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 .
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and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114.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 March 18, 2025 has been entered.
Response to Amendment
Applicant’s amendments filed March 18, 2025 have been entered; Claims 1, 2, 4-7, 9 and 11 have been amended; support for the amendments can be found at least in cancelled claim 8 and paragraph [0013] of the Published U.S. Patent Application US 20220216512 A1. Claim 8 has been cancelled. Claims 1-2, 4-7, and 9-11 remain pending and have been examined on their merits in this office action.
Response to Arguments
Applicant’s arguments filed March 18, 2025 have been fully considered. Applicant’s arguments regarding are considered moot in view of the new grounds of rejection below in view of Applicant’s amendments to the independent claim 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.
This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention(s) absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and effective filing dates of each claim that was not commonly owned as of the effective filing date of the later invention in order for the examiner to consider the applicability of 35 U.S.C. 102(b)(2)(C) for any potential 35 U.S.C. 102(a)(2) prior art against the later invention.
Claims 1-2, 4-5, and 9-10 are rejected under 35 U.S.C. 103 as being unpatentable over Suk et al. (KR 20160013630 A) in view of Kim et al. (KR 20140083181 A), and as evidenced by Sella et al. (Published U.S. Patent Application US 20210013494 A1) and by Matmake.com (“Electrical Conductivity of Common Polymers and Plastics”), hereinafter referred to as Suk, Kim, Sella, and Matmake.
Regarding claim 1, Suk teaches an electrode layer of the all-solid-state battery containing an active material, a solid electrolyte, and additional conductive particles (“an electrode for an all-solid-state battery comprising a solid electrolyte composite, an electrode active material, and a conductive material”) (see e.g., paragraph [0008]). Suk teaches the solid electrolyte includes sulfide-based solid electrolyte particles (“a particulate solid electrolyte material” and “wherein the particulate solid electrolyte material comprises a sulfide-based solid electrolyte material containing sulfur (S)”) and a polymer coating layer coated on the surface of the sulfide-based solid electrolyte particles (“a passivation film covering all or at least part of the solid electrolyte material”) (see e.g., paragraph [0016]).
Suk does not explicitly teach wherein the passivation film comprises a polyvinylene carbonate-based polymer and wherein the passivation film has ionic conductivity of 1 × 10-5 s/cm or above and electronic conductivity of 1 × 10-9 s/cm or less.
However, Kim teaches a protective film (“a passivation film”) to suppress side reactions between the electrodes and electrolyte and thereby improve the cycle characteristics of a battery (see e.g., Abstract and paragraph [0006]). Kim teaches that the protective film comprises a polyvinylene carbonate-based polymer having ion conductivity (“wherein the passivation film comprises a polyvinylene carbonate-based polymer”) (see e.g., paragraph [0006]). Kim teaches the polyvinylene carbonate copolymer is excellent in mechanical strength and is chemically stable without causing side reactions with lithium metal, such as an electrode (see e.g., paragraph [0035]).
Therefore, it would have been obvious before the effective filing date of the claimed invention that one of ordinary skill in the art would modify the polymer coating layer of Suk to comprise a polyvinylene carbonate-based polymer, as taught by Kim, in order to reduce the side reactions between the electrolyte and electrode as it is chemically stable and is excellent in mechanical strength (see e.g., paragraph [0035]), and thereby improve the cycle characteristics of the battery (see e.g., paragraph [0006]).
Suk, as modified by Kim, does not explicitly teach wherein the passivation film has ionic conductivity of 1 × 10-5 s/cm or above and electronic conductivity of 1 × 10-9 s/cm or less.
However, Sella teaches a layer of an ionic-conductive polymer to facilitate lithium ion transfer through the coating while preventing direct fluid communication with the anode material particles and electrolyte contact thereto, and the coating is configured to keep the anode resistance low while preventing electrolyte decomposition thereupon, enhancing cell stability and cycling lifetime (see e.g., Abstract). Sella teaches the coating 105, wherein the coating is poly(vinylene carbonate), has an ionic conductivity above 4 × 10-7 S/cm (see e.g., paragraph [0016]). Therefore, when Suk, as modified by Kim, teach a polymer coating layer comprising the polyvinylene carbonate-based polymer, then inherently, the ionic conductivity would be 4 × 10-7 S/cm or above as also evidenced by the electrical conductivities of polymer taught by Sella. In addition, the presently claimed property of electronic conductivity of 1 × 10-9 s/cm or less would have obviously been present once the Suk, as modified by Kim, product is provided. In re Best, 195 USPQ 433 (CCPA 1997).
It has been held in the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art,” and because the ionic conductivity above 4 × 10-7 S/cm overlaps with the recited range, a “prima facie” case of obviousness exists (see MPEP 2144.05(l)).
Therefore, it would have been obvious before the effective filing date of the claimed invention that one of ordinary skill in the art would have a polymer coating layer comprising a polyvinylene carbonate-based polymer of Suk, as modified by Kim, to have an ionic conductivity of 9.82 × 105 S cm-1, as taught by Sella, in order to produce batteries with stable charge/discharge profiles, considerable rate capability, excellent cycling performance, and decent safety characteristics (see e.g., Abstract).
Suk, as modified by Kim and Sella, does not explicitly teach wherein the passivation film has electronic conductivity of 1 × 10-9 s/cm or less.
However, Matmake teaches polymers generally exhibit poor electrical conductivity compared to metals and other conductive materials because the molecular structure of most polymers consists of long chains or large molecules with limited charge mobility. Matmake provides a table of electrical conductivity values for a variety of polymers in which the electrical conductive is 1 × 10-9 s/cm or less (see e.g., Table).
Therefore, when Suk, as modified by Kim and Sella, teach a polymer coating layer comprising the polyvinylene carbonate-based polymer, then inherently, the electronic conductivity would be 1 × 10-9 s/cm or less as also evidenced by the electrical conductivities of polymer taught by Matmake. In addition, the presently claimed property of electronic conductivity of 1 × 10-9 s/cm or less would have obviously been present once the Suk, as modified by Kim and Sella, product is provided. In re Best, 195 USPQ 433 (CCPA 1997).
Regarding claim 2, Suk, as modified by Kim, Sella, and Matmake, teaches the instantly claimed invention of claim 1, as previously described.
Suk teaches the polymer is coated on the surface of the sulfide-based electrolyte particles in a thickness of 1 to 1000 nm (“wherein the passivation film is 10 nm to 1 µm in thickness”) (see e.g., paragraph [0016]).
Regarding claim 4, Suk, as modified by Kim, Sella, and Matmake, teaches the instantly claimed invention of claim 1, as previously described.
Suk, as modified by Kim, Sella, and Matmake, does not explicitly teach the polyvinylene carbonate-based polymer comprises vinylene carbonate as a polymerizable unit.
However, Kim teaches the polyvinylene carbonate-based polymer material is obtained by polymerizing a liquid-phase vinylene carbonate monomer (“the polyvinylene carbonate-based polymer comprises vinylene carbonate as a polymerizable unit”) as the polyvinylene carbonate polymer when coated on the surface reduces possible reactions with oxygen, nitrogen, moisture, and the like to help stabilize the coated surface (see e.g., paragraph [0023]).
Therefore, it would have been obvious before the effective filing date of the claimed invention that one of ordinary skill in the art would modify the coating layer of Suk, as modified by Kim, Sella, and Matmake, to have the polyvinylene carbonate-based polymer material be obtained by polymerizing a liquid-phase vinylene carbonate monomer, as taught by Kim, in order to reduce possible reactions with oxygen, nitrogen, moisture, and the like to help stabilize the coated surface (see e.g., paragraph [0023]).
Regarding claim 5, Suk, as modified by Kim, Sella, and Matmake, teaches the instantly claimed invention of claim 4, as previously described.
Suk, as modified by Kim, Sella, and Matmake, does not explicitly teach the polyvinylene carbonate-based polymer further comprises a second polymerizable unit that can be polymerized with the vinylene carbonate, and the second polymerizable unit is at least one selected from the group consisting of acrylonitrile, methyl methacrylate, styrene, vinyl pyrrolidone, vinyl acetate, vinyl alcohol, and vinyl chloride.
However, Kim teaches the vinylene carbonate (“the polyvinylene carbonate-based polymer comprises vinylene carbonate as a polymerizable unit”) and polyvinylene carbonate-based copolymer (“a second polymerizable unit that can be polymerized with the vinylene carbonate”) are synthesized by using vinylene carbonate monomer as SEI film forming additive, and a functional group for forming a protective film of lithium electrode because since the polyvinylene carbonate polymer can easily be melted or swelled, it is preferably to use a copolymer (see e.g., paragraph [0025]). Kim teaches the examples of the copolymer material (“the second polymerizable unit”) that can be used for copolymerization with the vinylene carbonate can include polyacrylonitrile, poly methyl methacrylate, polystyrene, polyvinyl pyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, and the like can be used (see e.g., paragraph [0026]).
Therefore, it would have been obvious before the effective filing date of the claimed invention that one of ordinary skill in the art would modify the coating layer of Suk, as modified by Kim, Sella, and Matmake, to have the polyvinylene carbonate-based polymer material be obtained by polymerizing a liquid-phase vinylene carbonate monomer and a polyvinylene carbonate-based copolymer, as taught by Kim, in order to prevent possible melting and swelling of the polyvinylene carbonate polymer (see e.g., paragraph [0025]).
Regarding claim 9, Suk, as modified by Kim, Sella, and Matmake, teaches the instantly claimed invention of claim 1, as previously described.
Suk, as modified by Kim, Sella, and Matmake, teaches an all-solid-state battery comprising the electrode according to claim 1 (“an all-solid-state battery”) (see e.g., Suk paragraph [0001]).
Regarding claim 10, Suk, as modified by Kim, Sella, and Matmake, teaches the instantly claimed invention of claim 9, as previously described.
Suk teaches the all-solid-state battery comprising a positive electrode, a negative electrode, and a solid electrolyte composite (“wherein the all-solid-state battery comprises a negative electrode, a positive electrode, and a solid electrolyte membrane interposed between the negative electrode and the positive electrode”) (see e.g., paragraph [0044]), wherein one of the electrode layers comprises the solid electrolyte composite (“the negative electrode or the positive electrode or both the negative and the positive electrode comprise the solid electrolyte composite”) (see e.g., paragraph [0008]).
Claims 6-7 are rejected under 35 U.S.C. 103 as being unpatentable over Suk et al. (KR 20160013630 A) in view of Kim et al. (KR 20140083181 A), and as evidenced by Sella et al. (Published U.S. Patent Application US 20210013494 A1) and by Matmake.com (“Electrical Conductivity of Common Polymers and Plastics”), and further in view of Gauthier et al. (JP 2000340261 A), hereinafter referred to as Gauthier.
Regarding claim 6, Suk, as modified by Kim, Sella, and Matmake, teaches the instantly claimed invention of claim 1, as previously described.
Suk, as modified by Kim, Sella, and Matmake, do not explicitly teach the solid electrolyte material further comprises a polymer-based solid electrolyte.
Gauthier teaches an electrochemical generator containing a first solid electrolyte and a second electrolyte (see e.g., Abstract). Gauthier teaches that first solid electrolyte is preferably vitreous and conductive for Li+ ions (see e.g., paragraph [0015], and the second solid electrolyte (“the solid electrolyte material further comprises a polymer-based solid electrolyte”) is preferably a dried or gelled polymer electrolyte that is a mixed conductor of ions that acts as a deformable binder (see e.g., paragraph [0007]). Gauthier teaches that the second solid electrolyte is dispersed to ensure ionic conductivity while also acting as a deformable binder (see e.g., paragraph [0007]).
Therefore, it would have been obvious before the effective filing date of the claimed invention that one of ordinary skill in the art would modify the solid electrolyte particle of Suk, as modified by Kim, Sella, and Matmake, to also include a second solid electrolyte in the form of a gelled polymer, as taught by Gauthier, in order to ensure optimal ionic conductivity of the composite electrolyte while the second solid electrolyte as a deformable binder to maintain contact with other components of the electrochemical generator (see e.g., paragraph [0007]).
Regarding claim 7, Suk, as modified by Kim, Sella, and Matmake, teaches the instantly claimed invention of claim 6, as previously described.
Suk teaches the sulfide-base solid electrolyte particle having high ionic conducting (e.g., conductivity of 10-4 S/cm or more) and may be represented by the Chemical Formula 1: MaPNbScXd wherein M is Li, Na, N is selected from the group consisting of B, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Hf, Ta, W, and X is selected from the group consisting of O, Se, Te, and combinations thereof (“wherein the oxide-based solid electrolyte contains oxygen (O) and has ionic conductivity of a metal belonging to Group I or Group II of the periodic table” and “the oxide-based solid electrolyte comprises at least one selected from the group consisting of a perovskite-based compound”) (see e.g., paragraphs [0064]-[0068]).
Claim 11 is rejected under 35 U.S.C. 103 as being unpatentable over Suk et al. (KR 20160013630 A) in view of Kim et al. (KR 20140083181 A), and as evidenced by Sella et al. (Published U.S. Patent Application US 20210013494 A1) and by Matmake.com (“Electrical Conductivity of Common Polymers and Plastics”), and further in view of Lee et al. (Published U.S. Patent Application US 20170294678 A1), hereinafter referred to as Lee.
Regarding claim 11, Suk, as modified by Kim, Sella, and Matmake, teaches the instantly claimed invention of claim 1, as previously described.
Suk teaches the method of manufacturing a solid electrolyte complex (“a method for manufacturing the solid electrolyte composite in the electrode”) comprises preparing a mixed solution of a polymer and a solvent, adding sulfide-based solid electrolyte particles to the mixed solution, and uniformly dispersing the sulfide-based solid electrolyte particles in the mixed solution to obtain a solid electrolyte composite including sulfide-based solid electrolyte particles coated with a polymer (“(S1) coating the passivation layer composition on a surface of the particulate solid electrolyte material”) (see e.g., paragraph [0073]). Suk teaches the step of obtaining a solid electrolyte complex including polymer-coated sulfide-based solid electrolyte particles by removing a solvent in the mixed solution after evenly dispersing the sulfide-based solid electrolyte particles in the mixed solution (see e.g., paragraph [0075]); therefore, Suk does not explicitly teach (S2) providing the coated solid electrolyte material to polymerization reaction.
However, Kim teaches the protective film (“the passivation film”) is formed by coating a solution containing a protective film composition on the surface (see e.g., paragraph [0039]), and the protective film composition comprises vinylene carbonate (“vinylene carbonate”) that is copolymerized with polyacrylonitrile, poly methyl methacrylate, polystyrene, polyvinyl pyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride and the like (“a polymerization initiator”) to have excellent adhesion with the coated surface and chemically stable without causing side reactions (see e.g., paragraph [0035]). Kim teaches the polymer is mixed with a non-aqueous organic solvent (“a non-aqueous organic solvent”) (see e.g., paragraph [0039]).
Therefore, it would have been obvious before the effective filing date of the claimed invention that one of ordinary skill in the art would modify method of producing the coating layer of Suk, as modified by Kim, Sella, and Matmake, to also include vinylene carbonate that is copolymerized with polyacrylonitrile, poly methyl methacrylate, polystyrene, polyvinyl pyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride and mixed with a non-aqueous organic solvent, as taught by Kim, in order to have excellent adhesion with the coated surface and chemically stable without causing side reactions (see e.g., paragraph [0035]).
Suk, as modified by Kim, Sella, and Matmake, does not explicitly teach the method wherein the passivation layer composition comprises a lithium salt.
However, Lee teaches a solid electrolyte with improved electrochemical safety and stability (see e.g., paragraph [0036]). Lee teaches a composite solid electrolyte that include a lithium ion conductive solid electrolyte (“a particulate solid electrolyte material”) and a polymer-containing electrolyte coating layer (“a passivation layer”). Lee teaches the polymer-containing electrolyte coating layer may further include at least one selected from inorganic particles (“a lithium salt”) and a solvate ionic liquid (“a non-aqueous organic solvent”) including a lithium salt and a glyme-based material as the composite solid electrolyte may have enhanced mechanical and physical properties and enhanced ionic conductivity at room temperature (see e.g., paragraph [0049]).
Therefore, it would have been obvious before the effective filing date of the claimed invention that one of ordinary skill in the art would modify the method of producing the coating layer of Suk, as modified by Kim, Sella, and Matmake, to include a lithium salt and a solvate ionic liquid, as taught by Lee, in order to enhance the mechanical and physical properties of the coating layer and increase the ionic conductivity of the coating layer at room temperature (see e.g., paragraph [0049]).
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to Katherine N Higgins whose telephone number is (703)756-1196. The examiner can normally be reached Mondays - Thursdays 7:30-4:30 EST, Fridays 7:30 - 11:30 EST.
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/KATHERINE N HIGGINS/Examiner, Art Unit 1728
/MATTHEW T MARTIN/Supervisory Patent Examiner, Art Unit 1728