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 .
Claim Rejections - 35 USC § 102
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of the appropriate paragraphs of 35 U.S.C. 102 that form the basis for the rejections under this section made in this Office action:
A person shall be entitled to a patent unless –
(a)(1) the claimed invention was patented, described in a printed publication, or in public use, on sale, or otherwise available to the public before the effective filing date of the claimed invention.
(a)(2) the claimed invention was described in a patent issued under section 151, or in an application for patent published or deemed published under section 122(b), in which the patent or application, as the case may be, names another inventor and was effectively filed before the effective filing date of the claimed invention.
Claim(s) 1 and 4-8 and 17 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Thoi et al. (US 2021/0408549 A9).
Claim 1: Thoi discloses a battery cathode for a lithium-sulfur battery (Abstract; [0012]) comprising a cathode current collector (a 12.7 mm carbon-paper current-collector disc onto which the cathode slurry is cast) and a cathode active material layer disposed on the cathode current collector (the cast slurry of metal-organic framework, sulfur, carbon, and PVDF binder) [0083]. The cathode active material layer comprises a metal-organic framework (a defected/lithiated Zr-based metal-organic framework, e.g., UiO-66 and MOF-808; [0053]). Thoi further discloses that, during the discharge cycle, elemental sulfur and lithium polysulfides at the cathode are reduced to lithium sulfide (Li2S) at the cathode (FIG. 2; [0015]). The claimed cathode is a product claim that does not recite a state of charge; in the device of Thoi, the cathode active material layer therefore comprises lithium sulfide (Li2S) and a metal-organic framework, and the cathode is for a lithium battery.
Claim 4: Thoi discloses that the metal-organic framework is a porous crystalline compound ([0043-0044]) comprising a Group 2–15 metal ion or metal ion cluster (a hexa-zirconium oxo-hydroxo node/cluster; [0053]) chemically bonded to an organic ligand (1,4-benzenedicarboxylic acid / benzene-1,3,5-tricarboxylate; [0054], [0056]).
Claim 5: Thoi discloses that the metal ion comprises zirconium ([0052]), and that the organic ligand is derived from an aromatic dicarboxylic acid (terephthalic acid, [0054]) or an aromatic tricarboxylic acid (benzene-1,2,4-tricarboxylic acid, [0056]).
Claim 6: Thoi discloses UiO-66, a compound built on a hexanuclear zirconium node of the generic formula Zr6(μ3-O)4(μ3-OH)4(RCOO)12 ([0053]; FIG. 1), whose organic linker is 1,4-benzenedicarboxylic acid, a ditopic linker (bearing two carboxylate groups) that occupies all of the carboxylate sites of the node ([0054]). UiO-66 reads on Formula 1 (MmOkXlLp) as follows: M is Zr4+, and m = 6 (the hexanuclear Zr node); the μ3-oxo groups provide the oxygen O (k within 0 to 10); the μ3-hydroxo groups provide X, which Formula 1 permits to be OH- (letter l within 0 to 10); and L is the 1,4-benzenedicarboxylate ligand of the form R—(*COO-#), wherein R is the benzene ring C6H4; a substituted or unsubstituted monocyclic C6–C30 aryl group, which is one of the R groups permitted by Formula 1; and q = 2 carboxylate groups (the ligand being ditopic). Each carboxylate group is bonded to the zirconium of the node through its oxygen atom (#), as shown by the node formula (RCOO)12 and FIG. 1 ([0053]–[0054]; FIG. 1). Because the twelve carboxylate sites of the node are occupied by ditopic 1,4-benzenedicarboxylate linkers (two carboxylate sites per linker), there are six such ligands per node, so p = 6.
Claim 7: Thoi discloses UiO-66 and MOF-808, each a zirconium metal-organic framework built on a hexanuclear zirconium node ([0053]). Thoi discloses that the organic linker of UiO-66 is 1,4-benzenedicarboxylic acid (H2BDC) ([0054]) and that the organic linker of MOF-808 is 1,3,5-benzenetricarboxylate (BTC) ([0056]). The 1,4-benzenedicarboxylate linker of UiO-66 has the formula C6H4(CO2)2, which Formula 2 of the instant claims defines as terephthalate (L′ = C6H4(CO2-)2 (terephthalate)); and the 1,3,5-benzenetricarboxylate linker of MOF-808 is a benzene-1,3,5-tricarboxylate, a further L′ recited in Formula 2. Accordingly, Thoi's UiO-66 and MOF-808 each read on a compound represented by Formula 2 (M′mOkX′lL′p), with M′ = Zr4+ and L′ = C6H4(CO2-)2 (terephthalate) or benzene-1,3,5-tricarboxylate, respectively.
Claim 8: Thoi discloses UiO-66, a metal-organic framework built on a hexanuclear zirconium oxo-hydroxo node of the formula Zr6(μ3-O)4(μ3-OH)4(RCOO)12 ([0053]) with 1,4-benzenedicarboxylic acid (H2BDC) as its organic linker ([0054]). The zirconium oxo-hydroxo node supplies the zirconium (Zr) and oxygen (O), and the 1,4-benzenedicarboxylate linker supplies the C6H4(CO2)2 moiety, such that UiO-66 is a compound of zirconium, oxygen, and C6H4(CO2)2 that reads on “ZrO[C6H4(CO2)2]” recited in claim 8.
Claim 17: Thoi discloses a lithium battery comprising the cathode of claim 1 (above), an anode comprising lithium (a polished metallic lithium anode; [0084]; FIG. 2; FIG. 8), and an electrolyte layer between the cathode and the anode (Celgard separators wetted with a LiTFSI/DME/DOL electrolyte; [0084]; FIG. 8).
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.
This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention(s) absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and effective filing dates of each claim that was not commonly owned as of the effective filing date of the later invention in order for the examiner to consider the applicability of 35 U.S.C. 102(b)(2)(C) for any potential 35 U.S.C. 102(a)(2) prior art against the later invention.
Claim(s) 1-11, 13-15, and 17-20 are rejected under 35 U.S.C. 103 as being unpatentable over Arthur (US 2020/0052285 A1) in view of Choi (US 2020/0052330 A1) and Thoi (US 2021/0408549 A9).
Claim 1: Arthur ‘285 discloses a cathode for a lithium solid-state battery comprising a cathode current collector (positive electrode collector 108, of SUS, aluminum, nickel, iron, titanium, or carbon) and a cathode active material layer (positive electrode active material layer 102) disposed on the cathode current collector (FIG. 1; [0020], [0027]). Arthur discloses that the cathode active material layer comprises lithium sulfide (Li2S): the positive electrode active material includes a lithium sulfide–lithium phosphorus sulfide composite that contains Li2S, and lithium sulfide (Li2S) is combined as the discharge material to form the positive electrode active material ([0021], [0035] (positive electrode active material layer 102); FIG. 2 (step 202), [0032]–[0033]). Arthur does not expressly disclose that the cathode active material layer further comprises a metal-organic framework.
Choi ‘330 teaches, in the same field of endeavor (sulfide-based lithium batteries whose sulfur-containing materials generate hydrogen sulfide (H2S) upon exposure to moisture), a metal-organic framework combined with the sulfide material so that hydrogen sulfide generated due to moisture exposure is adsorbed, lowering the rate at which hydrogen sulfide is discharged and thereby suppressing the resulting deterioration of ionic conductivity ([0004], [0030], [0032]).
Arthur expressly recognizes that lithium sulfide decomposes into hydrogen sulfide (H2S) gas when exposed to moisture ([0018]). Choi teaches that combining a metal-organic framework with a sulfide material captures such hydrogen sulfide and thereby suppresses the resulting deterioration of ionic conductivity ([0032]). Thoi further evidences that a metal-organic framework (e.g., UiO-66, MOF-808) may be incorporated directly into the cathode active material layer of a lithium-sulfur cell ([0053], [0083]). It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to include a hydrogen-sulfide-adsorbing metal-organic framework in the lithium-sulfide-containing cathode active material layer of the cathode; that is, at the location of the lithium sulfide that is the source of the hydrogen sulfide in order to capture the hydrogen sulfide generated by the lithium sulfide, and therefore improving the moisture stability and cycle life of the cell.
Claim 2: The combination applies the metal-organic framework of Choi, which has a size of about 1 nanometer to about 1 micrometer ([0036]).
Claim 3: Choi discloses that the metal-organic framework has a substantially uniform diameter distribution of primary particles represented by Inequation 1 (0 < σ2/μ < 1) ([0038]–[0039]).
Claim 4: Choi discloses that the metal-organic framework is a porous crystalline compound comprising a Group 2–15 metal ion or metal ion cluster chemically bonded to an organic ligand ([0041]).
Claim 5: Choi discloses that the Group 2–15 metal ion comprises at least one of the recited metals (e.g., cobalt, nickel, titanium, zirconium, iron, copper, zinc, aluminum, chromium) and that the organic ligand is derived from an aromatic dicarboxylic acid, an aromatic tricarboxylic acid, an imidazole compound, a tetrazole, a triazole, or a pyrazole, among the recited ligands ([0043]).
Claim 6: Choi discloses that the metal-organic framework is a compound represented by Formula 1 ([0046]–[0056]).
Claim 7: Choi discloses that the metal-organic framework comprises a compound represented by Formula 2 ([0057]–[0059]).
Claim 8: Choi discloses that the metal-organic framework comprises at least one of the compounds recited in claim 8, including Ti8O8(OH)4[O2C–C6H4–CO2]6 and ZrO[C6H4(CO2)2] ([0060]–[0063]).
Claim 9: Choi discloses that the metal-organic framework has a pore size of about 5 nanometers or less ([0037]).
Claim 10 & 11: Arthur discloses that the cathode active material layer further comprises an ion-conductive lithium salt in the form of a lithium salt dopant, namely Li3N, Li3P, Li2O, or Li3BO3, and further a lithium halide ([0022]; Examples 1–2 ([0061]–[0062])). Li3N, Li3P, and Li2O are binary compounds and the lithium halide is a binary compound recited in claim 11, and Li3BO3 is a ternary compound recited in claim 11.
Claim 13: Arthur discloses that the cathode active material layer (positive electrode active material layer 102) further comprises a solid electrolyte ([0021] (positive electrode active material layer 102); Examples 1–2 ([0061]–[0062]), wherein the cathode is a mixture of lithium sulfide, carbon, and lithium thiophosphate).
Claim 14: Arthur discloses that the cathode active material layer includes a sulfide-based solid electrolyte (a lithium thiophosphate) ([0035]–[0036] & [0061]–[0062])). Choi discloses that the sulfide-based solid electrolyte may be Li2S–P2S5, which is one of the sulfide solid electrolytes recited in claim 14 ([0075]); Choi further discloses the argyrodite Li6PS5Cl ([0076]–[0077]), which reads on the recited Li7-xPS6-xClx (x = 1). It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to employ, as the sulfide solid electrolyte of Arthur's cathode active material layer, a sulfide solid electrolyte recited in claim 14 such as Choi's Li2S–P2S5 or argyrodite Li6PS5Cl.
Claim 15: Choi discloses that the sulfide-based solid electrolyte is an argyrodite-type solid electrolyte, namely Li6PS5Cl ([0076]–[0077]); a density of about 1.5 to about 2.0 g/cc is an inherent characteristic of Li6PS5Cl argyrodite. It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to employ the argyrodite Li6PS5Cl as the sulfide solid electrolyte of the cathode active material layer, as a known high-ionic-conductivity sulfide solid electrolyte.
Claim 17: Arthur discloses a lithium battery comprising the cathode (above), an anode (negative electrode active material layer 104), and an electrolyte layer (solid electrolyte layer 106) between the cathode and the anode (FIG. 1; [0020]), the combination with Choi being applied for the reasons given in the rejection of claim 1.
Claim 18: Arthur discloses that the electrolyte layer comprises a solid electrolyte (solid electrolyte layer 106) (FIG. 1; [0025]); Choi likewise teaches that the lithium battery may comprise a solid electrolyte or a gel electrolyte ([0087]).
Claim 19: Choi discloses that the electrolyte layer comprises a metal-organic framework; the sulfide solid electrolyte and metal-organic framework being disposed between the cathode and the anode ([0009], [0030]).
Claim 20: Arthur discloses that the anode comprises a lithiophilic material, namely a metal active material such as silicon, tin, aluminum, or indium that forms an alloy with lithium ([0023], negative electrode active material layer 104). Choi likewise discloses an anode active material comprising silicon, a silicon alloy, tin, a tin alloy, or a metal/metalloid alloyable with lithium ([0085]).
Claim 12 is rejected under 35 U.S.C. 103 as being unpatentable over Arthur in view of Choi, and further in view of Watanabe (US 2019/0296393 A1).
Claim 12: The combination of Arthur and Choi renders obvious claim 10 as set forth above. Neither reference expressly discloses that the carbon-based material comprises carbon nanostructures. Watanabe teaches, in a sulfide solid-state battery, that the conductive additive of the cathode mixture layer may be carbon nanotubes (CNT) or carbon nanofibers (CNF) ([0029], conductive additive of the cathode mixture layer 12). It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to employ carbon nanofibers or carbon nanotubes as the carbon-based conductive material of the cathode active material layer, as a known conductive additive suitable for a sulfide solid-state cathode, in order to provide electronic conductivity within the cathode.
Claim 16 is rejected under 35 U.S.C. 103 as being unpatentable over Arthur in view of Choi, and further in view of Liang et al. (US 2019/0173089 A1).
Claim 16: The combination of Arthur and Choi renders obvious claim 1 as set forth above. Arthur discloses that the cathode current collector is a metal foil (e.g., aluminum) (Arthur, [0027], positive electrode collector 108) but does not disclose a base film and a metal layer. Liang teaches a current collector for a lithium battery comprising a base film (an insulation layer of an organic polymer insulation material such as polyethylene (PE), polypropylene (PP), polybutylene terephthalate (PBT), polyimide (PI), or polyethylene terephthalate (PET), [0106]) and a metal layer (a conductive layer, made of aluminum for a positive electrode current collector, disposed on the base film), which reduces electrode weight relative to metal foil and improves safety [0118]. It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to provide the cathode current collector as a base film with a metal layer, in order to reduce the weight of the electrode assembly and to improve the safety of the cell.
Conclusion
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/ATEF A SHAT/Examiner, Art Unit 1712
/MICHAEL B CLEVELAND/Supervisory Patent Examiner, Art Unit 1712
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