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 .
Examiner Note
It is noted that all references hereinafter to Applicant’s specification (“spec”) are to the published application US-2024-0178402-A1, unless stated otherwise. Further, any italicized text utilized hereinafter is to be interpreted as emphasis placed thereupon.
Information Disclosure Statement
The information disclosure statements (IDS) filed 27NOV2023, 21MAY2024, and 21NOV2024 are in compliance with 37 CFR 1.97 and 37 CFR 1.98 and have been considered.
Claim Objections
Claims 1-2, 4 and 8 are objected to because of the following informalities. Suggested amendments for correction of each issue are indicated below as sub-bullets.
[claim 1] – improper spacing
“from 51:49 to 99:1”
[claim 2] – typographical/spelling error
“polyvinylidene fluoride-co-hexafluoropropene (PVDF-HFP)”
[claim 4] – improper spacing
“is 0.01 µm to 10 µm.”
[claim 8] – improper spacing
“1 nm to 300 nm”
Claim Rejections - 35 USC § 102 and/or 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 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.
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 1-3, 5, 7-12, and 14 are rejected under 35 U.S.C. 102(a)(2) as anticipated by or, in the alternative, under 35 U.S.C. 103 as being unpatentable over Takata (US 2023/0047382-A1; “Takata”).
Regarding Claim 1, Takata teaches that the anode (a negative electrode) ([0078]) of the lithium ion battery ([0076]) can include a current collector ([0052]) and a metal layer coated on the metal foil ([0052]) with a thickness of 2 μm-500 μm ([0053]) formed by vacuum deposition ([0054]) (a negative electrode active layer). Takata teaches that the coating layer protects (a protective layer) the lithium electrodes of lithium batteries ([0013]) and coats the metal layer ([0054]) (the negative electrode active material layer). Takata teaches that powders may be partially destructed and converted into the nanometer (nm) range particles (nanopowders) by suitable grinding. Pyrogenically prepared metal compounds are characterized by extremely small particle size, high specific surface area (BET), very high purity, spherical shape of primary particles, and the absence of pores ([0019]). Takata teaches that the coating layer present in the electrode comprises an organic binder and a metal compound nanopowder as previously described selected from the group consisting of aluminium oxide (Al2O3), silicon dioxide (SiO2), zirconium oxide (ZrO2), mixed oxides comprising zirconium, mixed oxides comprising aluminium, lithium zirconium phosphate, and mixtures thereof ([0018]). Moreover, Takata teaches a mixed oxide comprising Mg (magnesium oxide) and Zn (zinc oxide) ([0021]).
Takata also tests the weight ratio of the oxide particle (nanopowder):binder being 4:1 or 6:1 ([0135], please see Table 2-1), which falls within the claimed range of the weight ratio of nanopowder to binder from 51:49 to 99:1. Prior art which teaches a range within, overlapping, or touching the claimed range anticipates if the prior art range discloses the claimed range with sufficient specificity. See MPEP 2131.03.
Takata does not teach specific binding energies between the protective coating and the active material layer of the cathode as defined in the specification, which states, “the binding energy between nanopowder and lithium (ΔE) of the disclosure is determined by the following equation: ΔE = EC-Li–EC-ELi, wherein EC-Li represents the free energy of the binding reaction between nanopowder and lithium, EC represents the free energy of the nanopowder, and ELi represents the free energy of lithium (0 K, under vacuum)” ([0022]).
However, the coating layer, and the nanopowder thereof, of Takata Examples 4a ((i) below) and 9a ((ii) below) would have been substantially identical or identical to the claimed and disclosed protective layer and nanopowder thereof in Applicant’s specification in terms of comprising:
(i) β and γ- Al2O3 with BET = 130 m2/g and average primary particle size 15-25 nm ([0109], Table 1), which reads on the claimed and disclosed nanopowders (nanopowder has a specific surface area of 30 m2/g to 1,000 m2/g, and nanopowder has a mean primary particle size of 1nm to 300nm) with corresponding binding energies [Applicant’s specification [([0023], [0026] - Table 1, and [0054] – Example 1), claims 1 and 8]. Prior art which teaches a range within, overlapping, or touching the claimed range anticipates if the prior art range discloses the claimed range with sufficient specificity. See MPEP 2131.03.
(ii) ZrO2 with BET = 40 m2/g and average primary particle size 20-50 nm ([0109], Table 1), which reads on the claimed and disclosed nanopowders (nanopowder has a specific surface area of 30 m2/g to 1,000 m2/g, and nanopowder has a mean primary particle size of 1nm to 300nm) with corresponding binding energies [Applicant’s specification [([0023] and [0026] - Table 1), claims 1 and 8]. Prior art which teaches a range within, overlapping, or touching the claimed range anticipates if the prior art range discloses the claimed range with sufficient specificity. See MPEP 2131.03.
Given that the metal compound particles (i) and (ii) of Takata are identical to the claimed nanopowder and substantially identical or identical to the nanopowders disclosed in Applicant’s specification in terms of the foregoing elements (i)-(ii), it stands to reason, and there is a strong expectation, that the nanopowder would have exhibited a binding energy less than or equal to -2.5eV, as claimed, absent a showing of factually supported objective evidence to the contrary. See MPEP 2112(V); MPEP 2112.01(I) and (II); MPEP 2145; and MPEP 2145(I). "Where the claimed and prior art products are identical or substantially identical in structure or composition, or are produced by identical or substantially identical processes, a prima facie case of either anticipation or obviousness has been established”. The prima facie case can be rebutted by evidence showing that the prior art products do not necessarily possess the characteristics of the claimed products. In re Best, 195 USPQ 430, 433 (CCPA 1977), In re Spada, 15 USPQ2d 1655, 1658 (Fed. Cir. 1990).
Regarding Claim 2, Takata also teaches in Examples 4a and 9a that the binder is vinylidene fluoride and hexafluoropropylene ([0117], [0127]).
Regarding Claim 3, Takata teaches that the metal compound (the nanopowder) is aluminium oxide ([0117]) in Example 4a or zirconium oxide ([0127]) in Example 9a.
Regarding Claim 5, Takata teaches a lithium layer ([0111]) (negative electrode active material) covering the surface of a copper foil (current collector of the electrode) ([0111]) in Examples 4a ([0117]) and 9a ([0127]). The lithium layer is coated with alumina and PVDF-HFP polymer particles (the protective layer) ([0111]) (the lithium layer is the negative electrode active layer) ([0051-0052], ([0064-0065]).
Regarding Claim 7, Takata teaches a lithium layer ([0111]) (negative electrode active material) covering the surface of a copper foil (current collector of the electrode) ([0111]) in Examples 4a ([0117]) and 9a ([0127]) ([0051-0052]).
Regarding Claim 8, Takata teaches that β and γ- Al2O3 nanopowder with BET = 130 m2/g has an average primary particle size 15-25 nm ([0109], Table 1), and ZrO2 nanopowder with BET = 40 m2/g has an average primary particle size 20-50 nm ([0109], Table 1), which anticipates the claimed range of 1 nm to 300 nm for mean primary particle size of nanopowder. Prior art which teaches a range within, overlapping, or touching the claimed range anticipates if the prior art range discloses the claimed range with sufficient specificity. See MPEP 2131.03.
Regarding Claim 9, the rejection of claim 1 above is incorporated herein by reference. Takata discloses the battery – inclusive of the negative electrode set forth above in the rejection of claim 1 – further includes a separator or solid electrolyte, a cathode, and an anode and/or an electrolyte comprising a lithium salt ([0079]). Takata teaches that Li (anode)—Cu (cathode) asymmetrical cells were fabricated in which the metal compound coating layer of each electrode sheet was faced toward the separator and the first and second sheet were placed in sequence ([0158])(a positive electrode, wherein the negative electrode is separated from the positive electrode via the separator).
Regarding Claim 10, Takata teaches that the Li—Cu asymmetric cells, Example 4b, are in the liquid electrolyte (indicating the liquid electrolyte is immersed in the cell and consequently between the positive and negative electrode) ([0118]).
Regarding Claim 11, Takata teaches a cathode (positive electrode)([0080]) and an active cathode material layer (positive electrode active layer) ([0080]).
Regarding Claim 12, Takata teaches that the active cathode materials include materials capable of reversible intercalating/deintercalating lithium ions and are well known in the art and may include lithium metal, a lithium alloy, sulfur, lithium sulfide, silicon, silicon oxide, silicon carbide composite, silicon alloy, Sn, SnO2, or a transition metal compound, such as mixed oxides including Li, Ni, Co, Mn, Fe, P, Al, V or other transition metals ([0082]).
Regarding claim 14, Takata teaches that the cathode (positive electrode) of the lithium ion battery usually includes a current collector (positive electrode current-collecting layer) and an active cathode material layer (positive electrode active layer) formed on the current collector ([0080]).
Claims 4 is rejected under U.S.C. 103 as being unpatentable over Takata (US 2023/0047382-A1; “Takata”) as applied to claim 1 under 35 U.S.C. 102(a)(2)/103 above.
Takata teaches the limitations of Claim 1 as discussed above.
Takata teaches that the thickness of the protective layer is from 0.1-300 µm, of which overlaps with, and thereby renders prima facie obvious the claimed range of 0.01-10 µm (see MPEP 2144.05(I)).”
Claim 6 is rejected under U.S.C. 103 as being unpatentable over Takata (US 2023/0047382-A1; “Takata”) as applied to claim 5 under 35 U.S.C. 102(a)(2)/103 above, in view of Yoon (US 2015/0325843-A1; “Yoon”).
Takata teaches the limitations of Claim 5 as discussed above.
Takata teaches that the material of the organic binder is not particularly limited as long as this material allows efficient adhesion between the metal compound particles and the surface of the lithium layer ([0061]). Takata teaches that the binder is selected from the group consisting of poly(vinylidene fluoride), copolymer of vinylidene fluoride and hexafluoropropylene, poly(vinyl chloride), poly(urethane), and poly(acrylonitrile) ([0061]). However, this binder is in the protective layer ([0134]) and not the negative electrode active layer.
Takata does not teach a binder in the negative electrode active layer.
Yoon teaches a negative electrode active layer that includes a porous matrix containing lithium titanium oxide particles and metal nanoparticles (such as aluminum oxide – [0013]) that are alloyable with lithium (Abstract). Yoon teaches that according to an embodiment, the negative active layer 20 may further include a binder ([0070]). The binder may be selected from, for example, polyvinylidenefluoride (PVdF), polyacrylonitrile, polyvinylpyrrolidone, polytetrafluoroethylene, fluorine rubber, and a combination thereof ([0070]).
Takata and Yoon each constitute prior art which is directly analogous to claimed invention (MPEP 2141.01(a)(I)). It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the battery of Takata by incorporating a binder in the negative electrode active layer as taught by Yoon. Yoon teaches the binder may aid binding of the metal nanoparticles 24 and a current collector, binding of the lithium titanium oxide particles 22 and a current collector, or binding of the metal nanoparticles 24 and a conductive material (binding energy) ([0070]), providing the motivation for incorporating a binder in the negative electrode active layer.
Claims 13 is rejected under U.S.C. 103 as being unpatentable over Takata (US 2023/0047382-A1; “Takata”) as applied to claim 11 under 35 U.S.C. 102(a)(2)/103 above, in view of Lee (US 20140183407 A1; “Lee”).
Takata teaches the limitations of Claim 11 as discussed above.
Takata teaches that the material of the organic binder is not particularly limited as long as this material allows efficient adhesion between the metal compound particles and the surface of the lithium layer ([0061]). Takata teaches that the binder is selected from the group consisting of poly(vinylidene fluoride), copolymer of vinylidene fluoride and hexafluoropropylene, poly(vinyl chloride), poly(urethane), and poly(acrylonitrile) ([0061]). However, this binder is in the protective layer ([0134]) and not the positive electrode active layer. In Example 10b, Takata teaches a copper foil without a lithium metal layer where a formulation comprising a binder of Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF) mixed with Evonik LLZO precursor particle ([0129]) (see Table 1, [0109] for description). This forms the positive electrode active layer, as the cell acts as a cathode in Li-Cu asymmetric cell fabrication ([0158]).
Takata does not teach a binder in the positive electrode active layer as claimed.
Lee teaches the binder for the invention of Lee may be selected from the group consisting of: polyvinylidene fluoride, polyacrylonitrile, polyvinyl alcohol, carboxymethyl cellulose (CMC), polyvinylpyrrolidone, (SBR), and a fluorine rubber, or a mixture of two or more thereof ([0033]). Lee states that the binder is mixed in the cathode (positive) electrode active material layer composition (positive electrode active layer) ([0009], [0013]).
Takata and Lee each constitute prior art which is directly analogous to claimed invention (MPEP 2141.01(a)(I)). It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the battery of Takata by incorporating a binder in the positive electrode active layer. Lee teaches that the cathode active material composition may improve life characteristics, output characteristics, and rate capability by improving high voltage stability, providing the motivation for incorporating a binder in the negative electrode active layer ([0015]) as commonly taught in the art ([0038]).
Pertinent Prior Art
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure:
CN-103647034-A to Zhang et al. - teaches nitride ceramic particles preferably at least one of silicon nitride, aluminium nitride, titanium nitride, boron nitride; said nitride can be used alone, or in a plurality of matches (ceramic particles mixed with other oxide, wherein the particle size of the particle is preferably 400 to 800 nm ([0013]), wherein the oil-based slurry binder is a fluorinated hydrocarbon and its derivatives, preferably polyvinylidene fluoride or butyl benzene rubber and its modified polymers, polyvinyl alcohol, acrylonitrile polymers, polyacrylic acid, acrylic acid series resin adhesive or acrylic adhesive agent [0016]; the coating thickness (of the protective layer) is controlled between 2 to 10 microns ([0037]); for positive and/or negative electrode (Abstract)
US-20160093884-A1 to Cui et al. - teaches that the protective coating comprises an oxide, such as SiO2 ([0014]).
WO-2019149939-A1 to Rodrigo et al. - discloses lithium metal anode coated with a protective layer having a thickness of 0.01 to 10 μm (Page 3, line 37), consisting a polymer and up to 30 wt %, relative to polymer, of inorganic particles (Page 4, line 2) such as Al2O3, MnO, MnO2, SiO2, TiO2, ZnO, ZrO2, Fe2O3, CuO, silicate, alumosilicate, borosilicate (Page 3, lines 29-31), having an average particle diameter of 1-500 nm (Page 4, line 1); teaches that the polymer may be polybutadiene (Page 3, Line 26)
US-20140220439-A1 to Badding et al. - discloses an alkaline metal anode coated with a protective coating comprising inorganic particles ([0020]), such as those containing the elements Al, Mg, Fe, Sn, Si, B, Cd, Sb ([0021]), dispersed throughout a matrix of an organic compound ([0020]), such as pyrrolidine derivatives – alkylated pyrrolidine ([0023]).
US-20220166017-A1 to Su et al. - discloses a ceramic filler material containing Al2O3, SiO2, ZnO, ZrO2, AlN, and Si3N4 ([0015]) with a thickness of about 1 μm to about 10 μm ([0021]); it teaches polyvinylidene difluoride (PVdF), polytetrafluoroethylene (PTFE), ethylene propylene diene monomer (EPDM) rubber, or carboxymethyl cellulose (CMC) as the binder for the positive electrode active layer ([0088])
US 2016/0093884-A1 to Cui et al. - teaches that the binding energy between O atoms at (½ ½ 0), (100), (010) position of Li2O and surface Li is −2.2079 eV, −2.1945 eV and −2.1987 eV respectively ([0116]).
Conclusion
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/WILLIAM FADDOUL SAVAGE/
Examiner, Art Unit 1782
/AARON AUSTIN/ Supervisory Patent Examiner, Art Unit 1782
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