DETAILED ACTION
Introductory Notes
Any paragraph citation of the instant is in reference to the U.S. published patent application.
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and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114.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 8/20/2025 has been entered.
Claim Objections
Claim 21 is objected to because of the following informalities: “consisting of: comprises” in line 3 where “comprises” appears to be a clerical error. Appropriate correction is required.
Claim Rejections - 35 USC § 103
The text of those sections of Title 35, U.S. Code not included in this action can be found in a prior Office action.
Claims 1-3, 5, 7-10, 14 and 21 are rejected under 35 U.S.C. 103 as being unpatentable over WANG (CN 105811004 A, English translation used for citations) in view of LECUYER (US 20180175375 A1).
Regarding claim 1, WANG discloses a gel polymer electrolyte for an electrochemical cell that cycles lithium ions (“gel electrolyte that can be used in lithium ion batteries” [0010]), the gel polymer electrolyte comprising:
a polymer matrix infiltrated with a nonaqueous organic solvent, a first lithium salt in the nonaqueous organic solvent, and a second lithium salt in the nonaqueous organic solvent (“gel electrolyte comprising four components: (A) a high molecular polymer, (B) a lithium salt, (C) an organic solvent and (D) a functional additive” [0012] as well as “The lithium salt is a boric acid lithium salt and/or a sulfonimide lithium salt” [0014]),
wherein the polymer matrix comprises poly(vinylidene fluoride-co- hexafluoropropylene) (“polyvinylidene fluoride copolymer” [0013] as well as the use of PVDF-HFP in examples [0038,0042, etc.]),
the first lithium salt comprises lithium difluoro(oxalato)borate, and the second lithium salt comprises lithium bis(trifluoromethanesulfonyl)imide (“The boric acid lithium salt is … lithium bis(fluorooxalatoborate) (LiODFB). The sulfonyl imide lithium salt is preferably selected from lithium bis(trifluoromethylsulfonyl)imide (LiTFSI)” [0018]; notably LiODFB and LiDFOB are synonymous),
wherein the nonaqueous organic solvent, the first lithium salt, and the second lithium salt in combination constitute, by weight, greater than or equal to about 60% to less than or equal to about 95% of the gel polymer electrolyte, and the polymer matrix constitutes, by weight, greater than or equal to about 5% to less than or equal to about 40% of the gel polymer electrolyte (“mass fraction of the high molecular polymer in the gel electrolyte is 5-40%” [0015]).
Regarding “the polymer matrix comprises … an additional polymer selected from the group consisting of: poly(ethylene oxide), poly(acrylic acid), carboxymethyl cellulose, poly(vinyl alcohol), polyvinylpyrrolidone, and combinations thereof”, WANG discloses “polymers used in the physically cross-linked gel polymer electrolyte include polymethyl methacrylate (PMMA) and its copolymers, polyacrylonitrile (PAN) and its copolymers, etc.” [0006]. However, WANG does not expressly teach an additional polymer selected from the group consisting of: poly(ethylene oxide) (PEO), poly(acrylic acid) (PAA), carboxymethyl cellulose (CMC), poly(vinyl alcohol) (PVA), and polyvinylpyrrolidone (PVP).
LECUYER is directed to a polymer electrolyte including PVDF-HFP and LITFSI, like WANG. LECUYER discloses the polymer(s) “may be selected from polyolefins such as ethylene and propylene homopolymers or copolymers, or a mixture of at least two of these polymers” [0105] and specifically lists PEO and PVDF-HFP [0105]. Furthermore, in the examples listed in Table 3, a mixture of PVDF-HFP and PEO is used as the gel polymer electrolyte as discussed in paragraphs [0155-0161].
LECUYER teaches the battery of the invention “does not see its capacity reduced from the first cycles as compared with batteries of the prior art, indicating that disconnection of the grains of active material is avoided during cycling” [0107]; “stabilizes the battery capacity by limiting side reactions” [0108]; as well as that the “gelified polymer electrolyte allows the lithium ions to more easily reach the sulfur in the porosity of the carbon agent in comparison with a dry (i.e. solid) polymer electrolyte” [0109].
Before the effective filing date of the claimed invention, it would have been obvious to one of ordinary skill in the art to alter the PVDF-HFP of WANG such that it was a mixture of PVDF-HFP and PEO as taught by LECUYER to stabilize battery capacity while allowing lithium ions to reach the active material.
Therefore, modified WANG discloses an additional polymer selected from the group consisting of: poly(ethylene oxide), as taught by LECUYER.
Regarding claim 2, modified WANG discloses all the claim limitations as set forth above and WANG further discloses the gel polymer electrolyte is self-extinguishing (WANG notes "higher battery safety" [0016] and WANG teaches the claimed components of PVDF-HFP, LiDFOB, and LITFSI as well as solvents such as EC, PC, DMC, DEC, EMC [0018] that matches multiple solvents listed by the instant in paragraph [0074] which are noted to have "flame retardancy, self-extinguishing capabilities, and/or non-combustibility" per instant paragraph [0074]).
Regarding claim 3, modified WANG discloses all the claim limitations as set forth above and WANG further discloses the nonaqueous organic solvent comprises a mixture of a first solvent and a second solvent, the first solvent comprises propylene carbonate (“the organic solvent is preferably selected from … propylene carbonate (PC)” [0018]),
the second solvent comprises fluoroethylene carbonate (“the organic solvent also includes a fluorine-containing organic solvent … fluoroethylene carbonate (FEC)” [0018]), and
a volumetric ratio of the first solvent to the second solvent in the nonaqueous organic solvent is greater than or equal to about 0.5:9.5 to less than or equal to about 9.5:0.5 (WANG discloses an example electrolyte with “the following mass ratio: EC:EMC:PC:FEC is 3:4:2:1” [0053] wherein FEC is 10% of the total solvents or alternatively 50% relative to PC, both reading on the claimed range of anywhere from 5% to 95%).
Regarding claim 5, modified WANG discloses all the claim limitations as set forth above and WANG further discloses the gel polymer electrolyte consists essentially of the polymer matrix, the nonaqueous organic solvent, the first lithium salt, and the second lithium salt (“gel electrolyte comprising four components: (A) a high molecular polymer, (B) a lithium salt, (C) an organic solvent and (D) a functional additive” [0012]),
the first lithium salt consists essentially of lithium difluoro(oxalato)borate, and the second lithium salt consists essentially of lithium bis(trifluoromethanesulfonyl)imide (“The boric acid lithium salt is … lithium bis(fluorooxalatoborate) (LiODFB). The sulfonyl imide lithium salt is preferably selected from lithium bis(trifluoromethylsulfonyl)imide (LiTFSI)” [0018]; notably LiODFB and LiDFOB are synonymous).
Regarding claim 7, modified WANG discloses all the claim limitations as set forth above and WANG further discloses the polymer matrix further comprises: poly(methyl methacrylate), polyacrylonitrile, poly(vinyl alcohol), or a combination thereof (“polymers used in the physically cross-linked gel polymer electrolyte include polymethyl methacrylate (PMMA) and its copolymers, polyacrylonitrile (PAN) and its copolymers, etc.” [0006]).
Regarding claim 8, modified WANG discloses all the claim limitations as set forth above and WANG further discloses the gel polymer electrolyte further comprises: a third lithium salt selected from the group consisting of: comprises lithium bis(oxalato)borate, lithium tetracyanoborate, lithium tetrafluroborate, lithium bis(monofluoromalonato)borate, lithium trifluoromethanesulfonate, lithium bis(fluorosulfonyDimide, lithium —cyclo-difluoromethane-1,1-bis(sulfonylimide, lithium bis(perfluoroethanesulfonylimide, lithium cyclo-hexafluoropropane-1,1-bis(sulfonyl)imide, and combinations thereof (“The boric acid lithium salt is preferably one, two or three selected from lithium tetrafluoroborate (LiBF4), lithium bis(oxalatoborate) (LiBOB) and lithium bis(fluorooxalatoborate) (LiODFB).” [0018] this one, two, or three boric acid salts is notably in addition to the “sulfonyl imide lithium salt” [0018]).
Regarding claim 9, modified WANG discloses all the claim limitations as set forth above and WANG further discloses the gel polymer electrolyte is substantially free of lithium hexafluorophosphate (lithium hexafluorophosphate is notably absent from the salts listed by WANG in paragraph [0018]).
Regarding claim 10, modified WANG discloses all the claim limitations as set forth above and WANG further discloses an electrochemical cell that cycles lithium ions (“gel electrolyte that can be used in lithium ion batteries” [0010]), the electrochemical cell comprising:
a positive electrode current collector; a positive electrode layer disposed on the positive electrode current collector, the positive electrode layer having a facing surface and including electroactive material particles; a negative electrode current collector having a major surface, the major surface of the negative electrode current collector opposing the facing surface of the positive electrode layer; a porous separator disposed between the positive electrode layer and the negative electrode current collector; and a gel polymer electrolyte that infiltrates open pores in the positive electrode layer and in the porous separator (WANG discloses “Gel electrolyte preparation and battery cell production” [0034] and the steps that follow in paragraphs [0035-0039], which include lithium cobalt oxide and graphite as the active positive and negative materials; as well as “apply gel electrolyte to the positive and negative electrode sheets … stack the positive and negative electrode sheets together to obtain a battery cell containing gel electrolyte” [0051]),
wherein the gel polymer electrolyte comprises a polymer matrix infiltrated with a nonaqueous organic solvent, a first lithium salt in the nonaqueous organic solvent, and a second lithium salt in the nonaqueous organic solvent (“gel electrolyte comprising four components: (A) a high molecular polymer, (B) a lithium salt, (C) an organic solvent and (D) a functional additive” [0012] as well as “The lithium salt is a boric acid lithium salt and/or a sulfonimide lithium salt” [0014]),
wherein the polymer matrix comprises poly(vinylidene fluoride-co- hexafluoropropylene) (“polyvinylidene fluoride copolymer” [0013] as well as the use of PVDF-HFP in examples [0038,0042, etc.]),
the first lithium salt comprises lithium difluoro(oxalato)borate, and the second lithium salt comprises lithium bis(trifluoromethanesulfonyl)imide (“The boric acid lithium salt is … lithium bis(fluorooxalatoborate) (LiODFB). The sulfonyl imide lithium salt is preferably selected from lithium bis(trifluoromethylsulfonyl)imide (LiTFSI)” [0018]; notably LiODFB and LiDFOB are synonymous),
wherein the nonaqueous organic solvent, the first lithium salt, and the second lithium salt in combination constitute, by weight, greater than or equal to about 60% to less than or equal to about 95% of the gel polymer electrolyte, and the polymer matrix constitutes, by weight, greater than or equal to about 5% to less than or equal to about 40% of the gel polymer electrolyte (“mass fraction of the high molecular polymer in the gel electrolyte is 5-40%” [0015]).
Regarding “the polymer matrix comprises … an additional polymer selected from the group consisting of: poly(ethylene oxide), poly(acrylic acid), carboxymethyl cellulose, poly(vinyl alcohol), polyvinylpyrrolidone, and combinations thereof”, WANG discloses “polymers used in the physically cross-linked gel polymer electrolyte include polymethyl methacrylate (PMMA) and its copolymers, polyacrylonitrile (PAN) and its copolymers, etc.” [0006]. However, WANG does not expressly teach an additional polymer selected from the group consisting of: poly(ethylene oxide) (PEO), poly(acrylic acid) (PAA), carboxymethyl cellulose (CMC), poly(vinyl alcohol) (PVA), and polyvinylpyrrolidone (PVP).
LECUYER is directed to a polymer electrolyte including PVDF-HFP and LITFSI, like WANG. LECUYER discloses the polymer(s) “may be selected from polyolefins such as ethylene and propylene homopolymers or copolymers, or a mixture of at least two of these polymers” [0105] and specifically lists PEO and PVDF-HFP [0105]. Furthermore, in the examples listed in Table 3, a mixture of PVDF-HFP and PEO is used as the gel polymer electrolyte as discussed in paragraphs [0155-0161].
LECUYER teaches the battery of the invention “does not see its capacity reduced from the first cycles as compared with batteries of the prior art, indicating that disconnection of the grains of active material is avoided during cycling” [0107]; “stabilizes the battery capacity by limiting side reactions” [0108]; as well as that the “gelified polymer electrolyte allows the lithium ions to more easily reach the sulfur in the porosity of the carbon agent in comparison with a dry (i.e. solid) polymer electrolyte” [0109].
Before the effective filing date of the claimed invention, it would have been obvious to one of ordinary skill in the art to alter the PVDF-HFP of WANG such that it was a mixture of PVDF-HFP and PEO as taught by LECUYER in order to stabilize battery capacity while allowing lithium ions to reach the active material.
Therefore, modified WANG discloses an additional polymer selected from the group consisting of: poly(ethylene oxide), as taught by LECUYER.
Regarding claim 14, modified WANG discloses all the claim limitations as set forth above and WANG further discloses the gel polymer electrolyte is self-extinguishing (WANG notes "higher battery safety" [0016] and WANG teaches the claimed components of PVDF-HFP, LiDFOB, and LITFSI as well as solvents such as EC, PC, DMC, DEC, EMC [0018] that matches multiple solvents listed by the instant in paragraph [0074] which are noted to have "flame retardancy, self-extinguishing capabilities, and/or non-combustibility" per instant paragraph [0074]) and substantially free of lithium hexafluorophosphate (lithium hexafluorophosphate is notably absent from the salts listed by WANG in paragraph [0018]).
Regarding claim 21, modified WANG discloses all the claim limitations as set forth above and WANG further discloses the gel polymer electrolyte further comprises:a third lithium salt selected from the group consisting of: comprises lithium tetracyanoborate, lithium bis(monofluoromalonato)borate, lithium trifluoromethanesulfonate, lithium bis(fluorosulfonyl)imide, lithium cyclo-difluoromethane-1,1-bis(sulfonyl)imide, lithium bis(perfluoroethanesulfonyl)imide, lithium cyclo-hexafluoropropane-1,1-bis(sulfonyl)imide, and combinations thereof (“the lithium salt is preferably a boric acid lithium salt and/or a sulfonyl imide lithium salt … lithium bis(fluorosulfonyl)imide (LiFSI)” [0018]).
Claims 4 and 11 are rejected under 35 U.S.C. 103 as being unpatentable over WANG in view of LECUYER in view of XIAO (US 20220209297 A1).
Regarding claim 4, WANG discloses a total concentration of the first lithium salt and the second lithium salt in the nonaqueous organic solvent is greater than or equal to about 1.5 moles per liter to less than or equal to about 4.0 moles per liter (“The lithium salt is a boric acid lithium salt and/or a sulfonimide lithium salt” [0014] and “the molar concentration of the lithium salt in the gel electrolyte is 0.5-2 mol/L” [0015]).
WANG does not expressly teach the concentration of LiDFOB and LiTFSI or that the concentration of LiDFOB is greater than LiTFSI.
XIAO is directed to nonflammable electrolytes. XIAO teaches “embodiments of the disclosed nonflammable electrolytes are safer than conventional, flammable electrolytes, are cost-effective, safe, provide high CE, and/or provide stable cycling of rechargeable batteries” [0111].
In relation to the claim, XIAO discloses a concentration of the first lithium salt (LiDFOB [0080]) in the nonaqueous organic solvent is greater than or equal to about 0.8 moles per liter to less than or equal to about 2.0 moles per liter (“LiTFSI/LiFSI/LiDFOB/LiPF6/LiPO2F2 (1/1/2/1/1 molar ratio)” [0080] wherein the molar ratio may be multiplied by the taught total range of 0.5 to 5 M [0083] to arrive at a taught range of LiDFOB of 0.17 M to 1.67 M which reads the claimed range),
a concentration of the second lithium salt (LiTFSI [0080]) in the nonaqueous organic solvent is greater than or equal to about 0.05 moles per liter to less than or equal to about 2.0 moles per liter (“LiTFSI/LiFSI/LiDFOB/LiPF6/LiPO2F2 (1/1/2/1/1 molar ratio)” [0080] wherein the molar ratio may be multiplied by the taught total range of 0.5 to 5 M [0083] to arrive at a taught range of LiTFSI of 0.08 M to 0.83 M which is within the claimed range),
a concentration of the first lithium salt in the nonaqueous organic solvent is greater than a concentration of the second lithium salt in the nonaqueous organic solvent (“LiDFOB may be present in a molar concentration that is 1.5× to 5× higher than the molar concentration of any of the other salts in the nonflammable electrolyte” [0078] as well as “LiTFSI/LiFSI/LiDFOB/LiPF6/LiPO2F2 (1/1/2/1/1 molar ratio)” [0080] wherein the ratio of LiDFOB to LiTFSI is 2:1),
a total concentration of the first lithium salt and the second lithium salt in the nonaqueous organic solvent is greater than or equal to about 1.5 moles per liter to less than or equal to about 4.0 moles per liter (“0.5 M to 5 M” [0083] wherein the ranges have significant overlap and the same median value, furthermore the components are used for the same functionality).
Before the effective filing date of the claimed invention, it would have been obvious to one of ordinary skill in the art to utilize the concentrations for LiDFOB and LiTFSI of XIAO as the concentrations for the same salts of WANG because the combined salts at the taught concentrations would provide a safe, high CE, and stable electrolyte.
In an alternative interpretation consistent with the instant disclosures use of “about” (instant specification [0044]) and the claim relying on that definition in order for both LiDFOB and LiTFSI to have a maximum of 2.0 M even though LiDFOB is claimed to greater than LiTSFI: XIAO discloses a two-salt mixture of “LiTFSI/LiDFOB (1/1 molar ratio)” in [0092] and XIAO also discloses all numbers are to modified by the term “about” [0022]. Therefore, this about 1 to about 1 mixture of XIAO given in [0092] reads on the 0.05 to 2 M individual concentrations, the first salt being greater than second salt limitation, as well as the total concentration when combined with the disclosed range for total concentration in XIAO of “0.5 M to 5 M” [0083].
Regarding claim 11, WANG discloses the nonaqueous organic solvent comprises a mixture of propylene carbonate and fluoroethylene carbonate (“the organic solvent is preferably selected from … propylene carbonate (PC)” [0018]; and “the organic solvent also includes a fluorine-containing organic solvent … fluoroethylene carbonate (FEC)” [0018]).
WANG does not expressly teach the concentration of LiDFOB and LiTFSI or that the concentration of LiDFOB is greater than LiTFSI.
XIAO discloses LiDFOB is the primary salt and “LiDFOB may be present in a molar concentration that is 1.5× to 5× higher than the molar concentration of any of the other salts in the nonflammable electrolyte” [0078] as well as “LiTFSI/LiFSI/LiDFOB/LiPF6/LiPO2F2 (1/1/2/1/1 molar ratio)” [0080] wherein the ratio of LiDFOB to LiTFSI is 2:1. XIAO teaches “embodiments of the disclosed nonflammable electrolytes are safer than conventional, flammable electrolytes, are cost-effective, safe, provide high CE, and/or provide stable cycling of rechargeable batteries” [0111].
Before the effective filing date of the claimed invention, it would have been obvious to one of ordinary skill in the art to utilize the concentration ratios for LiDFOB and LiTFSI as taught by XIAO as the concentration ratios for the same salts of WANG because the combined salts at the taught concentrations would provide a safe, high CE, and stable electrolyte.
Claims 13 and 15-20 are rejected under 35 U.S.C. 103 as being unpatentable over WANG in view of LECUYER in view of JANG (US 20230096724 Al, cited in a previous office action).
Regarding claim 13, WANG discloses “improves the interface stability between electrolyte and electrode” [0031], however WANG does not expressly teach a lithium metal negative electrode layer electrochemically deposited on the major surface of the negative electrode current collector.
Similar to WANG, JANG notably discloses many of the limitations of claim 10:
a positive electrode current collector (“cathode current collector 18” [0144]); a positive electrode layer (“cathode layer 16” [0144]) disposed on the positive electrode current collector, the positive electrode layer having a facing surface and including electroactive material particles (“cathode active material” [0144]);
a negative electrode current collector having a major surface (“anode current collector 12” [0144]), the major surface of the negative electrode current collector opposing the facing surface of the positive electrode layer (Fig. 2(B));
a porous separator disposed between the positive electrode layer and the negative electrode current collector (“separator 15” [0144]);
and a gel polymer electrolyte (“a gel or a “solvent-in-polymer”” [0019]; “hybrid electrolyte” per claim 1) that infiltrates open pores in the positive electrode layer and in the porous separator (“electrolyte composition is designed to permeate into the internal structure of the cathode and to be in physical contact or ionic contact with the cathode active material in the cathode, and to permeate into the anode electrode to be in physical contact or ionic contact with the anode active material where/if present” [0058] as well as “the hybrid electrolyte is present in the anode, the cathode, the separator” [0084]),
wherein the gel polymer electrolyte comprises a polymer matrix (“polymer” Abstract) infiltrated with a nonaqueous organic solvent (“first liquid solvent is selected from the group consisting of vinylene carbonate, ethylene carbonate, fluoroethylene carbonate, …” [0017]), a first lithium salt (“LiDFOB” [0187]) in the nonaqueous organic solvent, and a second lithium salt (“LiTFSI” [0187]) in the nonaqueous organic solvent (“LIDFOB” [0036]),
wherein the polymer matrix comprises poly(vinylidene fluoride-co- hexafluoropropylene) (“PVDF-HFP” [0051] and used in example 5 [0186]), the first lithium salt comprises lithium difluoro(oxalato)borate (“LiDFOB” [0187]), and the second lithium salt comprises lithium bis(trifluoromethanesulfonyl)imide (“LiTFSI” [0187]).
Furthermore, and directly relevant to claim 13, JANG discloses a lithium metal negative electrode layer electrochemically deposited on the major surface of the negative electrode current collector (“lithium metal 20 plated on a surface (or two surfaces) of the anode current collector 12” [0144]), the lithium metal negative electrode layer having a facing surface that opposes the facing surface of the positive electrode layer (Fig. 2(B));
and an interfacial layer formed in situ (“in situ cured polymer” [0019]) on the facing surface of the lithium metal negative electrode layer, the interfacial layer extending substantially continuously along an interface between the porous separator and the facing surface of the lithium metal negative electrode layer (“interface between the anode and the separator” [0012]),
the interfacial layer comprises an electrochemical reduction product selected from the group consisting of: a fluorine-containing oligomer, a boron-containing oligomer, lithium bis[N-(trifluoromethylsulfonylimino)] trifluoromethanesulfonate, lithium fluoride, lithium oxide, lithium sulfide, lithium dithionite, lithium sulfite, lithium nitride, and combinations thereof (reaction scheme 2 and “LiF-rich solid electrolyte interface layer” in [0190] wherein LiF is lithium fluoride).
JANG teaches the disclosed electrolyte is able to “provide a safe, flame/fire-resistant, … occupies a minimal proportion of the total volume of an electrode, yet still forms a contiguous phase in the electrode and is in physical contact with substantially all the electrode active material particles” [0011].
Before the effective filing date of the claimed invention, it would have been obvious to one of ordinary skill in the art to form a lithium metal negative electrode layer and an interfacial layer as disclosed by JANG in the battery of WANG in order to provide a safe, contiguous phase with minimal proportion of the total volume of an electrode.
Regarding claim 15, WANG discloses an electrochemical cell that cycles lithium ions (“gel electrolyte that can be used in lithium ion batteries” [0010]), the electrochemical cell comprising:
a positive electrode current collector having a major surface; a positive electrode layer disposed on the major surface of the positive electrode current collector, the positive electrode layer including electroactive material particles; a negative electrode current collector having a major surface, the major surface of the negative electrode current collector opposing the major surface of the positive electrode current collector; a porous separator disposed between the positive electrode layer and the lithium metal negative electrode layer; and a gel polymer electrolyte that infiltrates open pores in the positive electrode layer and in the porous separator and extends substantially continuously between the major surface of the positive electrode current collector and the lithium metal negative electrode layer (WANG discloses “Gel electrolyte preparation and battery cell production” [0034] and the steps that follow in paragraphs [0035-0039], which include lithium cobalt oxide and graphite as the active positive and negative materials; as well as “apply gel electrolyte to the positive and negative electrode sheets … stack the positive and negative electrode sheets together to obtain a battery cell containing gel electrolyte” [0051]),
wherein the gel polymer electrolyte comprises a polymer matrix infiltrated with a nonaqueous organic solvent, a first lithium salt in the nonaqueous organic solvent, and a second lithium salt in the nonaqueous organic solvent (“gel electrolyte comprising four components: (A) a high molecular polymer, (B) a lithium salt, (C) an organic solvent and (D) a functional additive” [0012] as well as “The lithium salt is a boric acid lithium salt and/or a sulfonimide lithium salt” [0014]),
wherein the polymer matrix comprises poly(vinylidene fluoride-co- hexafluoropropylene) (“polyvinylidene fluoride copolymer” [0013] as well as the use of PVDF-HFP in examples [0038,0042, etc.]),
the first lithium salt comprises lithium difluoro(oxalato)borate, and the second lithium salt comprises lithium bis(trifluoromethanesulfonyl)imide (“The boric acid lithium salt is … lithium bis(fluorooxalatoborate) (LiODFB). The sulfonyl imide lithium salt is preferably selected from lithium bis(trifluoromethylsulfonyl)imide (LiTFSI)” [0018]; notably LiODFB and LiDFOB are synonymous),
wherein the nonaqueous organic solvent, the first lithium salt, and the second lithium salt in combination constitute, by weight, greater than or equal to about 60% to less than or equal to about 95% of the gel polymer electrolyte, and the polymer matrix constitutes, by weight, greater than or equal to about 5% to less than or equal to about 40% of the gel polymer electrolyte (“mass fraction of the high molecular polymer in the gel electrolyte is 5-40%” [0015]).
Regarding “the polymer matrix comprises … an additional polymer selected from the group consisting of: poly(ethylene oxide), poly(acrylic acid), carboxymethyl cellulose, poly(vinyl alcohol), polyvinylpyrrolidone, and combinations thereof”, WANG discloses “polymers used in the physically cross-linked gel polymer electrolyte include polymethyl methacrylate (PMMA) and its copolymers, polyacrylonitrile (PAN) and its copolymers, etc.” [0006]. However, WANG does not expressly teach an additional polymer selected from the group consisting of: poly(ethylene oxide) (PEO), poly(acrylic acid) (PAA), carboxymethyl cellulose (CMC), poly(vinyl alcohol) (PVA), and polyvinylpyrrolidone (PVP).
LECUYER is directed to a polymer electrolyte including PVDF-HFP and LITFSI, like WANG. LECUYER discloses the polymer(s) “may be selected from polyolefins such as ethylene and propylene homopolymers or copolymers, or a mixture of at least two of these polymers” [0105] and specifically lists PEO and PVDF-HFP [0105]. Furthermore, in the examples listed in Table 3, a mixture of PVDF-HFP and PEO is used as the gel polymer electrolyte as discussed in paragraphs [0155-0161].
LECUYER teaches the battery of the invention “does not see its capacity reduced from the first cycles as compared with batteries of the prior art, indicating that disconnection of the grains of active material is avoided during cycling” [0107]; “stabilizes the battery capacity by limiting side reactions” [0108]; as well as that the “gelified polymer electrolyte allows the lithium ions to more easily reach the sulfur in the porosity of the carbon agent in comparison with a dry (i.e. solid) polymer electrolyte” [0109].
Before the effective filing date of the claimed invention, it would have been obvious to one of ordinary skill in the art to alter the PVDF-HFP of WANG such that it was a mixture of PVDF-HFP and PEO as taught by LECUYER in order to stabilize battery capacity while allowing lithium ions to reach the active material.
Therefore, modified WANG discloses an additional polymer selected from the group consisting of: poly(ethylene oxide), as taught by LECUYER.
WANG discloses “improves the interface stability between electrolyte and electrode” [0031], however WANG does not expressly teach a lithium metal negative electrode layer electrochemically deposited on the major surface of the negative electrode current collector.
JANG discloses an electrochemical cell that cycles lithium ions (“rechargeable lithium battery” [Abstract]), the electrochemical cell comprising: a positive electrode current collector having a major surface (“cathode current collector 18” [0144]);
a positive electrode layer (“cathode layer 16” [0144]) disposed on the major surface of the positive electrode current collector, the positive electrode layer including electroactive material particles (“cathode active material” [0144]);
a negative electrode current collector having a major surface (“anode current collector 12” [0144]), the major surface of the negative electrode current collector opposing the major surface of the positive electrode current collector (Fig. 2(B));
a lithium metal negative electrode layer electrochemically deposited on the major surface of the negative electrode current collector (“lithium metal 20 plated on a surface (or two surfaces) of the anode current collector 12” [0144]);
a porous separator disposed between the positive electrode layer and the lithium metal negative electrode layer (“separator 15” [0144]);
and a gel polymer electrolyte (“a gel or a “solvent-in-polymer”” [0019]; “hybrid electrolyte” per claim 1) that infiltrates open pores in the positive electrode layer and in the porous separator and extends substantially continuously between the major surface of the positive electrode current collector and the lithium metal negative electrode layer (“electrolyte composition is designed to permeate into the internal structure of the cathode and to be in physical contact or ionic contact with the cathode active material in the cathode, and to permeate into the anode electrode to be in physical contact or ionic contact with the anode active material where/if present” [0058] as well as “the hybrid electrolyte is present in the anode, the cathode, the separator” [0084]), wherein the gel polymer electrolyte comprises a polymer matrix (“polymer” Abstract) infiltrated with a nonaqueous organic solvent (“first liquid solvent is selected from the group consisting of vinylene carbonate, ethylene carbonate, fluoroethylene carbonate, …” [0017]), a first lithium salt (“LiDFOB” [0187]) in the nonaqueous organic solvent, and a second lithium salt (“LiTFSI” [0187]) in the nonaqueous organic solvent,
wherein the polymer matrix comprises poly(vinylidene fluoride-co- hexafluoropropylene) (“PVDF-HFP” [0051] and used in example 5 [0186]), the nonaqueous organic solvent comprises a mixture of propylene carbonate and fluoroethylene carbonate (“propylene carbonate…fluoroethylene carbonate (FEC)… or a combination thereof” [0029] as well as “fluoroethylene carbonate” [0017]), the first lithium salt comprises lithium difluoro(oxalato)borate (“LiDFOB” [0187]), and the second lithium salt comprises lithium bis(trifluoromethanesulfonyl)imide (“LiTFSI” [0187]).
JANG teaches the disclosed electrolyte is able to “provide a safe, flame/fire-resistant, … occupies a minimal proportion of the total volume of an electrode, yet still forms a contiguous phase in the electrode and is in physical contact with substantially all the electrode active material particles” [0011].
Before the effective filing date of the claimed invention, it would have been obvious to one of ordinary skill in the art to form a lithium metal negative electrode layer as disclosed by JANG in the battery of WANG in order to provide a safe, contiguous phase with minimal proportion of the total volume of an electrode.
Regarding claim 16, modified WANG discloses all the claim limitations as set forth above and JANG further discloses each of the electroactive material particles in the positive electrode layer is at least partially encased in the gel polymer electrolyte (“electrolyte composition is designed to permeate into the internal structure of the cathode and to be in physical contact or ionic contact with the cathode active material in the cathode” [0058]).
Regarding claim 17, modified WANG discloses all the claim limitations as set forth above and JANG further discloses the gel polymer electrolyte fills, by volume, greater than or equal to about 5% to less than or equal to about 100% of the open pores in the positive electrode layer and in the porous separator (“electrolyte composition is designed to permeate into the internal structure of the cathode and to be in physical contact or ionic contact with the cathode active material in the cathode” [0058] as well as “the hybrid electrolyte is present in the anode, the cathode, the separator” [0084]; furthermore “occupies from 3% to 40% by volume of the cathode” per Claim 1 and [0012]).
Regarding claim 18, modified WANG discloses all the claim limitations as set forth above and JANG further discloses the porous separator comprises a microporous polymeric membrane (“porous PE/PP film or nonwoven of electro-spun PAN nano-fibers” [0190], wherein PP-PE as well as non-woven material, e.g., a mat of directionally or randomly oriented fibers are noted as being within the meets and bounds in instant paragraph [0067]).
Regarding claim 19, modified WANG discloses all the claim limitations as set forth above and JANG further discloses
the porous separator comprises a solid electrolyte layer that includes inorganic solid electrolyte material particles (“the separator layer comprises an inorganic solid electrolyte material” per Claim 35),
the inorganic solid electrolyte material particles are electrically insulating and ionically conductive (“particles of inorganic solid electrolyte material are preferably selected from an oxide type, sulfide type, hydride type, halide type, borate type, phosphate type, lithium phosphorus oxynitride (LiPON), garnet-type, lithium superionic conductor (LISICON) type, sodium superionic conductor (NASICON) type, or a combination thereof” [0052] overlapping with the instant definition of such particles in instant paragraph [0091]), and
each of the inorganic solid electrolyte material particles is at least partially encased in the gel polymer electrolyte (“ISE particles can be combined with an in situ cured polymer to form a hybrid solid-state or quasi-solid electrolyte in an anode, a cathode, and/or a separator” [0179]).
Regarding claim 20, modified WANG discloses all the claim limitations as set forth above and JANG further discloses the lithium metal negative electrode layer (“lithium metal 20” [0144]) comprises, by weight, greater than or equal to about 97% lithium (the “anode only contains a current collector or a protected current collector” [0145] as well as the plating of the metal discussed in [0144]),
and the electroactive material particles of the positive electrode layer comprise a lithium transition- metal oxide represented by the following formula: LiMeO2, LiMePO4, Li3Me2(PO4)3, LiMe204, LiMeS04F LiMePO4F, or a combination thereof, where Me is Co, Ni, Mn, Fe, Al, V, or a combination thereof (“the cathode comprises a cathode active material selected from lithium nickel manganese oxide (LiNiaMn2−aO4, 0<a<2), lithium nickel manganese cobalt oxide (LiNinMnmCo1−n−mO2, 0<n<1, 0<m<1, n+m<1), lithium nickel cobalt aluminum oxide (LiNicCodA1−c−dO2, 0<c<1, 0<d<1, c+d<1), lithium manganate (LiMn2O4), lithium iron phosphate (LiFePO4), lithium manganese oxide (LiMnO2), lithium cobalt oxide (LiCoO2), lithium nickel cobalt oxide (LiNipCo1−pO2, 0<p<1), or lithium nickel manganese oxide (LiNiqMn2−qO4, 0<q<2)” per Claim 25).
Response to Arguments
Regarding art-based rejections, applicant’s arguments with respect to the claims have been considered but are moot because the new ground of rejection does not rely on any interpretation applied in the prior rejection of record for any teaching or matter specifically challenged in the argument.
Conclusion
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/T.L.M./Examiner, Art Unit 1721
/ALLISON BOURKE/Supervisory Patent Examiner, Art Unit 1721