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 .
Priority
Receipt is acknowledged of certified copies of papers required by 37 CFR 1.55.
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.
Claim(s) 1, 3, 8, 11, and 15-17 is/are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Suzuki et al. (US 20200313164 A1, as cited in the 7/17/24 IDS).
Regarding claim 1, Suzuki teaches An all-solid secondary battery (An all-solid lithium secondary battery abstract) comprising:
a cathode layer (a cathode including a cathode active material layer, abstract);
an anode layer (an anode including an anode active material layer, abstract); and
a solid electrolyte layer (a solid electrolyte layer, abstract) between the cathode layer and the anode layer (30 between 10 and 20, Fig. 1 and [0084]),
wherein,
the cathode layer comprises a cathode current collector and a cathode active material layer on at least one surface of the cathode current collector (10 comprises 12 disposed on 11, Fig. 1 and [0045]),
at least one of the cathode active material layer or the solid electrolyte layer comprises a first two-dimensional (solid electrolyte layer 30, [0084] – where “layer” implies 2-D; thickness exaggerated in drawings per [0032]) sulfide-based solid electrolyte (a sulfide-based solid electrolyte material, [0085]), and
the anode layer comprises an anode current collector and a first anode active material layer on at least one surface of the anode current collector (20 comprises 22 disposed on 21, Fig. 1 and, and [0057])
wherein an initial charge capacity (B) of the first anode active material layer is less than about 50 % of an initial charge capacity (A) of the cathode active material layer (a ratio of the initial charge capacity of the cathode active material layer to the initial charge capacity of the anode active material layer satisfies 0.01<b/a<0.5, wherein a is the initial charge capacity of the cathode active material layer, and b is the initial charge capacity of the anode active material layer; Abstract).
Regarding claim 3, Suzuki teaches the limitations of claim 1 above and teaches a surface of the first two-dimensional sulfide-based solid electrolyte has a … polygonal shape, and
the polygonal shape comprises … a rectangular shape (surface of solid electrolyte layer 30 appears substantially rectangular along its perimeter in Fig. 1).
Regarding claim 8, Suzuki teaches the limitations of claim 1 above and wherein,
the cathode active material layer (cathode active material layer 12, [0045]) comprises a cathode active material (the cathode active material, [0048]),
the cathode active material comprises an oxide-based cathode active material (such as a lithium cobalt oxide (hereinafter, LCO), a lithium nickel oxide, a lithium nickel cobalt oxide, a lithium nickel cobalt aluminum oxide (hereinafter, NCA), a lithium nickel cobalt manganese oxide (hereinafter, NCM), a lithium manganese oxide; [0048]), a sulfide-based cathode active material (a lithium sulfide, [0048]; D and F’ in the exemplary formulas in [0049] may be sulfur(S)), or a combination thereof (…or a combination thereof., [0048]),
the oxide-based cathode active material comprises a lithium transition metal oxide, a metal oxide, or a combination thereof (examples in [0048-0049]),
the lithium transition metal oxide comprises lithium cobalt oxide (lithium cobalt oxide - LCO, [0048]), lithium nickel oxide (lithium nickel oxide, [0048]), lithium nickel cobalt oxide (lithium nickel cobalt oxide, [0048]), lithium nickel cobalt aluminum oxide (lithium nickel cobalt aluminum oxide - NCA, [0048]), lithium nickel cobalt manganese oxide (lithium nickel cobalt manganese oxide - NCM, [0048]), lithium manganate (lithium manganese oxide, [0048]), lithium iron phosphate (lithium phosphate iron oxide, [0048]), or a combination thereof (or a combination comprising at least one of the foregoing compounds may be used, [0048]),
the metal oxides comprise iron oxide, vanadium oxide, or a combination thereof (B’ and G in the exemplary oxide formulas may each be iron (Fe) or vanadium (V) per [0049]; vanadium oxide V2O5 also listed in [0049]),
the sulfide-based cathode active material [is optional per preceding limitations already being met to satisfy the “or” statements in the claim, but “Li2S” as claimed is the known general formula of “lithium sulfide” recited in Suzuki [0048]].
Regarding claim 11, Suzuki teaches the limitations of claim 1 above and wherein the cathode active material layer further comprises at least one selected from among a conductive material and a binder (cathode active material layer 12 may further include, for example, a conducting agent, a binder, an auxiliary ionic conducting agent; [0056]), and wherein the conductive material comprises a carbon-based conductive material (conducting agent may be, for example, graphite, carbon black, acetylene black, ketjen black, carbon fibers; [0056]).
Regarding claim 15, Suzuki teaches the limitations of claim 1 above and wherein the first anode active material layer comprises an anode active material and a binder (by the inclusion of the binder, the anode active material layer may be stabilized on the anode current corrector; [0076]), and wherein the anode active material has a particle form and an average particle diameter of about 4 μm or less (the metal or metalloid anode active material may have a particle diameter of, for example, about 4 micrometers (μm); [0072]).
Regarding claim 16, Suzuki teaches the limitations of claim 15 above and wherein the anode active material comprises at least one selected from among a carbon-based anode active material and a metal-based anode active material (anode active material layer may include amorphous carbon as the only anode active material able to form an alloy or compound with lithium, or may further include a metal or metalloid in addition to the amorphous carbon; [0071]), and
wherein, the carbon-based anode active material comprises amorphous carbon ([0059, 0071], … and
the metal-based anode active material comprises gold (Au), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), zinc (Zn), or a combination thereof (gold, platinum, palladium, silicon, silver, aluminum, bismuth, tin, … zinc, or a combination thereof; [0071]).
Regarding claim 17, Suzuki teaches the limitations of claim 15 above and the anode active material comprises a mixture of first particles and second particles (anode active material layer may include a mixture of the amorphous carbon and a metal or metalloid, [0071-0075]),
wherein the first particles comprise amorphous carbon, and the second particles comprise a metal or metalloid (anode active material including a metal or metalloid in addition to the amorphous carbon, [0071]), and
wherein a content of the second particles is in a range of about 8 wt% to about 60 wt% with respect to a total weight of the mixture (amorphous carbon – corresponding to claimed first particles – are 33 wt.% to 95 wt.% within the anode active material per [0073-0074], thus second particles corresponding to metal or metalloid would be the balance of 5 wt.% to 67 wt.% within the active mixture, see also [0074] – which substantially overlaps the instantly claimed range).
Claim Rejections - 35 USC § 103
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.
Claim(s) 2 is/are rejected under 35 U.S.C. 103 as being unpatentable over Suzuki et al. (US 20200313164 A1, as cited in the 7/17/24 IDS) as applied to claim 1 above, and further in view of Visco et al. (US 20160156065 A1) and Yushin et al. (US 20130224594 A1).
Regarding claim 2, Suzuki teaches the limitations of claim 1 above and teaches the first two-dimensional sulfide-based solid electrolyte is defined by a length and a thickness (“layer” necessarily has length and thickness; solid electrolyte layer 30, [0084] and Fig. 1), but fails to explicitly teach: an aspect ratio of the length to the thickness is about 3 or more, the first two-dimensional sulfide-based solid electrolyte has a length of about 1 μm to about 50 μm and a thickness of about 10 nm to about 30 μm, and the first two-dimensional sulfide-based solid electrolyte comprises a plate structure, a flake structure, a sheet structure, or a combination thereof.
Visco is analogous in the art of solid electrolytes and teaches a sulfide-based lithium ion-conductive solid electrolyte (abstract) and teaches the solid electrolyte in the form of a rectangular sheet having ([0098]) and has an aspect ratio (l/w) of greater than 10 or greater than 20 ([0032-0033]), and the sheet may be cut into pieces of any suitable size for use ([0033]), with a thickness in the range of 5 to 100 μm ([0011]) for use as a separator between a positive electrode and a negative lithium electroactive layer. Visco teaches the large aspect ratio is beneficial to impart flexibility ([0032]). This thickness overlaps the claimed range of 10 nm to about 30 μm.
Yushin is analogous in the art of batteries relying on lithium and sulfur and teaches composites formed with a substantially planar, flake morphology having a dense metal-sulfide core ([0064] and Fig. 9). Yushin Fig. 10 shows the flake composites having apparently large aspect ratios and sufficient flexibility for agglomeration. Yushin teaches that the planar morphology provides several key advantages in terms of power capabilities because planar particles offer higher electrical conductivity due to larger area contacts and the ability to propagate charge therethrough ([0065]). Yushin also teaches that the flakes are nanoflakes (i.e., nano-scale size) having the planar morphology ([0063]).
It would have been obvious, at the time of filing, for a person having ordinary skill in the art to modify the solid electrolyte of Suzuki with the thin thickness and high aspect ratio as taught by Visco to impart flexibility and usefulness as a separator between positive and negative electrode layers, and to cut to a desired length suitable for this use as taught toward by Visco, such as the nano-scale flake morphology as taught by Yushin also having large aspect ratio of length to thickness to impart desirably large electrical contact area, flexibility for agglomeration, and ability to propagate charge over desired length. Changes in size/proportion and shape are design choices within the ambit of a person having ordinary skill in the art (MPEP2144.04 IV A-B), and routine experimentation to optimize result effective-variables is obvious per MPEP 2144.05 II, such that optimizing the length and aspect ratio of the solid electrolyte within modified Suzuki to achieve desired effects in view of the Visco and Yushin teachings would have been obvious.
Thus, the instant claim 2 is rendered obvious.
Claim(s) 4-5 and 13-14 is/are rejected under 35 U.S.C. 103 as being unpatentable over Suzuki et al. (US 20200313164 A1, as cited in the 7/17/24 IDS) as applied to claim 1 above, and further in view of Yushin et al. (US 20130224594 A1).
Regarding claim 4, Suzuki teaches the limitations of claim 1 above but fails to teach wherein
the first two-dimensional sulfide-based solid electrolyte comprises a core and a shell on the core, and wherein,
the core comprises a carbon-based material, a polymer, a metal-containing inorganic material, a sulfide-based solid electrolyte, an oxide-based solid electrolyte, or a combination thereof,
the shell comprises a sulfide-based solid electrolyte, an oxide-based solid electrolyte, a coating material, or a combination thereof,
at least one of the core or shell comprises a sulfide-based solid electrolyte, and
the core comprises a two-dimensional nanostructure, and
wherein the two-dimensional nanostructure comprises graphene, graphene oxide, reduced graphene oxide, carbon nanobelts, carbon nanosheets, carbon nanoplates, carbon nanoflakes, SiO2, TiO2, Al2O3, AlN, SiC, BaTiO3, or a combination thereof.
Yushin is analogous in the art of batteries relying on lithium and sulfur (Suzuki [0048, 0085] and Yushin [0016, 0037]) and teaches battery cathode electrode composition is provided comprising core-shell composites (Abstract) that are formed with a substantially planar, flake morphology of the core and shell ([0064]) which include:
a first two-dimensional sulfide-based solid [layer, see below citation to Yushin [0076, 0080] in view of Suzuki [0085] reading on “electrolyte”] (structure 930 on 2D backbone 902, Fig. 9 and [0064]) comprises a core (sulfide core 104, Fig. 9 and [0064]) and a shell on the core (multi-functional shell 106, [0064] and Fig. 9), and wherein,
the core comprises a carbon-based material (backbone 902 e.g. multi-layer graphene, [0064] and Fig. 9; conductive additives 302 can be added to the core in the form of smaller carbon nanoflakes, graphene segments, etc. per [0064]), … a metal-containing inorganic material (dense metal-sulfide cores, [0064]), a sulfide-based solid electrolyte (lithium sulfide-based structures, Yushin [0076, 0080] – in view of Suzuki [0085] teaching toward lithium sulfide-based structures suitable as solid electrolyte material), … or a combination thereof,
the shell comprises … an oxide-based solid electrolyte (multi-functional shell 106 can be made of metal-ion-conductive ceramics e.g., oxide based, [0049]), a coating material (material from which the multi-functional shell 106 is formed may comprise a composite coating, [0049]) …
at least one of the core or shell comprises a sulfide-based solid electrolyte (dense metal-sulfide cores, [0064]; lithium sulfide-based structures, Yushin [0076, 0080] – in view of Suzuki [0085] teaching toward lithium sulfide-based structures suitable as solid electrolyte material), and
the core comprises a two-dimensional nanostructure (conductive additives 302 can be added to the core in the form of smaller carbon nanoflakes, graphene segments; [0064] and Fig. 9), and
wherein the two-dimensional nanostructure comprises graphene, … carbon nanoflakes (carbon nanoflakes, graphene segments; [0064] as cited above).
Yushin teaches that the planar morphology provides several key advantages in terms of power capabilities because planar particles offer higher electrical conductivity due to larger area contacts and the ability to propagate all the way from the current collector to the surface of the electrode ([0065]). Yushin teaches the dense metal-sulfide core (e.g., lithium sulfide per [0076]) accommodates metal insertion/extraction, allowing overall composite size to remain constant and the multi-functional shell 106 to remain intact ([0064]), whereby the shell is beneficial to protect the core in terms of stability ([0058]), protection of the core, and increases metal ion storage capacity of the electrode ([0038]). Yushin teaches that there is a need in the art for better addressing the low electrical and ionic conductivity as well as physical instability of sulfur-based cathodes in metal-ion batteries which is addressed by their inventive cathode material ([0036]).
As welcomed by Suzuki [0048] and [0055], the cathode active material can include solid electrolyte such as lithium sulfide-based material. Therefore, it would have been obvious, at the time of filing, for a person having ordinary skill in the art to modify the cathode layer of Suzuki to include the lithium-sulfide based dense core material as well as the multifunctional shell coating on the core to form the planar morphology cathode active structure as taught by Yushin with the motivation of achieving the above-cited benefits including better power capabilities and stability of the cathode.
Thus, the instant claim 4 is rendered obvious.
Regarding claim 5, Suzuki, as modified by Yushin, teaches the limitations of claim 4 above But fails to explicitly teach a ratio of a first thickness of the core to a second thickness of the shell is in a range of about 1:0.01 to about 1:1,000, and a ratio of a first length of the core to a second length of the shell is in a range of about 1:1 to about 1:100.
However, in Yushin Fig. 9 (as applied to modified Suzuki above) appears to teach a thickness of shell 106 being substantially thinner than a thickness of core 104, such that the ratio of the core thickness to the shell thickness (T1:T2) is approximated at 1:0.17 (as shown and calculated in annotated Fig. 9 below) which falls within and obviates the claimed range (MPEP 2144.05 I). Suzuki [0065] also teaches with the planar morphology, the core thickness can be reduced, which helps to mitigate sulfur's low electrical and ionic conductivities. Thus, the thickness of the core is also a result-effective variable which would be obvious to routinely optimize to achieve desired trade-off with conductivity (MPEP 2144.05 II).
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Further, Yushin Fig. 9 (as applied to modified Suzuki above) appears to also teach a length of the shell 106 to be marginally longer than a length of the core 104, such that the ratio of the core length to the shell length (L1:L2) is approximated at 1:1.04 (as shown and calculated in annotated Fig. 9 below) which falls within and obviates the claimed range (MPEP 2144.05 I). Suzuki [0065] also teaches with the planar morphology, the surface area (which is necessarily a function of length) is larger which imparts higher electrical conductivity. Thus, the length of the planar core-shell composite is a result-effective variable which would also be obvious to routinely optimize to achieve desired conductive contact area (MPEP 2144.05 II).
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Thereby, claim 5 is rendered obvious.
Regarding claim 13, Suzuki teaches the limitations of claim 1 above but fails to explicitly teach wherein the solid electrolyte layer comprises the first two-dimensional sulfide-based solid electrolyte arranged in one direction.
However, Suzuki shows in Fig. 1 the overall solid electrolyte layer 30 being substantially planar. Suzuki teaches in [0120] that the solid electrolyte layer 30 may be formed by pressing only solid electrolyte material particles, which implies a substantially flat, unidirectional, two-dimensional resultant arrangement of particles.
Further, Yushin is analogous in the art of batteries relying on lithium and sulfur (Suzuki [0048, 0085] and Yushin [0016, 0037]) and teaches battery cathode electrode composition is provided comprising core-shell composites (Abstract) that are formed with a substantially planar, flake morphology of the core and shell ([0064]), and teaches that the planar morphology provides several key advantages in terms of power capabilities because planar particles offer higher electrical conductivity due to larger area contacts and the ability to propagate all the way from the current collector to the surface of the electrode ([0065]). Yushin further teaches a three-dimensional agglomerate structure formed from substantially planar, flake morphology composites can be shaped as a rod (Yushin [0066]), which reads on a unidirectional orientation of said flakes.
It would have been obvious, at the time of filing, for a person having ordinary skill in the art to modify the solid electrolyte particles of the solid electrolyte layer within Suzuki to have the planar, flake morphology taught by Yushin in order to impart large contact area and high electrical conductivity, as well as to arrange such two-dimensional flake particles in one direction to form an agglomerated rod-shape, since such is taught by Yushin to be an acceptable and functional embodiment. Changes in shape and rearrangement of parts are design choices within the ambit of a person having ordinary skill in the art per MPEP 2144.04 IV B and VI C.
Thus, the instant claim 13 is rendered obvious.
Regarding claim 14, modified Suzuki teaches the limitations of claim 1 above and teaches the first two-dimensional sulfide-based solid electrolyte is aligned in a direction substantially normal to a thickness direction of the solid electrolyte layer and is stacked in the thickness direction of the solid electrolyte layer (due to isostatic pressing as described in Suzuki [0120], in view of planar 30 in Suzuki Fig. 1), and
a content of the first two-dimensional sulfide-based solid electrolyte is about 50 wt% or more of a total weight of the solid electrolyte layer (to the Li6PS5Cl solid electrolyte, 1 weight % of a rubber-based binder with respect to the mass of the solid electrolyte was added, then solvent was added but subsequently vacuum-dried, to thereby manufacture a solid electrolyte layer; Suzuki [0141] – thus, accounting for the remaining 1 weight % rubber binder after solvent was removed from slurry via vacuum-drying, 99 weight % of the resultant electrolyte layer would expectedly be the Li6PS5Cl solid electrolyte, meeting the claimed condition of more than 50 wt%).
Claim(s) 6 is/are rejected under 35 U.S.C. 103 as being unpatentable over Suzuki et al. (US 20200313164 A1, as cited in the 7/17/24 IDS) as applied to claim 1 above, and further in view of Sakaida et al. (US 20200328465 A1).
Regarding claim 6, Suzuki teaches the limitations of claim 1 above and teaches
wherein the cathode active material layer comprises a first region adjacent to the cathode current collector (12 abutting 11, Suzuki Fig. 1) and a second region adjacent to the solid electrolyte layer (12 abutting 30, Suzuki Fig. 1), but fails to teach wherein:
the first two-dimensional sulfide-based solid electrolyte is in the first region and is absent from the second region;
the first two-dimensional sulfide-based solid electrolyte is in the second region and is absent from the first region; or
the first two-dimensional sulfide-based solid electrolyte is in each of the first region and the second region.
However, Suzuki does welcome in [0048] a lithium sulfide combined within the cathode active material, where sulfide-based materials with lithium and phosphorus are also known as solid electrolytes per Suzuki [0085-0086]. Suzuki also teaches in [0055] that the solid electrolyte included in the cathode active material layer 12 may be the same as, or different from, a solid electrolyte included in the solid electrolyte layer 30, and teaches in [0137] during formation of cathode layer, the prepared cathode active material, solid electrolyte, conducting agent, and binder were mixed together in a weight ratio of about 88:12:2:1 to obtain a mixture. This implies that the solid electrolyte is in each of the first region and the second region, meeting the third option of instant claim limitation.
Furthermore, Sakaida is analogous in the art of batteries with solid electrolyte (abstract) and teaches a cathode active material layer (cathode 201 with active material particles 211, Sakaida [0156] and Fig. 2) that comprises a first region adjacent to the cathode current collector (where 201 would abut the stainless steel current collector disposed on the upper part of the stacking structure, Sakaida Fig. 1 in view of [0193]) and a second region adjacent to the solid electrolyte layer (where 201 abuts first solid electrolyte layer 101, Sakaida [0030, 0149] and Fig. 2), and further teaches wherein:
the first two-dimensional (a shape of each of the first solid electrolyte particles 111 in the first embodiment is not particularly limited, and may be, for example, an acicular shape per Sakaida [0158] – acicular interpreted as two-dimensional because would exhibit the two dimensions of length and diameter) sulfide-based (sulfide solid electrolyte example, Sakaida [0114]) solid electrolyte (first solid electrolyte particles 111, Sakaida [0156]) is in each of the first region and the second region (particles 111 dispersed throughout cathode 201 alongside active particles 211, Sakaida Fig. 2 and [0156, 0160]).
Sakaida teaches in [0137] that when cathode 201 includes the above-mentioned sulfide solid electrolyte, ion conductivity is enhanced.
It would have been obvious, at the time of filing, for a person having ordinary skill in the art to modify the cathode of Suzuki to include sulfide solid electrolyte particles having good dispersion throughout the cathode layer alongside the cathode active material particles as taught by Sakaida with the motivation of achieving enhanced ion conductivity within the cathode.
Thus, the instant claim 6 is rendered obvious.
Claim(s) 7 and 9-10 is/are rejected under 35 U.S.C. 103 as being unpatentable over Suzuki et al. (US 20200313164 A1, as cited in the 7/17/24 IDS) as applied to claims 1 and 8 above, and further in view of Hoshina et al. (US 20140199598 A1).
Regarding claim 7, Suzuki teaches the limitations of claim 1 above and teaches a content of the first two-dimensional sulfide-based solid electrolyte (solid electrolyte included in the cathode active material layer 12 may be the same as a solid electrolyte included in the solid electrolyte layer 30, [0055]) is in a range of about 1 wt% to about 50 wt% of a total weight of the cathode active material layer (12 wt%: prepared cathode active material, solid electrolyte, conducting agent, and binder were mixed together in a weight ratio of about 88:12:2:1 to obtain a mixture, [0137]), but fails to teach
the cathode active material layer further comprises an irregular-shaped sulfide-based solid electrolyte that is distinguished from the first two-dimensional sulfide-based solid electrolyte, and
a weight ratio of the first two-dimensional sulfide-based solid electrolyte to the irregular-shaped sulfide-based solid electrolyte is in a range of about 1:99 to about 99:1.
Suzuki [0048] does welcome a lithium sulfide combined within the cathode active material, where sulfide-based materials with lithium and phosphorus are also known as solid electrolytes per Suzuki [0085-0086]. Suzuki [0055] welcomes that solid electrolyte included in the cathode active material layer 12 may be the same as, or different from, a solid electrolyte included in the solid electrolyte layer 30, thus welcoming various solid electrolytes within the cathode.
Hoshina is analogous in the art of batteries having solid electrolytes and teaches a solid electrolyte secondary battery according to embodiment comprises a positive electrode, a negative electrode, and a solid electrolyte layer (Hoshina [0014]) wherein the positive electrode layer contains active particles alongside first and second solid electrolyte particles, such that the electrolyte particles serve to fill gaps between active particles ([0017]). Hoshina [0027] teaches suitable examples of solid sulfide electrolyte which are lithium-ion conductive. Hoshina [0028] teaches that the shape of the first and second solid electrolyte particles is not limited, that the first and second solid electrolyte particles may contain a plurality of shapes of solid electrolyte particles, and that shape examples include irregular-shaped particles and plate-shaped particles. Hoshina teaches that the positive electrode layer is preferably adjusted to 50% by mass or more and 95% by mass or less of the active material particles, 10% by mass or more and 30% by mass or less of the first and second solid electrolyte particles, whereby first and second solid electrolyte particles can improve lithium ion conductivity in the positive electrode layer at an amount of 10% by mass or more and can achieve high energy density and high lithium ion conductivity at an amount of 30% by mass or less (Hoshina [0035-0036]). Hoshina also teaches in [0031] that volumetrically, the percentage of first solid electrolytes particles can be equivalent to or marginally greater than the percentage of second solid electrolyte particles.
It would have been obvious, at the time of filing, for a person having ordinary skill in the art to modify the cathode layer of Suzuki to include first and second solid electrolyte particles alongside the active materials as taught by Hoshina with the motivation of filling gaps between active particles and improving lithium ion conductivity within the cathode layer. From the above-cited teachings of Hoshina, it would have been further obvious to select a plurality of particle shaped such as irregular-shaped particles and plate-shaped particles for the first and second solid electrolytes since such options are taught suitable by Hoshina (see also MPEP 2144.04 IV B and 2144.07). It would have been further obvious to include said first and second electrolyte particles in equal amounts to one another or with marginally more of the first versus second solid electrolyte (falling within instantly claimed ratio range of 1:99 to about 99:1; see also MPEP 2144.05 I), and obvious to include both first and second solid electrolyte particles in a total mass of 10-30% compared to 50-95% mass of cathode active materials (which overlaps instantly claimed range of 1 wt% to about 50 wt%; see also MPEP 2144.05 I) in order to achieve high energy density and high lithium ion conductivity as taught by Hoshina.
Thus, the instant claim 7 is rendered obvious.
Regarding claim 9, Suzuki teaches the limitations of claim 8 above but fails to teach: wherein the Li2S-containing composite comprises a composite of Li2S and carbon, a composite of Li2S, carbon, and a solid electrolyte, a composite of Li2S and a solid electrolyte, a composite of Li2S and a lithium salt, a composite of Li2S, a lithium salt, and carbon, a composite of Li2S and a metal carbide, a composite of Li2S, carbon, and a metal carbide, a composite of Li2S and a metal nitride, a composite of Li2S, a carbon, and a metal nitride, or a combination thereof.
Hoshina is analogous in the art of batteries having solid electrolytes and teaches a solid electrolyte secondary battery according to embodiment comprises a positive electrode, a negative electrode, and a solid electrolyte layer (Hoshina [0014]) wherein the positive electrode layer contains active particles alongside first and second solid electrolyte particles, such that the electrolyte particles serve to fill gaps between active particles ([0017]) and promote lithium ion conductivity within the positive electrode ([0036]). Hoshina teaches suitable examples of solid sulfide electrolyte which are lithium-ion conductive, specifically teaching toward a composite of Li2S and a solid electrolyte with the example of THIO-LISICON compounds of the Li2S-GeS2-P2S5 system ([0027]).
Suzuki [0048] does welcome a lithium sulfide combined within the cathode active material, where sulfide-based materials with lithium and phosphorus (P) are also known as solid electrolytes per Suzuki [0085-0086], and further that cathode active material can include germanium (Ge) within a coating layer. Suzuki [0055] welcomes that solid electrolyte included in the cathode active material layer 12 may be the same as a solid electrolyte included in the solid electrolyte layer 30. Therefore, it would have been obvious, at the time of filing, for a person having ordinary skill in the art to modify the cathode active layer of Suzuki to further include a composite of Li2S and a solid electrolyte (specifically THIO-LISICON compounds of the Li2S-GeS2-P2S5 system) as taught by Hoshina with the motivation of filling gaps between the active particles and improving lithium ion conductivity within the cathode.
Thus, the instant claim 9 is rendered obvious.
Regarding claim 10, Suzuki teaches the limitations of claim 8 above but fails to teach wherein the Li2S-containing composite further comprises a second two-dimensional sulfide-based solid electrolyte, and wherein a size of the second two-dimensional sulfide-based solid electrolyte is smaller than a size of the first two-dimensional sulfide-based solid electrolyte.
Hoshina is analogous in the art of batteries having solid electrolytes and teaches a solid electrolyte secondary battery according to embodiment comprises a positive electrode, a negative electrode, and a solid electrolyte layer (Hoshina [0014]) wherein the positive electrode layer contains active particles alongside first and second solid electrolyte particles, such that the electrolyte particles serve to fill gaps between active particles ([0017]) and promote lithium ion conductivity within the positive electrode ([0036]). Hoshina teaches suitable examples of solid sulfide electrolyte which are lithium-ion conductive, specifically teaching compounds of the Li2S-GeS2-P2S5 system ([0027]) which reads on “Li2S-containing composite”. Hoshina teaches the shape of the first and second solid electrolyte particles is not limited, giving example of plate-shaped particles which reads on “two-dimensional”. Further, Hoshina teaches that a size of the one two-dimensional sulfide-based solid electrolyte is smaller than a size of the another two-dimensional sulfide-based solid electrolyte (the particle size ratio of the second solid electrolyte particle size D2 to the first solid electrolyte particle size D1 (D2/D1) satisfies the relation of 3<D2/D1<50, more preferably 8≤D2/D1≤20; Hoshina [0010, 0029]). Hoshina [0012] teaches that by defining the particle size ratio of the second solid electrolyte particle size D2 of the second solid electrolyte particles to the first solid electrolyte particle size D1 of the first solid electrolyte particles (D2/D1) to meet the above relationship (wherein D2>D1 as evidenced by D2/D1>1), the function of the first and second solid electrolyte particles can be effectively exhibited; specifically: ion (such as lithium ion) conductivity of the electrode itself can be improved, and when the electrode is applied to a solid electrolyte secondary battery comprising the solid electrolyte layer, the lithium ion conductivity can be increased between the electrode and the solid electrolyte layer ([0012]). D1 and D2 being “first” and “second” in Hoshina versus the claims is irrelevant since either of the two solid electrolytes of Hoshina can be mapped to first versus second in the claims.
Therefore, it would have been obvious, at the time of filing, for a person having ordinary skill in the art to modify the cathode active layer of Suzuki to specifically include a Li2S-composite including two different solid sulfide electrolytes with different particle sizes such that one was larger than the other in order to beneficially fill the gaps between active material particles to increase ion conductivity within the cathode and between the cathode and solid electrolyte layer, as taught by Hoshina.
Thereby, claim 10 is rendered obvious.
Claim(s) 12 and 19 is/are rejected under 35 U.S.C. 103 as being unpatentable over Suzuki et al. (US 20200313164 A1, as cited in the 7/17/24 IDS) as applied to claim 1 above, and further in view of Lee et al. (US 20210143412 A1, with publication fate of 05/13/2021).
Regarding claim 12, Suzuki teaches the limitations of claim 1 above but fails to teach further comprising an inactive member on at least one side surface of the cathode layer, wherein the inactive member is along the side surface of the cathode layer to surround the cathode layer and comprises a position determination portion configured to determine a position of the inactive member on the solid electrolyte layer.
Lee is analogous in the art of all-solid secondary batteries (title) and teaches an inactive member 40 on at least one side surface of the cathode layer, wherein the inactive member is along the side surface of the cathode layer 12 to surround the cathode layer ([0027], fig. 1) and comprises a position determination portion configured to determine a position of the inactive member on the solid electrolyte layer (the inactive member 40 may be disposed so that it surrounds one or more, for example all side surfaces of the cathode active material layer 12 and may thus correct an area error (e.g., mismatch) between the cathode active material layer 12 and the solid electrolyte layer 30; [0031]). Here, correction of contact area mismatch reads on “position determination”. Lee [0031] teaches such functionality of inactive member 40 beneficially corrects a difference between the area S1 of the cathode active material layer 12 and the area S2 of the solid electrolyte layer 30 (as shown in fig. 1), so that cracks generated in the solid electrolyte layer 30 by a pressure difference during a pressing process may be effectively suppressed.
It would have been obvious, at the time of filing, for a person having ordinary skill in the art to modify the all-solid state battery of Suzuki to further include the inactive member including the position determination portion as taught by Lee with the motivation of correcting contact area mismatch between the cathode and electrolyte layers and effectively suppressing cracks in the solid electrolyte layer.
Thus, the instant claim 12 is rendered obvious.
Regarding claim 19, Suzuki teaches the limitations of claim 1 above but fails to explicitly teach further comprising a second anode active material layer between the solid electrolyte layer and the anode current collector, wherein, the second anode active material layer is between the first anode active material layer and the anode current collector and/or between the first anode active material layer and the solid electrolyte layer, and the second anode active material layer is a metal layer comprising lithium metal or a lithium alloy.
However, Suzuki [0082] and Figs. 2-4 teach embodiments in which the all-solid lithium secondary battery may further include the metal layer 23 disposed, for example, between the anode current collector 21 and the anode active material layer 22; the all-solid lithium secondary battery 1 may further include the metal layer 23 disposed, for example, within the anode active material layer 22, through charging; the metal layer 23 may consist of, or consist essentially of, a lithium metal or a lithium alloy, such that the metal layer 23 may function as, for example, a lithium reservoir. Yet, Suzuki does not explicitly describe such additional lithium metal layer serving as a second anode active material layer.
Lee is analogous in the art of all-solid secondary batteries (title) and teaches
a second anode active material layer between the solid electrolyte layer and the anode current collector (a second anode active material layer between the anode current collector(s) 21 or 21a and 21b and the first anode active material layer(s) 22 or 22a and 22b; [0074] – thus also necessarily between solid electrolyte layer(s) 30[a,b] and anode collector(s) 21[a,b] per Lee Figs. 1-2), wherein,
the second anode active material layer is between the first anode active material layer and the anode current collector (a second anode active material layer between the anode current collector(s) 21 or 21a and 21b and the first anode active material layer(s) 22 or 22a and 22b; [0074]), …, and
the second anode active material layer is a metal layer comprising lithium metal or a lithium alloy (second anode active material layer is a metal layer including lithium or a lithium alloy, [0074]).
Lee teaches that such second anode active material layer serves as a lithium reservoir ([0074]) such that cycle characteristics of the all-solid secondary battery including the second anode active material layer may be further improved ([0076], and because the first anode active material layer(s) 22 cover the second anode active material layer, the first anode active material layer(s) 22 may serve as a protection layer for the second anode active material layer, and may suppress or reduce deposition growth of lithium dendrites at the same time, thus short-circuit and capacity deterioration of the all-solid secondary battery may be suppressed ([0076]).
It would have been obvious, at the time of filing, for a person having ordinary skill in the art to modify the battery of Suzuki to further include the second anode active material made of lithium and located between the corresponding layers as instantly claimed and taught toward by Lee (and similar to the embodiments welcomed by Suzuki Figs. 2-4 including lithium metal layer 23) to act as a lithium reservoir (as taught by both Suzuki and Lee, cited above) with motivation of achieving improved cycle characteristics, the first anode active layer protects the second, and lithium dendrite growth is suppressed to prevent short-circuiting and degradation as taught by Lee.
Thus, the instant claim 19 is rendered obvious.
Claim(s) 18 is/are rejected under 35 U.S.C. 103 as being unpatentable over Suzuki et al. (US 20200313164 A1, as cited in the 7/17/24 IDS) as applied to claim 15 above, and further in view of Guo et al. (US 20220259046 A1).
Regarding claim 18, Suzuki teaches the limitations of claim 15 above but fails to teach:
the anode active material comprises a carbon-based support and a metal-based anode active material supported on the carbon-based support, and
wherein, the metal-based anode active material comprises a metal, a metal oxide, a composite of a metal and a metal oxide, or a combination thereof,
the metal-based anode active material has a particle form and a particle diameter of about 1 nm to about 200 nm, and
the carbon-based support has a particle form and a particle diameter of about 10 nm to about 2 μm.
Suzuki does welcome in [0071-0072] the combination of carbon and metal-based material within composite anode active material, and specifically teaches in [0072] the metal included therein having a particle diameter of preferably 100 nm or less (which falls within the claimed range of 1-200 nm), but fails to teach the structure of said carbon as a support for said metal material.
Guo is analogous in the art of negative active material and teaches a lithium-carbon nanoparticle-porous skeleton composite material can be used as negative electrode material of a battery, to improve the cycle stability of the battery, and has a simple preparation process for mass production ([0013]). Guo teaches:
the anode active material comprises a carbon-based support (carbon-based porous microsphere material, [0026]; comprising e.g. the carbon nanotube or carbon nanofiber microsphere material is formed by entangling and agglomerating carbon nanotubes or carbon nanofibers with each other, [0027-0028] and Figs. 1-2) and a metal-based anode active material supported on the carbon-based support (there are nanoscale pores between the entangled and agglomerated carbon nanotubes or carbon nanofibers used to accommodate metallic lithium particles, [0028] and Figs. 1-2), and
wherein, the metal-based anode active material comprises a metal (metallic lithium particles, [0028]) …,
the metal-based anode active material has a particle form and a particle diameter of about 1 nm to about 200 nm (the pores contained in the microspheres may have a pore size distribution of 1 to 200 nm per [0029], and the lithium metal particles are held within nanoscale pores per [0028], such that it is understood that said lithium particles would have sizes that also fall within the 1 to 200 nm cited range in order to fit within said pores), and
the carbon-based support has a particle form and a particle diameter of about 10 nm to about 2 μm (the carbon nanotube or carbon nanofiber microsphere material is spherical or spheroidal particles with an average diameter of preferably 1 μm to 25 μm, [0029] – which overlaps claimed range from 1-2 μm).
Since Suzuki [0071] already welcomes composite carbon and metal anode active material, it would have been obvious, at the time of filing, for a person having ordinary skill in the art to modify this anode active material with the negative active material (i.e., entangled porous carbon support holding lithium metal particles therein) as taught by Guo (and meeting the claimed sizes, as cited above) with the motivation of achieving improved cycle stability of the battery and simpler preparation process for mass production per Guo [0013]. Further, simple substitution of one known element for another (e.g., anode material), and the selection of known suitable material are obvious and within the ambit of a person having ordinary skill in the art (MPEP 2143 I B and 2144.07, respectively).
Thus, the instant claim 18 is rendered obvious.
Claim(s) 20 is/are rejected under 35 U.S.C. 103 as being unpatentable over Suzuki et al. (US 20200313164 A1, as cited in the 7/17/24 IDS) as applied to claim 1 above, and further in view of Kwon et al. (US 20140370351 A1).
Regarding claim 20, Suzuki teaches the limitations of claim 1 above and teaches at least one of the cathode current collector or the anode current collector comprises … a metal layer, … the metal layer comprises indium (In), copper (Cu), magnesium (Mg), titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), germanium (Ge), lithium (Li), or an alloy thereof (cathode current collector 11 may include a metal such as indium, copper, magnesium, … titanium, iron, cobalt, nickel, zinc, aluminum, germanium, lithium, an alloy thereof; [0046] / material of the anode current collector 21 may be, for example, copper, … titanium, iron, cobalt, nickel; [0058]); but Suzuki fails to teach:
at least one of the cathode current collector or the anode current collector further comprises a base film and
the metal layer is on at least one surface of the base film, and wherein,
the base film comprises a polymer, the polymer comprising polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polybutylene terephthalate (PBT), polyimide (PI), or a combination thereof.
Kwon is analogous in the art of electrodes for secondary batteries (a sheet-form electrode for a secondary battery, comprising a current collector and an electrode active material layer formed on one surface of the current collector; Abstract). Kwon teaches their sheet-form electrode has supporting layers on at least one surfaces thereof to exhibit surprisingly improved flexibility (Abstract) and teaches specifically the sheet-form electrode comprising a second supporting layer on another surface of the current collector and that the second supporting layer may be a polymer film which may be made of polyolefin or polyimide ([0028-0029]). Kwon teaches the second supporting layer 50 being on an opposite surface of current collector 10 versus the active material layer 20 ([0078-0079] and figs. 2-3), and that beneficially the second supporting layer 50 can inhibit a short circuit of the current collector 10, thereby further improving the flexibility of the electrode ([0083]). Kwon teaches an example wherein a polyethylene film was compressed on one surface of a sheet-form current collector being an aluminum foil, to form a second supporting layer ([0153]), the laminate of which was then used as a cathode current collector ([0154-0155]). The aluminum foil layer of Kwon meets the instantly claimed metal layer, and the polyethylene film of Kwon meets the instantly claimed base film, and the compressed lamination of the aluminum foil and polyethylene film meets the claimed structure of the metal layer on at least one surface of the base film.
It would have been obvious, at the time of filing, for a person having ordinary skill in the art to modify at least the cathode current collector of Suzuki (which can be aluminum as cited above) to further include a base film made of polyethylene as taught by Kwon to serve as a supporting layer with the motivation of improving flexibility of the current collector and preventing short circuit of the electrode as taught by Kwon.
Thus, the instant claim 20 is rendered obvious.
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure. Woo et al. (US 20160190565 A1) teaches a composite cathode material which can have Li2S core and coated with composite including solid electrolyte and a mesoporous conductor material, where this composite cathode material is within a cathode layer adjacent a solid electrolyte layer (Fig. 3) in an all-solid lithium battery (abstract).
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/JESSIE WALLS-MURRAY/Primary Examiner, Art Unit 1728
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