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 .
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 1, 3-8 and 10-16 are rejected under 35 U.S.C. 103 as being unpatentable over SAKUMA et al. (US 2014/0234696 A1) in view of CHOI et al. (KR 20220010175 A, a machine translation is provided).
Regarding claim 1: SAKUMA (paragraphs [0081] and [0122]- [0124] and CHOI (paragraphs [0007] and [0010] – [0011]) both teach an electrolyte solution for a lithium secondary battery comprising a solvent, lithium salt, and an additive. However, SAKUMA lacks an explicit disclosure of a metal additive selected silver (Ag), gold (Au), or platinum (Pt). CHOI remedies this deficiency by explicitly introducing a fractional noble metal additive silver (Ag), directly into a liquid lithium secondary battery electrolyte to act as lithiophilic nucleation sites that promote uniform lithium deposition and passivate the interface (paragraphs [0007], [0024], [0035] – [0037] and [0073]). It would have been obvious to a person of ordinary skill in the art at the time of the invention to modify the electrolyte solution baseline of SAKUMA by incorporating the providing the metal element (Ag), taught by CHOI to simultaneously exploit the interfacial passivation stability of the dendrite suppressing nucleation kinetics of high-work function noble metals, resulting in a highly stable, high-capacity secondary lithium battery.
Extending this teaching to gold and platinum is prima facie obvious to a person of ordinary skill in the art because these adjacent noble metals share identical electrochemical behaviors in the context, they all possess reduction potentials vastly higher than lithium (-3.04 V), meaning they all spontaneously undergo identical galvanic displacement to create the exact same type of lithiophilic solid-solution alloy anchoring sites on a lithium anode. Substituting one noble metal carrier for another to achieve identical lithiophilic nucleation represents substitution of known chemical equivalents to achieve a predictable result.
Regarding claim 3: which depends upon claim1, SAKUMA further teaches the electrolyte solution utilizing high-purity lithium salts, specifically reciting lithium bis(fluorosulfonyl)amide (LFSI), lithium bis(trifluoromethanesulfonyl)amide (LiTFSI), lithium hexafluorophosphate (LiPF6), lithium tetraflurorborate (LiBF4), lithium perchlorate (LiClO4), lithium hexafluoroarsenate (LiAsF6), lithium trifluoromethane sulfonate (LiCF3SO3), lithium tetrachloroaluminate (LiAlCl4), lithium chloride (LiCl), and lithium bromide (LiBr) (paragraphs [0123] – [0124]).
Regarding claim 4: which depends upon claim 1, CHOI further teaches the electrolyte solution utilizing a nitrate of the metal element, specifically silver nitrate (AgNO3) (paragraph [0055] – [0056]). Furthermore, it was widely known in the chemical arts that nitrates and halogens of noble metals (AgNO3, AuBr3 (gold tribromide), etc.) to form a highly ionic-conductive Li3N phase in the solid electrolyte interphase (SEI) layer. It would have been obvious to a person of ordinary skill in the art to select these specific nitrate configurations as a predictable design choice to introduce the desired metal ions into the electrolyte solution, facilitating spontaneous electrochemical displacement or reduction onto the negative electrode substrate.
Regarding claim 5: which depends upon claim 1, CHOI further explicitly teaches the electrolyte solution’s use of AgNO3 as a functional liquid electrolyte additive to guide uniform lithium plating (paragraphs [0049] and [0073]). As set forth in claims 1 and 4, a person of ordinary skill in the art would substitute for or combine this with AuBr3 or Pt(NO3)4 (platinum nitrate) as it represents a predictable paring of known noble metal cations (Ag, Au, Pt) with known dissociative, organic-solvent-compatible counter anions (nitrates and bromides) to safely dissolve according to basic solubility limits.
Regarding claim 6: which depends upon claim 1, CHOI further teaches the electrolyte solution optimizing functional noble metal additive within fractional, dilute concentration of 0.01 wt% to 0.5 wt% of AgNO3 (paragraphs [0055] and [0072]) to provide uniform anode seeding without triggering massive corrosion or excessive galvanic displacement of the active lithium metal. It would have been obvious to a person of ordinary skill in the art to optimize the specific weight percentage of the additive down to the claimed range of 0.05 wt% to 0.1 wt%. The motivation to do so represents routine optimization of a known result effective variable. A person of ordinary skill in the art would experiment with lower fractional weight percentages to find the minimum amount of additive required to maximize cell capacity while safely avoiding an unnecessary increase in electrolyte viscosity or bulk cell resistance.
Regarding claim 7: SAKUMA teaches a lithium secondary battery layout comprising an anode current collector (22A, FIG. 2, paragraph [0059]), a separator (23, FIG. 2, (paragraph [0078]), a cathode active material layer (21B, FIG. 2, paragraphs [0050] – [0051]), a cathode current collector (21A, FIG. 2, paragraph [0050]), and an impregnated electrolyte solution (paragraph [0139]). SAKUMA further teaches an electrolyte solution comprising a solvent, a lithium salt, and an additive (paragraphs [0081] and [0122]- [0124]). However, SAKUMA lacks an explicit disclosure of a metal additive. CHOI remedies this deficiency by explicitly introducing a fractional noble metal additive (Ag, AgNO3) wherein the work function is higher than a work function of the anode current collector (paragraphs [0138] – [0140], FIG. 4).
It would have been obvious to a person of ordinary skill in the art to combine these teachings. The motivation is to construct a physical battery cell configuration where the high work function metal interface naturally guides uniform, smooth lithium plating to mitigate spatial dendritic growth, housed within a highly stable fluorosulfonamide fluid medium.
Regarding claim 8: which depends upon claim 7, SAKUMA further teaches the lithium secondary battery with an anode current collector configuration comprising a copper (Cu) substrate (paragraph [0059]). A person of ordinary skill in the art could construct the current collector layout of SAKUMA by providing a thin noble metal layer directly on a copper substrate. It inherently results in the formation of a localized alloy layer of copper and the metal element at the physical junction due to standard atomic interdiffusion during processing of subsequent electrochemical cycling. Under MPEP 2112.01, because the physical architecture taught by SAKUMA inherently exhibits this interfacial alloy characteristic, this limitation imparts no patentable weight.
Regarding claim 10: which depends on claim 7, SAKUMA further teaches the lithium secondary battery and utilization of high-purity lithium salts, specifically reciting lithium bis(fluorosulfonyl)amide (LFSI), lithium bis(trifluoromethanesulfonyl)amide (LiTFSI), lithium hexafluorophosphate (LiPF6), lithium tetraflurorborate (LiBF4), lithium perchlorate (LiClO4), lithium hexafluoroarsenate (LiAsF6), lithium trifluoromethane sulfonate (LiCF3SO3), lithium tetrachloroaluminate (LiAlCl4), lithium chloride (LiCl), and lithium bromide (LiBr) (paragraphs [0123] – [0124]).
Regarding claim 11: which depends upon claim 7, Under MPEP 2112.01, the applicant’s recitation of a specific work function range between 4.7 eV and 6 eV does not impart patentable weight to the claim as it merely describes an inherent, unalterable physical property of the metal element already rendered obvious by the prior art. CHOI explicitly discloses the lithium secondary battery utilizing the metal elecment (Ag) as the electrolyte additive (paragraph [0007]), and standard chemical homology makes the selection of adjacent metals like gold and platinum obvious. The fundamental physical constants for the clean work functions for these metals are universally known (gold [Au ~ 5.1-5.47 eV], silver [Ag ~ 4.72 – 4.74 eV] and platinum [Pt ~ 5.6 -5.93 eV]).
Therefore, once a person having ordinary skill in the art selects the noble metals (Ag, Au, or Pt) to act as lithiophilic nucleation sites as suggested by CHOI, the battery system inherently and inevitably operates with a metal element possessing a work function within the claimed range of being greater than 4.7 eV and smaller than or equal to 6 eV. Measuring or reciting an inherent physical constant of an otherwise obvious material choice lacks an inventive step.
Regarding claim 12: which depends upon claim 7, CHOI further teaches the lithium secondary battery introducing a fractional noble metal additive (Ag), directly into a liquid lithium secondary battery electrolyte to act as lithiophilic nucleation sites that promotes uniform lithium deposition and passivate the interface (paragraphs [0007], [0010], [0013], [0024] and [0073]).
Regarding claim 13: which depends upon claim 7, SAKUMA explicitly teaches the lithium secondary battery comprising the standard structural utilization of a copper negative current collector (paragraph [0059]) to support lithium metal electrodeposition. CHOI explicitly teaches that when the liquid electrolyte solution containing a dissolved noble metal (Ag+ from the AgNO3 additive) comes into direct physical contact with the negative electrode current collector, a spontaneous galvanic displacement reaction occurs to the massive potential difference.
Under MPEP 2112.01, because the reduction potential of copper (+0.34 V vs. standard hydrogen electrode (SHE)) and lithium (-3.04 V vs. SHE) are significantly lower than those of the metal virtues (Ag+ at +0.80 V, Au3+ at +1.50 V, Pt2+ at +1.18 V), the noble metal ions inherently deposit onto and interdiffuse into the surface grains of the copper current collector during initial cell assembly and early electrochemical cycling. It is inevitable physics reality that this galvanic displacement and thermal/electrochemical diffusion form a localized surface alloy (specifically a copper-silver, copper-gold, or copper-platinum alloy phase). Because this alloy layer is the natural, unavoidable thermodynamic consequence of adding the noble metal salt of CHOI onto the current copper collector of SAKUMA, the structural limitation is fully inherent.
Regarding claim 14: which depends upon claim 7, CHOI further teaches the lithium secondary battery utilizing a nitrate of the metal element, specifically AgNO3 (paragraph [0013]). Furthermore, it was widely known in the chemical arts that nitrates and halogens of noble metals (AgNO3, AuBr3, etc.) form a highly ionic-conductive Li3N phase in the SEI layer. It would have been obvious to a person of ordinary skill in the art to select these specific nitrate configurations as a predictable design choice to introduce the desired metal ions into the electrolyte solution, facilitating spontaneous electrochemical displacement or reduction onto the negative electrode substrate.
Regarding claim 15: which depends upon claim 7, CHOI further explicitly teaches the lithium secondary battery utilizing AgNO3 as a functional liquid electrolyte additive to guide uniform lithium plating (paragraphs [0007] and [0024] – [0025]). A person of ordinary skill in the art would substitute for or combine this with AuBr3 or Pt(NO3)4 as it represents a predictable paring of known noble metal cations (Ag, Au, Pt) with known dissociative, organic-solvent-compatible counter anions (nitrates and bromides) to safely dissolve accordioning to basic solubility limits.
Regarding claim 16: which depends upon claim 7, CHOI further teaches the lithium secondary battery optimizing functional noble metal additive within fractional, dilute concentration of of 0.01 wt% to 0.5 wt% of AgNO3 (paragraphs [0055] and [0072]) to provide uniform anode seeding without triggering massive corrosion or excessive galvanic displacement of the active lithium metal. It would have been obvious to a person of ordinary skill in the art to optimize the specific weight percentage of the additive down to the claimed range of 0.05 wt% to 0.1 wt%. The motivation to do so represents routine optimization of a known result effective variable. A person of ordinary skill in the art would experiment with lower fractional weight percentages to find the minimum amount of additive required to maximize cell capacity while safely avoiding an unnecessary increase in electrolyte viscosity or bulk cell resistance.
Claim 2 is rejected under 35 U.S.C. 103 as being unpatentable over SAKUMA et al. (US 2014/0234696 A1) in view of CHOI et al. (KR 20220010175 A, a machine translation is provided) as applied to claim 1 above, and further in view of XUE et al. “FSI-inspired solvent and ‘full fluorosulfonyl’ electrolyte for 4 V class lithium-metal batteries” (Energy & Environmental Science 2019).
Regarding claim 2: which depends upon claim 1, SAKUMA (paragraphs [0081] and [0122]- [0124] and CHOI (paragraphs [0007] and [0010]) both teach an electrolyte solution for a lithium secondary battery comprising a solvent, lithium salt, and an additive. CHOI explicitly introduces a fractional noble metal additive silver (Ag) (paragraphs [0007], [0024] and [0035]).
XUE further explicitly teaches the electrolyte solution’s foundational solvent matrix of the non-aqueous electrolyte is dimethylsulfamoyl fluoride (DMSF or FSA) as the core organic solvent for high-performance rechargeable lithium batteries to establish high coulombic efficiency and excellent anodic stability (page 2, paragraph 3). It would have been obvious to a person of ordinary skill in the art to utilize the DMSF solvent of XUE as the baseline for lithiophilic metal additives taught by CHOI or a disulfonyl compound of SAKUMA (paragraphs, [0014] – [0020], formulas (1) and (2)) to leverage DMSF’s inherent high-voltage oxidation resistance.
Claims 9 and 17-18 is rejected under 35 U.S.C. 103 as being unpatentable over SAKUMA et al. (US 2014/0234696 A1) in view of CHOI et al. (KR 20220010175 A, a machine translation is provided) as applied to claim 7 above, and further in view of XUE et al. “FSI-inspired solvent and ‘full fluorosulfonyl’ electrolyte for 4 V class lithium-metal batteries” (Energy & Environmental Science 2019).
Regarding claim 9: which depends upon claim 7, XUE further explicitly teaches the lithium secondary battery that comprises the solvent dimethylsulfamoyl fluoride to establish high coulombic efficiency and excellent anodic stability (page 2, paragraph 3). It would have been obvious to a person of ordinary skill in the art to utilize the DMSF solvent of XUE as the baseline for lithiophilic metal additives taught by CHOI or a disulfonyl compound of SAKUMA (paragraphs, [0014] – [0020], formulas (1) and (2)) to leverage DMSF’s inherent high-voltage oxidation resistance.
Regarding claim 17: which depends upon claim 7, SAKUMA further teaches a lithium secondary battery comprising a SEI layer between the cathode active material layer and the separator and between the anode current collector and the separator (paragraph [0144] and [0149] – [0150]).
However, the applicant’s negative claim limitation specifying that the SEI layer does not comprise an organic material is an inherent functional property directly dictated by the baseline medium taught by XUE. In conventional lithium batteries, organic SEI species form exclusively due to the radical reduction pathways of standard cyclic/acyclic organic carbonate solvents (like ethylene carbonate (EC), diethyl carbonate (DEC), or dimethyl carbonate (DMC)). Furthermore, XUE completely replaces these organic carbon solvent families with a full flurosulfonyl electrolyte composed entirely of LiFSI salt dissolved in a DMSF solvent (FIG. 1). SAKUMA also teaches a disulfonyl compound (formula (1) with a halogen, X, abstract paragraphs 1-2). under MPEP 2112.01, because the molecular structures of both LiFSI and DMSF lack traditional alkyl chains and consist entirely of inorganic-like fluorosulfonyl (-SO2F) and sulfamoyl linkages, their electrochemical reduction pathway cannot produce organic reduction polymers. A cycled lithium battery utilizing this specific baseline matrix inherently produces a purely inorganic, organic-free SEI consisting entirely of LiF, lithium sulfites, and inorganic nitrogenous fragments. The total absence of organic material in the interphase in the natural, inevitable chemical signature of the baseline solvent system of XUE.
Regarding claim 18: which depends upon claim 7, SAKUMA further teaches a lithium secondary battery comprising a SEI layer between the cathode active material layer and the separator and between the anode current collector and the separator (paragraph [0144] and [0149] – [0150]).
The functional limitation that the resulting SEI layer comprises LiF, Li2CO3 or LiO is an inherent chemical property of the decomposition products yielded of an LiFSI salt and SDMF solvent taught by XUE. It is widely recognized in the secondary battery arts the electrochemical reduction of highly fluorinated salts and fluorosulfonamide solvents at an alkali-metal interface inherently deposits lithium fluoride (LiF), lithium carbonates, and lithium oxides onto the active current collector boundaries. Under MPEP 2112,01, because the baseline components taught by XUE or SAKUMA inherently react to form these exact inorganic species, this limitation imparts no patentable distinction.
Conclusion
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/KENDRA DAWN CORONADO/Examiner, Art Unit 1743
/GALEN H HAUTH/Supervisory Patent Examiner, Art Unit 1743
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