112, fourth paragraph:
Subject to the following paragraph [i.e., the fifth paragraph of pre-AIA 35 U.S.C. 112], a claim in dependent form shall contain a reference to a claim previously set forth and then specify a further limitation of the subject matter claimed. A claim in dependent form shall be construed to incorporate by reference all the limitations of the claim to which it refers.
Claim 10 is rejected under 35 U.S.C. 112(d) or pre-AIA 35 U.S.C. 112, 4th paragraph, as being of improper dependent form for failing to further limit the subject matter of the claim upon which it depends, or for failing to include all the limitations of the claim upon which it depends.
Claim 10 requires a formula for the LLZO, which includes the doping element D.
Claim 10 depends on claim 7 via claim 8. Claim 7 defines a formula for the LLZO, which does not allow for the presence of the doping element D.
As such, claim 10 broadens the scope of claim 7, rather than limiting it.
Applicant may cancel the claim, amend the claim to place the claim in proper dependent form, rewrite the claim in independent form, or present a sufficient showing that the dependent claim complies with the statutory requirements.
Claim Rejections - 35 USC § 102
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 1-7, 12-14 and 16-19 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by J. Ind. Eng. Chem, 36, p 279-283, hereinafter Kim, with evidence from U.S. Pre-Grant Publication No. 2021/0198117, hereinafter Durham.
Regarding claim 1, Kim teaches a method of producing LLZO having a cubic crystal phase (abstract).
The method comprises a step of providing an aqueous solution comprising Zr and La. The aqueous solution has a pH of 11 (p. 283, Synthesis process of precursor).
The method further comprises a step of coprecipitating to form a precursor (“intermediate”) precipitate comprising lanthanum hydroxide and zirconium hydroxide from the Zr and the La in the aqueous solution (abstract and p. 283, Synthesis process of precursor). It is known in the art that the precipitate resulting from the reaction is La(OH)3 and Zr(OH)4 (see, e.g. Durham, paragraph [0004]). La(OH)3 is a crystalline material and Zr(OH)4 is an amorphous material.
The method further comprises a step of recovering and washing the precursor (“intermediate”) precipitate (p. 283, Synthesis process of precursor).
The method further comprises a step of calcining (“heat treating”) the washed precursor (“intermediate”) precipitate with a Li source at a temperature of 700°C and 800°C (abstract and p. 283, Calcining and sintering process of Li7La3Zr2O12).
Regarding claims 2 and 3, Kim teaches that a Zr precursor is added to the aqueous solution. The Zr precursor is Zr oxy-nitrate (p. 283, Synthesis process of precursor).
Regarding claims 4 and 5, Kim teaches that a La precursor is added to the aqueous solution. The La precursor is La nitrate (p. 283, Synthesis process of precursor).
Regarding claim 6, Kim teaches that the Li source is LiOH (p. 283, Calcining and sintering process of Li7La3Zr2O12).
Regarding claim 7, Kim teaches that the LLZO has the formula Li7La3Zr2O12 (abstract).
Regarding claim 12, Kim teaches that the Li precursor was added according to the stoichiometric ratio Li:La:Zr = 7:3:2 (p. 283, Calcining and sintering process of Li7La3Zr2O12) – it is therefore understood that Li was provided in excess of 0%.
Regarding claim 13, Kim teaches mixing the Zr precursor and the La precursor and then adjusting the pH of the aqueous phase to be 11 (p. 283, Synthesis process of precursor).
Regarding claim 14, Kim teaches mixing the Zr precursor and the La precursor and then adjusting the pH of the aqueous phase to be 11 (p. 283, Synthesis process of precursor).
Kim fails to teach separately adjusting the pH of each of the Zr precursor solution and the La precursor solution.
It would have been obvious to the ordinarily skilled artist before the effective filing date of the claimed invention to adjust the pH of each of the Zr precursor solution and the La precursor solution and then mixing them together to have a final pH of 11 would be an obvious variation and would have the same effect as first mixing the Zr precursor and the La precursor and then adjusting the pH of the mixture to 11.
Regarding claims 16 and 17, Kim teaches maturing (“aging”) the precursor (“intermediate”) at room temperature (22°C) for 24 hours (p. 283, Synthesis process of precursor).
Regarding claim 18, Kim teaches that the washing step is performed using water (p. 283, Synthesis process of precursor).
Regarding claim 19, Kim teaches that the LLZO particles generated at 700°C have lengths of 300-600 nm and widths of 50-100 nm (p. 280, 3rd paragraph).
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.
Claims 8-10 are rejected under 35 U.S.C. 103 as being unpatentable over J. Ind. Eng. Chem, 36, p 279-283, hereinafter Kim as applied to claim 7 above and further in view of U.S. Pre-Grant Publication No. 2021/0198117, hereinafter Durham.
Regarding claims 8-10, Kim teaches LLZO with the formula Li7La3Zr2O12 (abstract).
Kim fails to teach a dopant.
The inclusion of Al as a dopant in LLZO for the purpose of stabilizing the cubic phase is well-known in the art – see, e.g. Durham (paragraph [0003]). Durham teaches an LLZO comprising Al as a dopant. The LLZO has the formula Li6.25La3Zr2Al0.25O12 (paragraph [0041]). This formula satisfies the instantly claimed formula with x = 0.75 and y = 0.25.
Therefore it would have been obvious to the ordinarily skilled artist before the effective filing date of the claimed invention to include Al as a dopant and form an LLZO with the formula Li6.25La3Zr2Al0.25O12 for the purpose of stabilizing the cubic phase.
Claim 20 is rejected under 35 U.S.C. 103 as being unpatentable over J. Ind. Eng. Chem, 36, p 279-283, hereinafter Kim as applied to claim 1 above and further in view of Japanese Patent Publication No. 2014-220177, hereinafter Sugiura.
Regarding claim 20, Kim teaches a method of forming LLZO.
Kim fails to teach performing the steps of providing, forming and recovering in a controlled environment substantially free of CO2.
It is recognized in the art that the exposure of LLZO to CO2 is detrimental to the material, because it may result in the deposition of Li2CO3, which has a negative effect on the ionic conductivity of LLZO – see, e.g. Sugiura who teaches forming LLZO in an environment free of CO2 (paragraph [0013]).
Therefore it would have been obvious to the ordinarily skilled artist before the effective filing date of the claimed invention to perform Kim’s full method, including the steps of providing, forming and recovering, in a controlled environment substantially free of CO2 for the purpose of excluding the possibility of exposing the material to CO2.
Claims 1-10, 12-14 and 18 are rejected under 35 U.S.C. 103 as being unpatentable over U.S. Pre-Grant Publication No. 2021/0198117, hereinafter Durham.
Regarding claim 1, Durham teaches a method of producing LLZO having a cubic crystal phase (paragraphs [0003, 0058]).
The method comprises a step of providing an aqueous solution comprising Zr and La (paragraphs [0047, 0049]). The aqueous solution has a pH of 11 (paragraph [0054]).
The method further comprises a step of coprecipitating to form a precursor (“intermediate”) precipitate comprising La(OH)3 and Zr(OH)4 from the Zr and the La in the aqueous solution (paragraph [0045]). La(OH)3 is a crystalline material and Zr(OH)4 is an amorphous material.
The method further comprises a step of recovering and washing the precursor (“intermediate”) precipitate (paragraph [0051]).
The method further comprises a step of calcining (“heat treating”) the washed precursor (“intermediate”) precipitate with a Li source at a temperature in the range 500°C and 1100°C (paragraph [0052]).
Kim's optimum range overlaps the instant application's optimum range of 400°C to 850°C. It has been held that in the case where claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists. See MPEP 2144.05.
Regarding claims 2 and 3, Durham teaches that a Zr precursor is added to the aqueous solution. The Zr precursor is Zr nitrate or Zr sulfate (paragraphs [0051, 0054]).
Regarding claims 4 and 5, Durham teaches that a La precursor is added to the aqueous solution. The La precursor is La nitrate or La sulfate (paragraphs [0051, 0054]).
Regarding claim 6, Durham teaches that the Li source is LiOH, LiNO3, LiCl or lithium acetate (paragraphs [0044, 0056]).
Regarding claims 7-10, Durham teaches that the LLZO comprises Al as a dopant.
The LLZO has the formula Li6.25La3Zr2Al0.25O12 (paragraph [0041]).
This formula satisfies the instantly claimed formula with x = 0.75 and y = 0.25.
Regarding claim 12, Durham teaches adding the Li precursor in an excess of the stoichiometric ratio Li:La:Zr = 7:3:2 of 20 mol% (paragraphs [0029, 0044]).
Regarding claim 13, Durham teaches mixing the Zr precursor and the La precursor and then adjusting the pH of the aqueous phase to be 11 (paragraph [0054]).
Regarding claim 14, Durham teaches mixing the Zr precursor and the La precursor and then adjusting the pH of the aqueous phase to be 11 (paragraph [0054]).
Durham fails to teach separately adjusting the pH of each of the Zr precursor solution and the La precursor solution.
It would have been obvious to the ordinarily skilled artist before the effective filing date of the claimed invention to adjust the pH of each of the Zr precursor solution and the La precursor solution and then mixing them together to have a final pH of 11 would be an obvious variation and would have the same effect as first mixing the Zr precursor and the La precursor and then adjusting the pH of the mixture to 11.
Regarding claim 18, Durham teaches that the washing step is performed using water (paragraph [0054]).
Claim 20 is rejected under 35 U.S.C. 103 as being unpatentable over U.S. Pre-Grant Publication No. 2021/0198117, hereinafter Durham as applied to claim 1 above and further in view of Japanese Patent Publication No. 2014-220177, hereinafter Sugiura.
Regarding claim 20, Durham teaches a method of forming LLZO.
Durham fails to teach performing the steps of providing, forming and recovering in a controlled environment substantially free of CO2.
It is recognized in the art that the exposure of LLZO to CO2 is detrimental to the material, because it may result in the deposition of Li2CO3, which has a negative effect on the ionic conductivity of LLZO – see, e.g. Sugiura who teaches forming LLZO in an environment free of CO2 (paragraph [0013]).
Therefore it would have been obvious to the ordinarily skilled artist before the effective filing date of the claimed invention to perform Durham’s full method, including the steps of providing, forming and recovering, in a controlled environment substantially free of CO2 for the purpose of excluding the possibility of exposing the material to CO2.
Claims 1-9, 11, 13-15, 18 and 19 are rejected under 35 U.S.C. 103 as being unpatentable over U.S. Pre-Grant Publication No. 2018/0248223, hereinafter Kim’223, with evidence from U.S. Pre-Grant Publication No. 2021/0198117, hereinafter Durham.
Regarding claim 1, Kim’223 teaches a method of producing LLZO having a cubic crystal phase (paragraphs [0046, 0082]).
The method comprises a step of providing an aqueous solution comprising Zr (in the form of zirconium nitrate) and La (in the form of lanthanum nitrate) (paragraphs [0047, 0049]). The aqueous solution has a pH of 10 to 12 (paragraph [0054]).
The method further comprises a step of coprecipitating to form an intermediate precipitate (paragraph [0047]). It is known in the art that the precipitate resulting from the reaction is La(OH)3 and Zr(OH)4 (see, e.g. Durham, paragraph [0004]). La(OH)3 is a crystalline material and Zr(OH)4 is an amorphous material.
The method further comprises a step of recovering and washing the intermediate precipitate (paragraph [0062]).
The method further comprises a step of calcining (“heat treating”) the washed intermediate precipitate with a Li source at a temperature in the range 600°C to 1000°C (paragraphs [0064, 0072, 0076]).
Kim’223's optimum range overlaps the instant application's optimum range of 400°C to 850°C. It has been held that in the case where claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists. See MPEP 2144.05.
Regarding claims 2 and 3, Kim’223 teaches that a Zr precursor is added to the aqueous solution. The Zr precursor is Zr nitrate (paragraphs [0047, 0048]).
Regarding claims 4 and 5, Kim’223 teaches that a La precursor is added to the aqueous solution. The La precursor is La nitrate (paragraphs [0047, 0048]).
Regarding claim 6, Kim’223 teaches that the Li source is selected from LiOH and LiNO3 (paragraph [0065]).
Regarding claim 7, Kim’223 teaches that the LLZO has the formula LixLayZrzO12, with 6 ≤ x ≤ 9, 2 ≤ y ≤ 4 and 1 ≤ z ≤ 3 (paragraphs [0013, 0014]).
Kim’223's optimum range overlaps the instant application's optimum ranges for x, y and z of 7±0.3, 3±0.3 and 2±0.3, respectively. It has been held that in the case where claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists. See MPEP 2144.05.
Regarding claims 8 and 9, Kim’223 teaches that the LLZO includes the dopant Al (paragraph [0015]).
Regarding claim 11, Kim’223 teaches that the La and Zr precursors may be provided at a ratio a:b, where a ranges from 2 to 4 and b ranges from 1 to 3.
This ratio includes an excess amount of La of up to 10% over the stoichiometric ratio La:Zr = 3:2.
Kim’223's optimum range overlaps the instant application's optimum range for the excess amount of La of up to 10%. It has been held that in the case where claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists. See MPEP 2144.05.
Regarding claim 13, Kim’223 teaches mixing the Zr precursor and the La precursor and then adjusting the pH of the aqueous phase to be 11 (paragraphs [0084, 0085]).
Regarding claim 14, Kim’223 teaches mixing the Zr precursor and the La precursor and then adjusting the pH of the aqueous phase to be 11 (paragraphs [0084, 0085]).
Kim’223 fails to teach separately adjusting the pH of each of the Zr precursor solution and the La precursor solution.
It would have been obvious to the ordinarily skilled artist before the effective filing date of the claimed invention to adjust the pH of each of the Zr precursor solution and the La precursor solution and then mixing them together to have a final pH of 11 would be an obvious variation and would have the same effect as first mixing the Zr precursor and the La precursor and then adjusting the pH of the mixture to 11.
Regarding claim 15, Kim’223 teaches that the aqueous solution has a pH of 10 to 12 (paragraph [0054]).
Kim’223's optimum range overlaps the instant application's optimum range for the pH of 8.5 to 10.5. It has been held that in the case where claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists. See MPEP 2144.05.
Regarding claim 18, Kim’223 teaches that the washing step is performed using water (paragraph [0063]).
Regarding claim 19, Kim’223 teaches in examples that the LLZO has a particle size of 500 nm (paragraph [0116] and Table 1).
Claim 20 is rejected under 35 U.S.C. 103 as being unpatentable over U.S. Pre-Grant Publication No. 2018/0248223, hereinafter Kim’223 as applied to claim 1 above and further in view of Japanese Patent Publication No. 2014-220177, hereinafter Sugiura.
Regarding claim 20, Kim’223 teaches a method of forming LLZO.
Kim’223 fails to teach performing the steps of providing, forming and recovering in a controlled environment substantially free of CO2.
It is recognized in the art that the exposure of LLZO to CO2 is detrimental to the material, because it may result in the deposition of Li2CO3, which has a negative effect on the ionic conductivity of LLZO – see, e.g. Sugiura who teaches forming LLZO in an environment free of CO2 (paragraph [0013]).
Therefore it would have been obvious to the ordinarily skilled artist before the effective filing date of the claimed invention to perform Kim’223’s full method, including the steps of providing, forming and recovering, in a controlled environment substantially free of CO2 for the purpose of excluding the possibility of exposing the material to CO2.
Conclusion
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/STEWART A FRASER/Primary Examiner, Art Unit 1724
LILIA V. NEDIALKOVA
Examiner
Art Unit 1724
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