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 .
Continued Examination Under 37 CFR 1.114
A request for continued examination under 37 CFR 1.114, including the fee set forth in 37 CFR 1.17(e), was filed in this application after final rejection. Since this application is eligible for continued examination under 37 CFR 1.114, and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114. Applicant's submission filed on October 17, 2025, has been entered.
Claim Rejections - 35 USC § 112
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 28 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. Formula I of claim 1 does not allow for the inclusion of tantalum. Applicant may cancel the claim(s), amend the claim(s) to place the claim(s) in proper dependent form, rewrite the claim(s) in independent form, or present a sufficient showing that the dependent claim(s) complies with the statutory requirements.
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.
Claim(s) 1, 4, 6, 9, 11-15, 19-22, 24, 27, and 28 is/are rejected under 35 U.S.C. 103 as being unpatentable over Xu et al. ("Dual-Phase Single-Ion Pathway Interfaces for Robust Lithium Metal in Working Batteries", Advanced Materials 31(19), 1808392, March 25, 2019) in view of Djenadic et al. ("Nebulized spray pyrolysis of Al-doped Li7La3Zr2O12 solid electrolyte for battery applications," Solid State Ionics 263, pp. 49-56, October 1, 2014) and Zhang et al. (US 2022/0158237 A1).
Regarding claim 1, Xu teaches an electrode for a lithium battery, comprising a metal layer (lithium) coated with a coating layer comprising
an organic binder (Nafion™), and
a mixed oxide comprising zirconium (LLZTO) (Xu 1.2. Fabrication of dual-phase artificial solid electrolyte layers),
with an average particle size of 66 nm (Xu Fig. S2), which falls within the claimed range of 5-100 nm,
wherein a weight ratio of the metal compound to the organic binder in the coating layer is 1 (monolayer coating, Xu 1.2. Fabrication of dual-phase artificial solid electrolyte layers), which falls within the claimed range of 1-6.
Xu does not teach that the particles are obtained by a pyrogenic process. Djenadic teaches that pyrogenic cubic LLZO (garnet type doped with an element selected from a group including Ta) requires reduced processing and is suited to production on industrial scales (Djenadic Introduction). It would have been obvious to one of ordinary skill in the art before the effective filing date of the instant invention to use pyrogenic LLZO for the battery of Xu in order to reduce processing requirements and facilitate industrial production.
Xu does not teach that the oxide particles are aggregates of primary particles. Applicant has indicated that pyrogenic compounds form aggregates during processing (p. 4, lines 7-25 of the instant specification). Pyrogenic LLZO is therefore assumed to have this property.
Xu teaches that the thickness of the coating layer is 5 μm (Xu Fig. 2), which falls within the range of the instant claim.
Xu does not teach the use of PVDF-HFP. Xu teaches the use of Nafion (PTFE) for a polymer-inorganic composite electrolyte layer (Xu Abstract). Zhang teaches that both PTFE and PVDF-HFP (i.e. a copolymer of vinylidene fluoride and hexafluoropropylene) are suitable binders for composite solid electrolyte layers (Zhang [0028]). The two are therefore art-recognized equivalents for the same purpose, and substitution of equivalents is prima facie obvious (MPEP 2144.06 II). It would have been obvious to one of ordinary skill in the art before the effective filing date of the instant invention to select either of PTFE or PVDF-HFP, since they are art-recognized equivalents for the same purpose.
Xu teaches that the metal compound comprises the mixed oxide comprising zirconium, and wherein the mixed oxide comprising zirconium is a compound of the formula Li6.75La3Zr1.75Ta0.25O12- (Xu Abstract). Djenadic teaches that Al-doped LLZO has a higher conductivity than Ta-doped LLZO (Djenadic Introduction, first paragraph). It would have been obvious to one of ordinary skill in the art before the effective filing date of the instant invention to replace the Ta-doped LLZO of Xu with the Al-doped LLZO of Djenadic to increase conductivity, which would give a composition corresponding to the formula (I) of the instant claim (LiaZrbMcO0.5a+2b+d) for a=6.75, b=1.75, M=La and Al, cLa=3, and cAl=0.25, all of which fall within the ranges of the instant claim.
Regarding claim 4, modified Xu teaches that adding a lithium salt such as LiPF6 or LiTFSI to the polymer allows charge transport within the layer (Zhang [0018]-[0020]). It would have been obvious to one of ordinary skill in the art before the effective filing date of the instant invention to add LiPF6 or LiTFSI to the layer to allow charge transport.
Regarding claim 6, modified Xu does not teach any particular aggregate particle size. However, the coating of modified Xu is 4 µm thick (Xu Fig. 2). The typical aggregate particle size must therefore be less than 4 µm, 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 9, Xu teaches that the metal layer comprises lithium (Xu Fig. 1).
Regarding claim 11, Xu teaches that the thickness of the coating layer is 4 μm (Xu Fig. 2), which falls within the range of the instant claim.
Regarding claim 12, modified Xu teaches a process for preparing an electrode comprising
(1) preparing a mixture comprising:
the organic binder (PVDF-HFP),
the metal compound (LLZO),
a solvent (propylene carbonate, PC),
wherein the weight ratio of the metal compound to the organic binder is from 9, which falls within the range of the instant claim;
(2) coating the mixture prepared in (1) on a surface of the metal layer, to obtain the coating layer; and
(3) drying the coating layer prepared in (2) (Xu 1.2. Fabrication of dual-phase artificial solid electrolyte layers).
Regarding claim 13, Xu teaches the use of propylene carbonate (Xu 1.2. Fabrication of dual-phase artificial solid electrolyte layers).
Regarding claim 14, modified Xu teaches a method of constructing a battery, comprising:
providing the electrode as a constituent in a lithium metal battery (Xu 1.4. Electrochemical cycling tests).
Regarding claim 15, modified Xu teaches a battery comprising the electrode (Xu 1.4. Electrochemical cycling tests).
Regarding claims 19 and 20, modified Xu teaches the use of PVDF-HFP.
Regarding claim 21, the coating of modified Xu is applied directly to the metal layer substrate (Xu Fig. 1b).
Regarding claims 22, 24, and 27, modified Xu teaches the use of fumed, aluminum-doped LLZO particles.
Regarding claim 28, the Al-doped LLZO of Djenadic does not contain tantalum.
Claim(s) 5 is/are rejected under 35 U.S.C. 103 as being unpatentable over Xu in view of Djenadic and Zhang as applied to claim 1 above, and further in view of Yan et al. ("Garnet-rich composite solid electrolytes for dendrite-free, high-rate, solid-state lithium-metal batteries", Energy Storage Materials 26, pp. 448-456, November 21, 2019).
Regarding claim 5, modified Xu does not teach that the metal compound is surface treated with a surface treatment agent selected from the group consisting of an organosilane, a silazane, an acyclic polysiloxane, a cyclic polysiloxane, and a mixture thereof. Yan teaches that modifying LLZO particles with an organosilane (3-(trimethoxysilyl)propyl methacrylate) improves Li ion conduction and mechanical strength in polymer/nanoparticle composites for lithium batteries (Yan Introduction and 4.2. Fabrication of silane-modified Li6.28La3Al0.24Zr2O12 (s@LLAZO) nanofibers). It would have been obvious to one of ordinary skill in the art before the effective filing date of the instant invention to treat the surface of the nanoparticles of modified Xu with an organosilane as taught by Yan in order to improve Li ion conduction and mechanical strength.
Claim(s) 26 is/are rejected under 35 U.S.C. 103 as being unpatentable over Xu in view of Djenadic and Zhang as applied to claim 1 above, and further in view of Ren et al. (“Systematic Optimization of Battery Materials: Key Parameter Optimization for the Scalable Synthesis of Uniform, High-Energy, and High Stability LiNi0.6Mn0.2Co0.2O2 Cathode Material for Lithium-Ion Batteries”, ACS Applied Materials & Interfaces 9(41), pp. 35811-35819, September 2017).
Regarding claim 26, the pyrogenic particles of modified Xu have an average primary particle size of 7-9 nm (Djenadic 3.1 As-synthesized powders), which falls within the range of the instant claim.
Modified Xu does not teach any particular aggregate particle size. However, the coating of modified Xu is 4 µm thick (Xu Fig. 2). The typical aggregate particle size must therefore be less than 4 µm, 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).
Modified Xu does not teach any particular particle size span. Ren teaches that a narrow particle size span (1.2, which falls within the range of the instant claim) implies homogeneous and uniform synthesis (Ren p. 35814, last full paragraph). It would have been obvious to one of ordinary skill in the art before the effective filing date of the instant invention to select a narrow span of 1.2 to ensure homogeneous and uniform synthesis of the LLZO particles of modified Xu.
Conclusion
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/J.A.C/ Examiner, Art Unit 1722
/NIKI BAKHTIARI/ Supervisory Patent Examiner, Art Unit 1722