DETAILED ACTION
Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Continued Examination Under 37 CFR 1.114
A request for continued examination under 37 CFR 1.114, including the fee set forth in 37 CFR 1.17(e), was filed in this application after final rejection. Since this application is eligible for continued examination under 37 CFR 1.114, and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114. Applicant's submission filed on 02 April 2026 has been entered.
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 is incorrect, any correction of the statutory basis for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention 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, 4, 6-7, 9-10, 12-13 and 15 are rejected under 35 U.S.C. 103 as being unpatentable over Mikhaylik et al (US 2014/0062411 A1) in view of Huang et al (US 2004/0122178 A1). These prior art references being cited to as Mikhaylik and Huang, respectively, hereinafter in this Office Action.
Regarding claim 1, Mikhaylik discloses an electrochemical device for a lithium-sulfur battery (“The lithium batteries described herein may include an anode having lithium ( e.g., lithium metal, a lithium intercalation compound, or a lithium alloy) as the active anode species and a cathode having sulfur as the active cathode species.” [0026]) comprising:
a positive electrode (“Cathode 30 may include an active cathode material 32” [0030]), a negative electrode (“anode 10 comprising an active anode material layer 18” [0030]), and an electrolyte complex (“battery 6 includes a first polymer layer 24 residing at the anode and a second polymer layer 40 residing at the cathode” [0039]);
wherein the positive electrode comprises sulfur (“an active cathode material 32 (e.g., sulfur)” [0030]),
wherein the negative electrode comprises lithium (“an active anode material layer 18 ( e.g., lithium metal)” [0030]),
wherein the electrolyte complex comprises a first solid phase electrolyte (“a second polymer layer 40 residing at the cathode” [0039]) and a second solid phase electrolyte (“a first polymer layer 24 residing at the anode” [0039]),
wherein the first solid phase electrolyte and the second solid phase electrolyte are different from each other (“a "heterogeneous electrolyte" is an electrolyte including at least two different liquid solvents ( oftentimes referred to herein as first and second electrolyte solvents, or anode-side and cathode-side electrolyte solvents)” [0028]) and form a layered structure (“The two different liquid solvents may be miscible or immiscible with one another, although in many aspects of the invention, electrolyte systems include one or more solvents that are immiscible ( or can be made immiscible within the cell) to the extent that they will largely separate and at least one can be isolated from at least one component of the cell. A heterogeneous electrolyte may be in the form of a liquid, a gel, or a combination thereof.” [0028], and furthermore “The first and second electrolyte solvents were chosen for this particular electrochemical cell because dibutyl Ether does not dissolve polysulfide and is immiscible with polysulfides Solutions in 1,2-dimethoxyethane. Accordingly, the first and second electrolytes were expected to partition in this electrochemical cell.” [0120]),
wherein the first solid phase electrolyte faces the positive electrode (“a second polymer layer 40 residing at the cathode” [0039]) and the second solid phase electrolyte faces the negative electrode (“a first polymer layer 24 residing at the anode” [0039]),
wherein the first solid phase electrolyte comprises a first organic solvent having dielectric constant of 30 or more (“The cathode-side electrolyte solvent may have a relatively higher solubility towards polysulfides, but may be more reactive towards lithium metal. By separating the electrolyte solvents during operation of the battery such that the anode-side electrolyte solvent is present disproportionately at the anode and the cathode-side electrolyte solvent is present disproportionately at the cathode, the battery can benefit from desirable characteristics of both electrolyte solvents (e.g., relatively low lithium reactivity of the anode-side electrolyte solvent and relatively high polysulfide solubility of the cathode-side electrolyte solvent).” [0026], “electrolyte Solvents such as 1,2-dimethoxyethane have relatively high polysulfide solubility but are more reactive towards lithium metal, and, therefore, can cause corrosion of the anode and/or poor lithium morphology. Accordingly, in Some embodiments, batteries described herein include a heterogeneous electrolyte comprising at least a first electrolyte solvent and a second electrolyte solvent, wherein the first electrolyte solvent, which has characteristics that are more favorable towards the anode, is present disproportionately at the anode during operation of the battery, and the second electrolyte solvent, which has characteristics that are more favorable towards the cathode, is present disproportionately at the cathode.” [0031], and “Specific liquid electrolyte solvents that may be favorable towards the cathode ( e.g., have relatively high polysulfide solubility, and/or can enable high rate capability and/or high sulfur utilization) include, but are not limited to dimethoxyethane (DME, 1,2-dimethoxyethane) or glyme, diglyme, triglyme, tetraglyme, polyglymes, sulfolane” [0062] with italics added for emphasis on the common rationale behind selecting compounds for the corresponding first organic solvent and on dimethoxyethane and sulfolane being an alternative compounds to each other where dimethoxyethane has a dielectric constant range between 3.5 to 7.2, and sulfolane has a dielectric constant of 43.4 and is sulfone-based), a first lithium salt (“a polymer layer is formed by depositing a mixture of a monomer and a solvent (e.g., an electrolyte solvent), optionally including other components such as crosslinking agents, lithium salts, etc., onto an electrode surface.” [0057] with italics added for emphasis, where “ionic electrolyte salts for use in the electrolytes of the present invention include, but are not limited to, LiSCN, LiBr, LiI, LiClO4, LiAsF6, LiSO3CF3, LiSO3CH3, LiBF4, LiB(Ph)4, LiPF6, LiC(SO2CF3)3, and LiN(SO2CF3)2.” [0070] and a “The cathode and porous separator were filled with 84 wt % of 1,2-dimethoxyethane and 16 wt % of salt-lithium bis(trifluoromethanesulfoneimide) ( e.g., a second electrolyte solvent).” [0116] was used in Example 6), a first polymer formed by polymerization of a first crosslinkable monomer (“a polymer layer is formed by depositing a mixture of a monomer and a solvent (e.g., an electrolyte solvent), optionally including other components such as crosslinking agents, lithium salts, etc., onto an electrode surface. The mixture may then be polymerized and/or crosslinked to form a polymer gel.” [0057]) and a first inorganic particle (“polymer layer(s) in contact with the anode or cathode, the polymer layer(s) may optionally comprise a filler. The filler may be dispersed within the polymer, may be added as a layer on the polymer, and/or may fill any pores in the polymer. The filler may comprise, for example, a metal, a polymer, or a ceramic. In one embodiment, the filler is a heterogeneous insoluble material. The filler may comprise, in some embodiments, a metal oxide, an oxy-hydroxide, a sulfide, a nitride, or a combination thereof. For example, the filler may include one or more of Al2O3, AlOOH, SiO2 , AlN, BN, and Li3N” [0054]),
wherein the second solid phase electrolyte comprises a second organic solvent having dielectric constant of 20 or less (“By separating the electrolyte solvents during operation of the battery such that the anode-side electrolyte solvent is present disproportionately at the anode and the cathode-side electrolyte solvent is present disproportionately at the cathode, the battery can benefit from desirable characteristics of both electrolyte solvents (e.g., relatively low lithium reactivity of the anode-side electrolyte solvent” [0026], “For instance, an electrolyte including the solvent dioxolane generally has relatively low reactivity towards lithium and has good lithium ion conductivity, but has relatively low polysulfide solubility” [0031], further supported in “partitioning of a heterogeneous electrolyte such that a first electrolyte solvent that has characteristics favorable towards the anode (e.g., low reactivity towards lithium, good lithium ion conductivity, and relatively low polysulfide solubility) is present disproportionately at the anode” [0043] with italics collectively added to link the common rationale behind selecting dioxolane as the corresponding second organic solvent, which is known in the art to have a dielectric constant of about 7.13), a second polymer formed by polymerization of a second crosslinkable monomer (“a polymer layer is formed by depositing a mixture of a monomer and a solvent (e.g., an electrolyte solvent), optionally including other components such as crosslinking agents, lithium salts, etc., onto an electrode surface. The mixture may then be polymerized and/or crosslinked to form a polymer gel.” [0057]) and a second inorganic particle (“polymer layer(s) in contact with the anode or cathode, the polymer layer(s) may optionally comprise a filler. The filler may be dispersed within the polymer, may be added as a layer on the polymer, and/or may fill any pores in the polymer. The filler may comprise, for example, a metal, a polymer, or a ceramic. In one embodiment, the filler is a heterogeneous insoluble material. The filler may comprise, in some embodiments, a metal oxide, an oxy-hydroxide, a sulfide, a nitride, or a combination thereof. For example, the filler may include one or more of Al2O3, AlOOH, SiO2 , AlN, BN, and Li3N” [0054]),
wherein the second lithium salt and the second polymer are dispersed in the second solid phase electrolyte (“a polymer layer is formed by depositing a mixture of a monomer and a solvent (e.g., an electrolyte solvent), optionally including other components such as crosslinking agents, lithium salts, etc., onto an electrode surface. The mixture may then be polymerized and/or crosslinked to form a polymer gel.” [0057] and “The filler may be dispersed within the polymer” [0054]),
wherein the second organic solvent is selected from the group consisting of tetrahydrofuran and dioxolane (“relatively low lithium reactivity of the anode-side electrolyte solvent” [0026], “For instance, an electrolyte including the solvent dioxolane generally has relatively low reactivity towards lithium” [0031]), and
wherein the first crosslinkable monomer and the second crosslinkable monomer are at least one selected from the group consisting of polyethylene glycol diacrylate (“Monomers can also be crosslinked, if desired, with any suitable crosslinker, such as aziridines, divinyibenzene, diacrylates,” [0053]), triethylene glycol diacrylate (“Monomers can also be crosslinked, if desired, with any suitable crosslinker, such as aziridines, divinyibenzene, diacrylates,” [0053]), trimethylolpropane ethoxylate triacrylate, and bisphenol A ethoxylate dimethacrylate (“Monomers can also be crosslinked, if desired, with any suitable crosslinker, such as aziridines, divinyibenzene, diacrylates, dimethacrylates,” [0053]).
Mikhaylik does not disclose wherein the first organic solvent is selected from the group consisting of carbonate-based organic solvent and gamma-butyrolactone (but does disclose “sulfolane” [0062] which is sulfone based and is known in the art as a strong polymer reaction solvent or plasticizer), and
wherein the first crosslinkable monomer and the second crosslinkable monomer are the same.
However, Huang discloses an electrochemical device for a lithium-sulfur battery (“a lithium ion battery” [0013] where “cathode active materials include … lithium sulfide” [0054]) comprising a positive electrode that comprises sulfur (“Such batteries can optionally contain the anode and cathode electrodes comprised of an anode or cathode active material” [0013] where “cathode active materials include … lithium sulfide” [0054]), a negative electrode that comprises lithium (“Such batteries can optionally contain the anode and cathode electrodes comprised of an anode or cathode active material” [0013] where “Anode intercalation materials include, but are not limited to lithium” [0077]), and an electrolyte complex (“rechargeable batteries employing Such crosslinked polymerS as the electrolyte” [0014]) that comprises a first polymer formed by polymerization of a first crosslinkable monomer (“the crosslinked polymers are comprised of a first monomer” [0061]) and a second polymer formed by polymerization of a second crosslinkable monomer (“one Second monomer” [0061]).
Huang teaches carbonate-based organic solvent and gamma-butyrolactone as organic solvents selected to be useful polymer plasticizers (“ethylene carbonate (EC) … γ-butryolactone (BL)” [0023] and [0067]), and
wherein the first crosslinkable monomer and the second crosslinkable monomer are the same (“the crosslinked polymers are comprised of a first monomer crosslinked to at least one Second monomer wherein the Second or other monomers are the same or different from the first monomer characterized in that the crosslinked polymer formed thereby is highly non-crystal
line” [0061] and “that the use of random, graft and block copolymers … room temperature conductivities of most of these polymers rarely exceeds 10--4 S/cm a value which is low for many applications” [0017] such that block copolymers known in the art to be polymers composed of different monomer in which this disclosure in [0017] at least suggests the use of the same monomer within the electrolyte complex from the perspective of maximizing electrolyte ion conductivity at room temperature).
Huang further teaches that the plasticizers improves conductivity of the electrolyte matrix without compromising the mechanical properties of the crosslinked polymer electrolytes ([0067]), and that utilizing the same monomer compound for both the first and second monomers forms crosslinked polymers that are non-crystalline and highly amorphous ([0061]) where simple crosslinking reactions allow for conversion of the crosslinked polymer electrolytes into rubbery materials with conductivities that rival liquid electrolytes ([0021]), and local relaxation and segmental motion of the polymer chains are a requirement for lithium ion transport ([0018]).
Therefore, it would have been obvious for a person having ordinary skill in the art to replace sulfolane as the first organic solvent of Mikhaylik with carbonate-based organic solvent (ethylene carbonate is one of the taught alternatives in Huang, and has a dielectric constant greater than 30) or gamma-butyrolactone, and to add a requirement for the monomer selection of the electrolyte matrix of Mikhaylik in view of Huang, wherein the first crosslinkable monomer and the second crosslinkable monomer are the same, in order to achieve improved conductivity of the electrolyte matrix without compromising the mechanical properties of the crosslinked polymer electrolytes, and a characteristically amorphous electrolyte matrix that has an ion conductivity comparable to liquid electrolytes at room temperature, and that ensures its capability to transport lithium ions within the lithium-sulfur battery.
Regarding claim 4¸ modified Mikhaylik discloses the electrochemical device for a lithium-sulfur battery with all the features set forth in claim 1 above, and wherein the first lithium salt is at least one selected from the group consisting of lithium bis(trifluoromethane sulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium perchlorate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium hexafluoroantimonate, lithium difluoromethane sulfonate, lithium aluminate, lithium tetrachloroaluminate, lithium chloride, lithium iodide, lithium bis(oxalate)borate, and lithium trifluoromethane sulfonyl imide (Mikhaylik [0070] “ionic electrolyte salts for use in the electrolytes of the present invention include, but are not limited to, LiSCN, LiBr, LiI, LiClO4, LiAsF6, LiSO3CF3, LiSO3CH3, LiBF4, LiB(Ph)4, LiPF6, LiC(SO2CF3)3, and LiN(SO2CF3)2.” and a “The cathode and porous separator were filled with 84 wt % of 1,2-dimethoxyethane and 16 wt % of salt-lithium bis(trifluoromethanesulfoneimide) ( e.g., a second electrolyte solvent).” [0116] was used in Example 6).
Regarding claim 6, modified Mikhaylik discloses the electrochemical device for a lithium-sulfur battery with all the features set forth in claim 1 above, and wherein the first inorganic particle is at least one selected from the group consisting of alumina (Al2O3), silicon dioxide (SiO2), titanium dioxide (TiO2), barium titanate (BaTiO3), lithium oxide (Li2O), lithium fluoride (LiF), lithium hydroxide (LiOH), lithium nitride (Li3N), barium oxide (BaO), sodium oxide (Na2O), lithium carbonate (Li2CO3), calcium carbonate (CaCO3), lithium aluminate (LiAlO2), strontium titanate (SrTiO3), tin oxide (SnO2), cerium oxide (CeO2), magnesium oxide (MgO), nickel oxide (NiO) calcium oxide (CaO), zinc oxide (ZnO), zirconium dioxide (ZrO2), and silicon carbide (SiC) (Mikhaylik [0054] “the filler may include one or more of Al2O3, AlOOH, SiO2, AlN, BN, and Li3N” with italics added for emphasis on the disclosed compounds that correspond to the claimed first inorganic particle).
Regarding claim 7, modified Mikhaylik discloses the electrochemical device for a lithium-sulfur battery with all the features set forth in claim 1 above, and wherein a thickness of the first solid phase electrolyte is 100 µm or less (Mikhaylik [0056] “The thickness of a polymer layer may vary, e.g., over a range from about 0.1 microns to about 100 microns”).
Regarding claim 9, modified Mikhaylik discloses the electrochemical device for a lithium-sulfur battery with all the features set forth in claim 1 above, and wherein the second organic solvent is dioxolane (Mikhaylik [0100] “A gel polymer electrolyte was formed by mixing 8.9 g of electrolyte ( dimethoxyethane ( 40% ), dioxolane ( 40% )” with italics added for emphasis in Example 1).
Regarding claim 10, modified Mikhaylik discloses the electrochemical device for a lithium-sulfur battery with all the features set forth in claim 1 above, and wherein the second lithium salt is at least one selected from the group consisting of lithium bis(trifluoromethane sulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium perchlorate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium hexafluoroantimonate, lithium difluoromethane sulfonate, lithium aluminate, lithium tetrachloroaluminate, lithium chloride, lithium iodide, lithium bis(oxalate)borate, and lithium trifluoromethane sulfonyl imide (Mikhaylik [0070] “ionic electrolyte salts for use in the electrolytes of the present invention include, but are not limited to, LiSCN, LiBr, LiI, LiClO4, LiAsF6, LiSO3CF3, LiSO3CH3, LiBF4, LiB(Ph)4, LiPF6, LiC(SO2CF3)3, and LiN(SO2CF3)2.” and a “The cathode and porous separator were filled with 84 wt % of 1,2-dimethoxyethane and 16 wt % of salt-lithium bis(trifluoromethanesulfoneimide) ( e.g., a second electrolyte solvent).” [0116] was used in Example 6).
Regarding claim 12, modified Mikhaylik discloses the electrochemical device for a lithium-sulfur battery with all the features set forth in claim 1 above, and wherein the second inorganic particle is at least one selected from the group consisting of alumina (Al2O3), silicon dioxide (SiO2), titanium dioxide (TiO2), barium titanate (BaTiO3), lithium oxide (Li2O), lithium fluoride (LiF), lithium hydroxide (LiOH), lithium nitride (Li3N), barium oxide (BaO), sodium oxide (Na2O), lithium carbonate (Li2CO3), calcium carbonate (CaCO3), lithium aluminate (LiAlO2), strontium titanate (SrTiO3), tin oxide (SnO2), cerium oxide (CeO2), magnesium oxide (MgO), nickel oxide (NiO) calcium oxide (CaO), zinc oxide (ZnO), zirconium dioxide (ZrO2), and silicon carbide (SiC) (Mikhaylik [0054] “the filler may include one or more of Al2O3, AlOOH, SiO2, AlN, BN, and Li3N” with italics added for emphasis on the disclosed compounds that correspond to the claimed first inorganic particle).
Regarding claim 13, modified Mikhaylik discloses the electrochemical device for a lithium-sulfur battery with all the features set forth in claim 1 above, and wherein a thickness of the second solid phase electrolyte is 100 µm or less (Mikhaylik [0056] “The thickness of a polymer layer may vary, e.g., over a range from about 0.1 microns to about 100 microns”).
Regarding claim 15, modified Mikhaylik discloses the electrochemical device for a lithium-sulfur battery with all the features set forth in claim 1 above, and wherein an interfacial resistance between the electrolyte complex and the positive or negative electrode is reduced by integration of the electrolyte complex and the positive or negative electrode (Mikhaylik [0060] “in one set of embodiments a heterogeneous electrolyte is used. Any liquid or gel material capable of storing and transporting ions ( e.g., lithium ions for a lithium battery) may be used, including a combination of liquids, a combination of liquid(s) and a polymer, etc., so long as the material(s) facilitates the transport of lithium ions between the anode and the cathode. The electrolyte may be electronically non-conductive to prevent short circuiting between the anode and the cathode.”).
Response to Arguments
Applicant’s arguments with respect to claim 1 has 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
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/CHARLENE BERMUDEZ/Examiner, Art Unit 1721
/ALLISON BOURKE/Supervisory Patent Examiner, Art Unit 1721
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