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 . The text of those sections of Title 35, U.S. Code not included in this action can be found in a prior Office action.
Claim Rejections - 35 USC § 103
The rejection of claims 1-3, 7, 8, 10, 11, 13-19, and 24 under 35 U.S.C. § 103 as being unpatentable over Zhamu et al. (US 2019/0319264 A1), hereinafter “Zhamu ‘264,” in view of Sugita et al. (US 2016/0254545 A1), hereinafter “Sugita,” Park (US 2024/0136567 A1), and He et al. (US 2019/0379021 A1), hereinafter “He,” is withdrawn because Applicant amended claims 1 and 24.
The rejection of claim 12 under 35 U.S.C. § 103 as being unpatentable over Zhamu ‘264 in view of Sugita, Park, He, and West et al. (2004/0214090 A1), hereinafter “West,” is withdrawn because Applicant amended claim 1.
The rejection of claims 20-23 under 35 U.S.C. § 103 as being unpatentable over Zhamu ‘264 in view of Park, and He is withdrawn because Applicant amended claim 1.
Claims 1-3,7, 8, 10, 11, 13-19, and 24 are rejected under 35 U.S.C. § 103 as being unpatentable over Zhamu ‘264 in view of Sugita, Park, and Zhamu et al. (US 2018/0166759 A1), hereinafter “Zhamu ‘759.”
Regarding claim 1, Zhamu ‘264 discloses a lithium secondary battery comprising a cathode, an anode, and an electrolyte or separator-electrolyte assembly disposed between said cathode and said anode (¶ [0013]), wherein said anode comprises:
an anode current collector (¶ [0013]); and
a thin layer of a high-elasticity polymer composite in ionic contact with said electrolyte and disposed between said anode current collector and electrolyte, in this case an elastomer may encapsulate the anode active material (¶ [0109]), wherein said polymer composite has a thickness from 2 nm to 100 μm, in this case 0.5 nm to 10 μm (e.g. ¶ [0013]), a fully recoverable tensile strain from 2% to 700%, in this case 5% to 1,000% (e.g. ¶ [0013]) and a lithium ion conductivity from 10-8 S/cm to 5 x 10--2 S/cm, in this case 10-7 S/cm to 5x10-2 S/cm (e.g. ¶ [0013]), wherein said elastic polymer comprises an elastomer selected from natural polyisoprene, synthetic polyisoprene, polybutadiene, chloroprene rubber, polychloroprene, metallocene-based poly(ethylene-co-octene) elastomer, poly(ethylene-co-butene) elastomer, epichlorohydrin rubber, polyacrylic rubber, silicone rubber, fluorosilicone rubber, perfluoroelastomers, polyether block amides, chlorosulfonated polyethylene, ethylene-vinyl acetate, thermoplastic elastomer, protein resilin, protein elastin, ethylene oxide-epichlorohydrin copolymer, polysiloxane, polyurethane, urethane-urea copolymer, urethane-acrylic copolymer, a copolymer thereof, a sulfonated version thereof, or a combination thereof (¶ [0015]-[0016]; [0110]).
Zhamu ‘264 does not disclose that the elastomer is urethane-acrylic copolymer, or a sulfonated version thereof, or a combination thereof. However, Park discloses that a copolymer of copolymer of a crosslinkable precursor including a urethane-containing polyfunctional acrylic monomer and a polyfunctional block copolymer as an organic material can improve ion conductivity, electrochemical characteristics, and mechanical and elastomeric properties (¶ [0064]). One having ordinary skill in the art would have realized that including such a copolymer in contact with the anode and electrolyte would have provided improved ion conductivity, electrochemical characteristics, and mechanical and elastomeric properties (¶ [0064]), thereby facilitating improved lithium secondary battery performance. Therefore, it would have been obvious to have included a urethane-acrylic copolymer in ionic contact with the electrolyte in order to facilitate improved lithium secondary battery performance.
Zhamu ‘264 does not disclose the urethane-acrylic copolymer. Park teaches the urethane-acrylic copolymer, but does not teach that it is sulfonated. However, Khan teaches that sulfonated polyacrylic acid copolymer is cheap, commercially available, and relatively non-toxic (¶ [0035]). One having ordinary skill in the art would have understood that substituting sulfonated urethane-acrylic copolymer for the urethane-acrylic copolymer of Park would have yielded the predictable result of providing a functional anode while reducing production costs and minimizing toxicity. See M.P.E.P. § 2143 I. B. Therefore, it would have been obvious to have substituted sulfonated urethane-acrylic copolymer for urethane-acrylic copolymer in order to have yielded the predictable result of providing a functional anode while reducing production costs and minimizing toxicity.
Zhamu ‘264 does not disclose a hybrid or composite electrolyte. However, Zhamu ‘759 teaches a hybrid electrolyte (¶ [0090], [0100], & [0102]). One having ordinary skill in the art would have understood that providing a hybrid electrolyte would have yielded a battery with improved safety (¶ [0100]). Therefore, it would have been obvious to have provided a hybrid electrolyte for the lithium secondary battery in order to have facilitated improved safety.
Regarding claim 2, Zhamu ‘264 further discloses that the anode initially has not lithium or lithium alloy supported by the anode current collector prior to initial battery charge and discharge, in this case the anode active material may be “selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), nickel (Ni), cobalt (Co), manganese (Mn), titanium (Ti), iron (Fe), and cadmium (Cd)…; (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, or Cd with other elements…; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ni, Co, Ti, Mn, or Cd, and their mixtures or composites…; (d) salts and hydroxides of Sn…; and (e) carbon or graphite materials (¶ [0033]).
Regarding claim 3, Zhamu ‘264 further discloses that the anode has an amount of lithium or lithium alloy supported by the anode current collector prior to initial charge and discharge, in this case the materials listed in the rejection of claim 2, above, may also include lithiated versions (¶ [0033]).
Regarding claim 5, Zhamu ‘264 further discloses that the electrolyte is selected from polymer electrolyte, polymer gel electrolyte, composite electrolyte, ionic liquid electrolyte, non-aqueous liquid electrolyte, soft matter phase electrolyte, solid-state electrolyte, or a combination thereof (¶ [0030]).
Regarding claim 7, Zhamu ‘264 further discloses that the elastomer may contain a cross-linked network of polymer chains having an ether linkage, nitrile-derived linkage, benzo peroxide-derived linkage, ethylene oxide linkage, propylene oxide linkage, vinyl alcohol linkage, cyano-resin linkage, triacrylate monomer-derived linkage, tetraacrylate monomer-derived linkage, or a combination thereof in said cross-linked network of polymer chains (¶ [0072]).
Regarding claim 8, Zhamu ‘264 further discloses that the elastomer contains a cross-linked network of polymer chains selected from nitrile-containing polyvinyl alcohol chains, cyanoresin chains, pentaerythritol tetraacrylate chains, pentaerythritol triacrylate chains, ethoxylated trimethylolpropane triacrylate (ETPTA) chains, ethylene glycol methyl ether acrylate (EGMEA) chains, or a combination thereof (¶ [0072]).
Regarding claim 10, Zhamu ‘264 further discloses that the elastomer may form a mixture with a lithium ion-conducting polymer selected from poly(ethylene oxide) (PEO), polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVDF), poly bis-methoxy ethoxyethoxide-phosphazene, polyvinyl chloride, polydimethylsiloxane, poly(vinylidene fluoride)- hexafluoropropylene (PVDF-HFP), a derivative thereof (e.g. sulfonated versions), or a combination thereof (¶ [0108]).
Regarding claim 11, Zhamu ‘264 does not disclose the flame retardant additive. However, Sugita discloses additive flame retardants such as phosphate and melamine- based compounds to electrodes (¶ [0031]) at a loading of 1 wt% to 70 wt% (¶ [0032]). One having ordinary skill in the art would have realized that adding such a compound at a similar loading to the polymer composite would yield the predictable result of conferring the same flame retardant property, thereby facilitating improved battery safety. See M.P.E.P. § 2143 I. Therefore, it would have been obvious to have included a flame retardant additive at a loading of 0.01 wt% to 95 wt% in order to facilitate improved battery safety.
Regarding claim 13, Zhamu ‘264 further discloses that the elastic polymer further comprises 0.1% to 50% by weight of a lithium ion-conducting additive that is different from the flame retardant additive (¶ [0171] & Table 1).
Regarding claim 14, Zhamu ‘264 further discloses that the elastic polymer further comprises a reinforcement material, in this case 0.1% by weight to 10% by weight of a reinforcement nanofilament selected from carbon nanotube, carbon nanofiber, graphene, or a combination thereof (¶ [0021]).
Regarding claim 15, Zhamu ‘264 further discloses that the lithium ion-conducting additive contains a lithium salt selected from lithium perchlorate (LiClO4), lithium hexafluorophosphate (LiPF6), lithium borofluoride (LiBF4), lithium hexafluoroarsenide (LiAsF6), lithium trifluoro-metasulfonate (LiCF3SO3), bis-trifluoromethyl sulfonylimide lithium (LiN(CF3SO2)2), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF2C2O4), lithium oxalyldifluoroborate (LiBF2C2O4), lithium nitrate (LiNO3), Li-fluoroalkyl-phosphate (LiPF3(CF2CF3)3), lithium bisperfluoro-ethysulfonylimide (LiBETI), lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), an ionic liquid-based lithium salt, or a combination thereof (¶ [0023]).
Regarding claim 16, Zhamu ‘264 further discloses that the lithium ion-conducting additive is selected from is selected from Li2CO3, Li2O, Li2C2O4, LiOH, LiX, ROCO2Li, HCOLi, ROLi, (ROCO2Li)2, (CH2OCO2Li)2, Li2S, LixSOy (¶ [0054]).
Regarding claim 17, Zhamu ‘264 further discloses that the elastomer forms a mixture or blend with a lithium ion-conducting polymer selected from poly(ethylene oxide) (PEO), polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVDF), poly bis-methoxy ethoxyethoxide-phosphazene, polyvinyl chloride, polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP), a sulfonated derivative thereof, or a combination thereof (¶ [0027]).
Regarding claim 18, Zhamu ‘264 further discloses that the cathode an inorganic cathode active material, such as a metal selenide (¶ [0035]).
Regarding claim 19, Zhamu ‘264 further discloses that the cathode active material is selected from a metal selenide (¶ [0035]).
Regarding claim 24, Zhamu ‘264 discloses a lithium secondary battery comprising a cathode, an anode, and an electrolyte or separator-electrolyte assembly disposed between said cathode and said anode (¶ [0013]), wherein said anode comprises:
an anode current collector (¶ [0013]); and
a thin layer of a high-elasticity polymer composite in ionic contact with said electrolyte and disposed between said anode current collector and electrolyte, in this case an elastomer may encapsulate the anode active material (¶ [0109]), wherein said polymer composite has a thickness from 2 nm to 100 μm, in this case 0.5 nm to 10 μm (e.g. ¶ [0013]), a fully recoverable tensile strain from 2% to 700%, in this case 5% to 1,000% (e.g. ¶ [0013]) and a lithium ion conductivity from 10-8 S/cm to 5 x 10--2 S/cm, in this case 10-7 S/cm to 5x10-2 S/cm (e.g. ¶ [0013]), wherein said elastic polymer comprises an elastomer selected from natural polyisoprene, synthetic polyisoprene, polybutadiene, chloroprene rubber, polychloroprene, metallocene-based poly(ethylene-co-octene) elastomer, poly(ethylene-co-butene) elastomer, epichlorohydrin rubber, polyacrylic rubber, silicone rubber, fluorosilicone rubber, perfluoroelastomers, polyether block amides, chlorosulfonated polyethylene, ethylene-vinyl acetate, thermoplastic elastomer, protein resilin, protein elastin, ethylene oxide-epichlorohydrin copolymer, polysiloxane, polyurethane, urethane-urea copolymer, urethane- acrylic copolymer, a copolymer thereof, a sulfonated version thereof, or a combination thereof (¶ [0015]-[0016]; [0110]).
Zhamu ‘264 does not disclose the flame retardant additive. However, Sugita discloses adding flame retardants such as phosphate and melamine-based compounds to electrodes (¶ [0031]) at a loading of 1 wt% to 70 wt% (¶ [0032]). One having ordinary skill in the art would have realized that adding such a compound at a similar loading to the polymer composite would yield the predictable result of conferring the same flame retardant property, thereby facilitating improved battery safety. See M.P.E.P. § 2143 I. Therefore, it would have been obvious to have included a flame retardant additive at a loading of 0.01 wt% to 95 wt% in order to facilitate improved battery safety.
Zhamu ‘264 does not disclose that the elastomer is urethane-acrylic copolymer, or a sulfonated version thereof, or a combination thereof. However, Park discloses that a copolymer of copolymer of a crosslinkable precursor including a urethane-containing polyfunctional acrylic monomer and a polyfunctional block copolymer as an organic material can improve ion conductivity, electrochemical characteristics, and mechanical and elastomeric properties (¶ [0064]). One having ordinary skill in the art would have realized that including such a copolymer in contact with the anode and electrolyte would have provided improved ion conductivity, electrochemical characteristics, and mechanical and elastomeric properties (¶ [0064]), thereby facilitating improved lithium secondary battery performance. Therefore, it would have been obvious to have included a urethane-acrylic copolymer in ionic contact with the electrolyte in order to facilitate improved lithium secondary battery performance.
Zhamu ‘264 does not disclose the urethane-acrylic copolymer. Park teaches the urethane-acrylic copolymer, but does not teach that it is sulfonated. However, Khan teaches that sulfonated polyacrylic acid copolymer is cheap, commercially available, and relatively non-toxic (¶ [0035]). One having ordinary skill in the art would have understood that substituting sulfonated urethane-acrylic copolymer for the urethane-acrylic copolymer of Park would have yielded the predictable result of providing a functional anode while reducing production costs and minimizing toxicity. See M.P.E.P. § 2143 I. B. Therefore, it would have been obvious to have substituted sulfonated urethane-acrylic copolymer for urethane-acrylic copolymer in order to have yielded the predictable result of providing a functional anode while reducing production costs and minimizing toxicity.
Zhamu ‘264 does not disclose a hybrid or composite electrolyte. However, Zhamu ‘759 teaches a hybrid electrolyte (¶ [0090], [0100], & [0102]). One having ordinary skill in the art would have understood that providing a hybrid electrolyte would have yielded a battery with improved safety (¶ [0100]). Therefore, it would have been obvious to have provided a hybrid electrolyte for the lithium secondary battery in order to have facilitated improved safety.
Claim 12 is rejected under 35 U.S.C. § 103 as being unpatentable over Zhamu ‘264, Sugita, Park, and Zhamu ‘759 as applied to claim 1, above, and further in view of West.
Regarding claim 12, Zhamu ‘264 does not disclose the flame retardant additive and Sugita does not disclose a flame retardant comprising a group bonded polysiloxane. However, West discloses that cyclic-type polysiloxanes provide flame-retardant properties (¶ [0027]). One having ordinary skill in the art would have understood that substituting the polysiloxane for the phosphate and melamine compounds would have yielded the predictable result of providing flame-retardant properties to the elastic polymer. See M.P.E.P. § 2143 I. B. Therefore, it would have been obvious to have substituted the polysiloxane of West for the phosphate and melamine compounds of Sugita in order to yield the predictable result of providing the flame-retardant property.
Claims 20-23 are rejected under 35 U.S.C. § 103 as being unpatentable over Zhamu ‘264, Sugita, Park, and Zhamu ‘759as applied to claims 18 and 19, above, and further in view of He.
Regarding claim 20, Zhamu ‘264 does not disclose the recited oxides, phosphates, and silicide as the inorganic material. However, He discloses that lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium vanadium oxide, lithium transition metal oxide, lithium-mixed metal oxide (e.g. the well-known NCM, NCA, etc.), transition metal fluoride, transition metal chloride, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, lithium mixed metal phosphates, transition metal sulfides, and combinations thereof may be substituted for selenides (¶ [0113]-[0116]). One having ordinary skill in the art would have understood that substituting the compounds disclosed by He for the selenide of Zhamu ‘264 would have yielded the predictable result of a functional cathode active material. See M.P.E.P. § 2143 I. B. Therefore, it would have been obvious to have substituted the materials disclosed by He for the selenide of Zhamu ‘264 in order to yield the predictable result of providing a functional cathode active material.
Regarding claim 21, Zhamu ‘264 does not disclose the recited silicates as the inorganic material. However, He discloses that silicates according to Li2MSiO4 may be substituted for selenides (¶ [0115]-[0116]). One having ordinary skill in the art would have understood that substituting the compounds disclosed by He for the selenide of Zhamu ‘264 would have yielded the predictable result of a functional cathode active material. See M.P.E.P. § 2143 I. B. Therefore, it would have been obvious to have substituted the materials disclosed by He for the selenide of Zhamu ‘264 in order to yield the predictable result of providing a functional cathode active material.
Regarding claim 22, Zhamu ‘264 does not disclose the recited vanadium oxides as the inorganic material. However, He discloses that vanadium oxides according to VO2, LixVO2, V2O5, LixV2O5, V3O8, LixV3O8, LixV3O7, V4O9, LixV4O9, V6O13, LixV6O13 may be substituted for selenides (¶ [0114]-[0116]). One having ordinary skill in the art would have understood that substituting the compounds disclosed by He for the selenide of Zhamu ‘264 would have yielded the predictable result of a functional cathode active material. See M.P.E.P. § 2143 I. B. Therefore, it would have been obvious to have substituted the materials disclosed by He for the selenide of Zhamu ‘264 in order to yield the predictable result of providing a functional cathode active material.
Regarding claim 23, Zhamu ‘264 does not disclose the recited materials as the inorganic material. However, He discloses that silicates according to Li2MSiO4 may be substituted for selenides (¶ [0115]-[0116]). One having ordinary skill in the art would have understood that substituting the compounds disclosed by He for the selenide of Zhamu ‘264 would have yielded the predictable result of a functional cathode active material. See M.P.E.P. § 2143 I. B. Therefore, it would have been obvious to have substituted the materials disclosed by He for the selenide of Zhamu ‘264 in order to yield the predictable result of providing a functional cathode active material.
Response to Arguments
Applicant’s arguments with respect to claims 1-3, 7, 8, and 10-24 have been considered but are moot because the new ground of rejection does not rely on any reference applied in the prior rejection of record for any teaching or matter specifically challenged in the argument.
Conclusion
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See M.P.E.P. § 706.07(a). Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
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/SCOTT J. CHMIELECKI/Primary Examiner, Art Unit 1729
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