DETAILED ACTION
Notice of Pre-AIA or AIA Status
1. The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Election/Restrictions
2. Applicant’s election without traverse of:
Species A-1, the ion-conductive polymer is polyanionic with mobile cations
Species B-1, the electrolyte medium is a solid electrolyte medium
Species C-2, the nanoparticle core of the hairy nanoparticle is an inorganic composition
in the reply filed on 8/7/2026 is acknowledged, with claims 1-4, 7-14, 17-22, and 24-27 reading thereon. Claims 5-6, 15-16, and 23 are withdrawn from further consideration pursuant to 37 CFR 1.142(b) as being drawn to a nonelected species, there being no allowable generic or linking claim.
Priority
3. The later-filed application must be an application for a patent for an invention which is also disclosed in the prior application (the parent or original nonprovisional application or provisional application). The disclosure of the invention in the parent application and in the later-filed application must be sufficient to comply with the requirements of 35 U.S.C. 112(a) or the first paragraph of pre-AIA 35 U.S.C. 112, except for the best mode requirement. See Transco Products, Inc. v. Performance Contracting, Inc., 38 F.3d 551, 32 USPQ2d 1077 (Fed. Cir. 1994).
The disclosure of the prior-filed application, Application No. 63/414,624 fails to provide adequate support or enablement in the manner provided by 35 U.S.C. 112(a) or pre-AIA 35 U.S.C. 112, first paragraph for all claims of this application. An analysis follows.
4. MPEP 2163.03, Section V with respect to written description support notes that a claim may lack written description support if a broad genus claim is presented but the disclosure only describes a narrow species with no evidence that the genus is contemplated. See Ariad Pharms., Inc. v. Eli Lilly & Co., 598 F.3d 1336, 1349-50 (Fed. Cir. 2010) (en banc). The instant independent claims each recite in part:
“a hairy nanoparticle composition comprising:
a nanoparticle core; and
an ion-conductive polymer chemically attached to the nanoparticle core, wherein the ion-conductive polymer is either polyanionic with mobile cations or polycationic with mobile anions.”
The language emphasized above does not exist in the provisional. The only narrow species described or taught is shown below (Scheme 2, page 9):
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While this narrow species is a singular example of an ion-conductive polymer that is polyanionic with mobile cations, there is no description or evidence that the entire broad genus claim limitation of “wherein the ion-conductive polymer is polyanionic with mobile cations” was contemplated at the filing date of the provisional application (claims 1-2, 10, 17, 21, and 24). There is also no disclosure whatsoever of a genus or species of an ion-conductive polymer that is polycationic with mobile anions (non-elected species, also within the claim). The issue extends to the breadth of: “an ion-conductive polymer” as presented in each independent claim. Instead, the provisional only teaches “a Li-ion conductive polymer” (description, paragraph 1 on page 2; page 4) or “single ion conducting polymer” or “single Li-ion conducting polymer” (page 5) versus any possible ion-conductive polymer, and the only species taught thereof is the one above, and is another example of where a broad genus claim (“an ion-conductive polymer”) is presented but the disclosure only describes a narrower species/sub-genus thereof (“single Li-ion conducting polymer”) with no evidence that the genus is contemplated such that written description/support is lacking (MPEP 2163.03; Ariad Pharms., Inc. v. Eli Lilly & Co., 598 F.3d 1336, 1349-50 (Fed. Cir. 2010) (en banc)).
Additionally, the provisional application does not support the breadth of: “a nanoparticle core” as presented in each independent claim. Instead, the provisional only teaches a ceramic nanosized core (or “a ceramic nanoparticle core”), versus any possible core material (see claim 1 of provisional; see also first paragraph of Description section), and is another example of where a broad genus claim is presented but the disclosure only describes a narrow species with no evidence that the genus is contemplated such that written description/support is lacking (MPEP 2163.03; Ariad Pharms., Inc. v. Eli Lilly & Co., 598 F.3d 1336, 1349-50 (Fed. Cir. 2010) (en banc)).
Accordingly, for at least these two reasons, the present effective filing date of all claims is considered to be that of the non-provisional application: 10/10/2023.
The above species and overall disclosure of the provisional also does not support at least:
that the mobile cations can be anything but lithium (claim 3);
the polyanion polymer contains moieties claimed within claims 4, 18, 25 with the exception of carboxylate (illustrated in the chemical structure in Scheme 2); note that the above circled species from Scheme 2 is lithium trifluoromethanesulfonyl imide (page 4 of provisional) versus the genus of “moieties from bis(fluorosulfonyl)imide”
the nanoparticle core has an inorganic composition (claims 7, 19, 26) (it is noted that the genus of ceramic is taught which is more specific than “inorganic” which allows for metallic options); the inorganic composition is an oxide composition (claims 8, 20, 27); and the oxide is one of those listed (claim 9)
wherein the electrolyte medium is a gel electrolyte medium
wherein the electrolyte medium is a liquid electrolyte medium
wherein the solid or gel electrolyte medium is a microporous polymer (organic or inorganic) with or without ionic groups (claim 12)
wherein the solid or gel electrolyte medium is selected from the options listed (claim 13) with the exception that PEO is supported in the context of a solid polymer electrolyte
the genus of a “metal-ion battery” versus a Li/Li symmetric testing cell utilizing lithium ions (the only battery taught is at page 7 in a Li/Li symmetric cell)
the genus of “an electrolyte” versus the narrow species taught of a solid polymer electrolyte (page 2, page 3, full disclosure)
These comments are made for clarity of the record.
Claim Objections
5. Claims 2-9 and 12 is objected to because of the following informalities: invocation of full and proper antecedent basis.
Claims 2-9: the preambles should each be amended to “The hairy nanoparticle composition of…”
Claim 12: “the solid or gel electrolyte” should be amended to “the solid or gel electrolyte medium”
Appropriate correction is required.
Claim Rejections - 35 USC § 112
6. The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
7. Claim 10, and thus dependent claims 11-14, 17-20; and claim 14 are rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
Claim 10 recites “the hairy nanoparticle composition” in line 2. There is insufficient antecedent basis for this limitation.
Claim 14 recites, “The electrolyte composition of claim 9” and “the solid or gel electrolyte medium” – there is insufficient antecedent basis for each of these limitations. It appears claim 14 should be corrected to depend from claim 11, and will be examined accordingly for compact prosecution purposes. This issue was highlighted in the Restriction Requirement and no correction was filed.
Appropriate correction is required.
Prior Art Reference Analysis
8. One of the references applied below is Bocharova et al., “Single Ion Conducting Hairy Nanoparticle Additive to Improve Cycling Stability of Solid Polymer Electrolytes,” ACS Appl. Energy Mater. 2023, 6, 8042-8052, published July 17, 2023 (copy provided), and is presently available as prior under 35 U.S.C. 102(a)(1) as a disclosure with a prior public availability date (7/17/2023) relative to the effective filing date of the present application (10/10/20231), the article sharing four inventors (highlighted below) with the instant application:
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18/378,373 inventors:
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The journal reference lists an additional eight co-authors, and as such, cannot be assumed an inventor-originated disclosure per MPEP 2153.01(a) (see added emphasis):
A disclosure made within the grace period is not prior art under AIA 35 U.S.C. 102(a)(1) if it is apparent from the disclosure itself that it is an inventor-originated disclosure. Specifically, Office personnel may not apply a disclosure as prior art under AIA 35 U.S.C. 102(a)(1) if the disclosure: (1) was made one year or less before the effective filing date of the claimed invention; (2) names the inventor or a joint inventor as an author or an inventor; and (3) does not name additional persons as authors on a printed publication or joint inventors on a patent. This means that in circumstances where an application names additional persons as joint inventors relative to the persons named as authors in the publication (e.g., the application names as joint inventors A, B, and C, and the publication names as authors A and B), and the publication is one year or less before the effective filing date, it is apparent that the disclosure is a grace period inventor disclosure, and the publication is not prior art under AIA 35 U.S.C. 102(a)(1). If, however, the application names fewer joint inventors than a publication (e.g., the application names as joint inventors A and B, and the publication names as authors A, B and C), it would not be readily apparent from the publication that it is an inventor-originated disclosure and the publication would be treated as prior art under AIA 35 U.S.C. 102(a)(1) unless there is evidence of record that an exception under AIA 35 U.S.C. 102(b)(1) applies.
9. It is noted that Applicant has at least the following options to avoid this specific reference as applicable to the claims:
1) MPEP 2155.01:
AIA 35 U.S.C. 102(b)(1)(A) provides that a grace period disclosure shall not be prior art to a claimed invention under AIA 35 U.S.C. 102(a)(1) if the disclosure was made by the inventor or a joint inventor. An applicant may show that a disclosure was made by the inventor or a joint inventor by way of an affidavit or declaration under 37 CFR 1.130(a) (an affidavit or declaration of attribution). See In re Katz, 687 F.2d 450, 455, 215 USPQ 14, 18 (CCPA 1982) and MPEP § 717.01(a)(1) . Where the authorship of the prior art disclosure includes the inventor or a joint inventor named in the application, an unequivocal statement from the inventor or a joint inventor that the inventor or joint inventor (or some combination of named inventors) invented the subject matter of the disclosure, accompanied by a reasonable explanation of the presence of additional authors, may be acceptable in the absence of evidence to the contrary. See In re DeBaun, 687 F.2d 459, 463, 214 USPQ 933, 936 (CCPA 1982).
When any claim of an application or a patent under reexamination is rejected, the applicant or patent owner may submit an appropriate affidavit or declaration to except a disclosure as prior art by establishing that the disclosure was made by the inventor or a joint inventor, or the subject matter disclosed was obtained directly or indirectly from the inventor or a joint inventor. However, an affidavit or declaration under 37 CFR 1.130(a) that is only a naked assertion of inventorship and that fails to provide any context, explanation or evidence to support that assertion is insufficient. See EmeraChem Holdings, LLC v. Volkswagen Grp. of Am., Inc., 859 F.3d 1341, 123 USPQ2d 1146 (Fed. Cir. 2017).
With regard to the above, it is noted that the affidavit should include a reasonable explanation, context, and/or support with respect to the absence of the eight journal co-authors in the instant application, especially given the disclosure of the provisional and the journal article appear to be nearly identical.
2) Applicant may amend the claims to be comply with the requirements of 35 U.S.C. 112(a) or the first paragraph of pre-AIA 35 U.S.C. 112 with respect to the provisional application filed 10/10/2022 such that the claims are accorded the effectively filing date thereof (10/10/2022) to disqualify this reference from being “prior art” (it is an intervening reference with respect to the provisional application filing date and the non-provisional application filing date).
Claim Rejections - 35 USC § 102
10. 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.
11. Claims 1-4, 7-11, 13-14, 17-22, and 24-27 are rejected under 35 U.S.C. 102(a) as being anticipated by Bocharova et al., “Single Ion Conducting Hairy Nanoparticle Additive to Improve Cycling Stability of Solid Polymer Electrolytes,” ACS Appl. Energy Mater. 2023, 6, 8042-8052, published July 17, 2023 (copy provided).
Regarding claim 1, Bocharova teaches a hairy nanoparticle composition comprising:
a nanoparticle core (of silica); and
a Poly(TSFI-Li) (“an ion-conductive polymer”) chemically attached to the nanoparticle core (of silica), wherein the Poly(TSFI-Li) (“ion-conductive polymer”) is polyanionic with mobile cations (abstract; Scheme 1; entire disclosure):
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Regarding claim 2, Bocharova teaches wherein the ion-conductive polymer is polyanionic with mobile cations (see Scheme 1).
Regarding claim 3, Bocharova teaches wherein the mobile cations are lithium (Li+) (see Scheme 1).
Regarding claim 4, Bocharova teaches wherein anions in the polyanionic polymer contain moieties selected from the group consisting of bis(fluorosulfonyl)imide and carboxylate (see Scheme 1).
Regarding claim 7, Bocharova teaches wherein the nanoparticle core is SiO2 (“has an inorganic composition”) (see Scheme 1).
Regarding claim 8, Bocharova teaches wherein the inorganic composition (SiO2) is an oxide composition (see Scheme 1).
Regarding claim 9, Bocharova teaches wherein the oxide composition is selected from the group consisting of silica (see Scheme 1).
Regarding claim 10, Bocharova teaches a solid polymer electrolyte composition (“an electrolyte composition”) comprising hairy nanoparticles incorporated into LiTFSI-doped polyethylene oxide (PEO) (“an ionically conductive electrolyte medium”), wherein the hairy nanoparticles each comprise:
a nanoparticle core (of silica); and
a Poly(TSFI-Li) (“an ion-conductive polymer”) chemically attached to the nanoparticle core (of silica), wherein the Poly(TSFI-Li) (“ion-conductive polymer”) is polyanionic with mobile cations (abstract; Scheme 1; entire disclosure):
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Regarding claim 11, Bocharova teaches wherein the electrolyte medium is a solid electrolyte medium (LiTFSI-doped PEO) (abstract).
Regarding claim 13, Bocharova teaches wherein the solid electrolyte medium is selected from the group named that includes polyethylene oxide (PEO) (abstract).
Regarding claim 14, Bocharova teaches wherein the solid electrolyte medium comprises LiTFSI-doped PEO with LiTFSI being a lithium salt.
Regarding claim 17, Bocharova teaches wherein the ion-conductive polymer is polyanionic with mobile cations (see Scheme 1).
Regarding claim 18, Bocharova teaches wherein anions in the polyanionic polymer are selected from the group named including bis(fluorosulfonyl)imide (Scheme 1).
Regarding claim 19, Bocharova teaches wherein the nanoparticle core has an inorganic composition (SiO2) (abstract; Scheme 1).
Regarding claim 20, Bocharova teaches wherein the inorganic composition is an oxide composition (SiO2) (abstract; Scheme 1).
Regarding claim 21, Bocharova teaches a Li/Li symmetric cell (“a metal-ion battery”) comprising:
(a) an anode (a lithium disc);
(b) a cathode (a lithium disc); and
(c) an electrolyte composition in contact with said anode (lithium disc) and cathode (lithium disc);
wherein said electrolyte composition comprises hairy nanoparticles incorporated into an LiTFSI-doped polyethylene oxide (PEO) (“an ionically conductive electrolyte medium”), wherein the hairy nanoparticle composition comprises:
a nanoparticle core (of silica); and
a Poly(TSFI-Li) (“an ion-conductive polymer”) chemically attached to the nanoparticle core (of silica), wherein the Poly(TSFI-Li) (“ion-conductive polymer”) is polyanionic with mobile cations (abstract; Scheme 1; entire disclosure):
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Regarding claim 22, Bocharova teaches wherein the electrolyte medium is a solid electrolyte medium (abstract)
Regarding claim 24, Bocharova teaches wherein the ion-conductive polymer is polyanionic with mobile cations (Scheme 1; abstract).
Regarding claim 25, Bocharova teaches wherein anions in the polyanionic polymer are selected from the group named including bis(fluorosulfonyl)imide (Scheme 1).
Regarding claim 26, Bocharova teaches wherein the nanoparticle core has an inorganic composition (SiO2) (abstract; Scheme 1).
Regarding claim 27, Bocharova teaches wherein the inorganic composition is an oxide composition. (SiO2) (abstract; Scheme 1).
12. Claims 1-4, 7-10, 17, and 19-20 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Zhao et al., “Fumed Silica-Based Single-Ion Nanocomposite Electrolyte for Lithium Batteries,” ACS Appl. Mater. Interfaces 2015, 7, 19335-19341 (copy provided).
Regarding claims 1-2, Zhao teaches a hairy nanoparticle composition of Si-PSSLi-PEGMA (see Figs. 1, 4, 6; entire disclosure relied upon) (note Fig. 5a shows the overall particle as ~15 nm diameter as described at p. 19338) comprising:
a nanoparticle core of silica (SiO2) (7-10 nm) (Experimental section, p. 19336) (“Si” in Si-PSSLi-PEGMA); and
co-polymerized lithium 4-styrenesulfonate (“PSSLi”) and poly(ethylene oxide) methacrylate (“PEGMA”) (i.e., “PSSLi-PEGMA” – illustrated in Fig. 4) (“an ion-conductive polymer”) chemically attached to the nanoparticle core, wherein the ion- conductive polymer (“PSSLi-PEGMA”) is polyanionic [see Fig. 4 illustrating both sulfonate (SO3-) and carboxylate (CO2-) anionic groups; abstract] with mobile Li+ cations (p.19338-39; entire disclosure relied upon; see also Figs 1, 4, and 6 reproduced below):
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It is noted that Zhao teaches that it is known, effective approach of increasing lithium transference number in solid-state polymer electrolytes to chemically attach the anions on the polymer backbone and limit anion mobility (p. 19335), with the paper describing nanoparticle systems where lithium counter-anions are immobilized on polyelectrolytes grown from nanoparticles (p. 19336). Zhao teaches that by grafting polyanions on the nanoparticles, the sample contains high lithium content and good ionic conductivity is thus expected and achieved (p. 19338, see ionic conductivity measurements in Fig. 5; Conclusions section), wherein the composite electrolyte including said nanoparticles has the potential to suppress lithium dendrite growth and enable the use of a lithium metal anode in rechargeable batteries (abstract) given polymer electrolytes with high lithium transference is known to prevent lithium dendrite formation (P. 19339). Zhao teaches that other polyelectrolyte and anion structures that give better dissociation of ions could further improve conductivity (Conclusions section).
Regarding claim 3, Zhao teaches wherein the mobile cations are selected from the claimed group that includes lithium (Li+) (see Figs. 1, 4, 6).
Regarding claim 4, Zhao teaches wherein anions in PSSLi-PEGMA (“the polyanionic polymer”) contain moieties selected from the claimed group including sulfonate (SO3-) and carboxylate (CO2-) (see Fig. 4).
Regarding claims 7-9, Zhao teaches wherein the nanoparticle core is silica (SiO2) (i.e., “has an inorganic composition that is an oxide selected from the claimed group including silica”) (pp. 19936-37; Figs. 1, 4-6).
Regarding claims 10 and 17, Zhao teaches an electrolyte composition [either Si-PSSLi-PEGMA/ PEGDME electrolyte (Fig. 5) or Si-PSSLi-PEGMA/PEO oligomer (p. 19338-39)] comprising hairy nanoparticles (Si-PSSLi-PEGMA) incorporated into an ionically conductive electrolyte medium (either PEGDME or PEO oligomer), wherein the hairy nanoparticles (Si-PSSLi-PEGMA) each comprise:
a nanoparticle core of silica (SiO2) (7-10 nm) (Experimental section, p. 19336) (“Si” in Si-PSSLi-PEGMA); and
co-polymerized lithium 4-styrenesulfonate (“PSSLi”) and poly(ethylene oxide) methacrylate (“PEGMA”) (i.e., “PSSLi-PEGMA” – illustrated in Fig. 4) (“an ion-conductive polymer”) chemically attached to the nanoparticle core, wherein the ion- conductive polymer (“PSSLi-PEGMA”) is polyanionic [see Fig. 4 illustrating both sulfonate (SO3-) and carboxylate (CO2-) anionic groups; abstract] with mobile Li+ cations (p.19338-39; entire disclosure relied upon; see also Figs 1, 4, and 6 reproduced above).
Regarding claims 19-20, Zhao teaches wherein the nanoparticle core is silica (SiO2) (i.e., “has an inorganic composition that is an oxide selected from the claimed group including silica”) (pp. 19936-37; Figs. 1, 4-6).
Claim Rejections - 35 USC § 103
13. 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.
14. Claim 12 is rejected under 35 U.S.C. 103 as being unpatentable over Bocharova et al., “Single Ion Conducting Hairy Nanoparticle Additive to Improve Cycling Stability of Solid Polymer Electrolytes,” ACS Appl. Energy Mater. 2023, 6, 8042-8052, published July 17, 2023 (copy provided) as applied to at least claims 10 and 11 above, and further in view of Zhou et al. (CN 103840205) (machine translation provided).
Regarding claim 12, Bocharova teaches wherein the solid electrolyte is PEO (“an organic polymer without ionic groups”). Bocharova is silent as to whether the solid electrolyte is microporous or not.
In the same field of endeavor, Zhou teaches analogous art of an electrolyte composition comprising SiO2 particles in a polymer electrolyte material intended for a lithium-ion battery (page 1). The achieved SiO2/PEO composite is taught as being a polymer microporous membrane, wherein the achieved polymer electrolyte membrane has a high tensile strength (page 1).
Therefore, it would have been obvious to one having ordinary skill in the art at the effective filing date of the invention to configure the solid electrolyte of Bocharova that is a PEO material to be a microporous PEO composition given Zhou teaches such a material is suitable for the intended use (MPEP 2144.07), and provides the predictable result of achieving a polymer electrolyte membrane having a high tensile strength (page 1).
15. Claims 11 and 13 are rejected under 35 U.S.C. 103 as being unpatentable over Zhao et al., “Fumed Silica-Based Single-Ion Nanocomposite Electrolyte for Lithium Batteries,” ACS Appl. Mater. Interfaces 2015, 7, 19335-19341 (copy provided) as applied to at least claim 10 above, and optionally in view of Deng, “Li-ion batteries: basics, progress, and challenge,” Energy Science & Engineering 2015; 3(5): 385-418 (copy provided).
Regarding claim 11, Zhao teaches lithium metal is the most promising anode for a rechargeable battery (p. 19335) and discusses the desire to achieve a solid-state polymer electrolyte (SPE) for use therewith as it can address safety issues related to the use of liquid electrolytes. The PEGDME and PEO oligomer utilized in the composite electrolyte composition would be understood to be liquid based electrolytes, which are used for testing purposes given Zhao teaches that solid PEO, the most widely used polymer electrolyte host, featured for its high crystallization degree in the solid state is not used to avoid in the influence of the PEO crystal structure in the material (p. 19338). Accordingly, the use of solid PEO, taught as the most widely used polymer electrolyte host for the final electrolyte composition, in conjunction with the taught hairy nanoparticles is considered an obvious expedient in view of the teachings of Zhao which are aimed at providing a solid-state polymer electrolyte (SPE) (p. 19335).
Optional Reference to Deng
Deng also teaches that benefits of utilizing solid electrolytes over liquid electrolytes including polymer solid electrolytes, and that PEO is the most widely studied polymer which is coupled with various lithium salts such as LiCF3SO3 and LiClO4 (p. 407).
Therefore, it would have been obvious to one having ordinary skill in the art at the effective filing date of the invention to select and implement solid PEO as the solid-state polymer electrolyte (SPE) desired by Zhao (p. 199335) given Deng teaches it is the most widely studied and used polymer electrolyte material for solid state polymer electrolytes (p. 407), the court holding the selection of a known material suitable for its intended use supports a prima facie case of obviousness (MPEP 2144.07).
Regarding claim 13, Zhao renders obvious the use of a solid electrolyte medium comprising polyethylene oxide (PEO) (p.19338). The optional teaching reference to Deng teaches solid PEO (p. 407).
16. Claim 12 is rejected under 35 U.S.C. 103 as being unpatentable over Zhao et al., “Fumed Silica-Based Single-Ion Nanocomposite Electrolyte for Lithium Batteries,” ACS Appl. Mater. Interfaces 2015, 7, 19335-19341 (copy provided), optionally in view of Deng, “Li-ion batteries: basics, progress, and challenge,” Energy Science & Engineering 2015; 3(5): 385-418 (copy provided), as applied to at least claims 10 and 11 above, and further in of Zhou et al. (CN 103840205) (machine translation provided).
Regarding claim 12, Zhao renders obvious the use of a solid electrolyte medium comprising polyethylene oxide (PEO) (p.19338). The optional teaching reference to Deng teaches solid PEO (p. 407). Zhao is silent as to whether the solid electrolyte is microporous or not.
In the same field of endeavor, Zhou teaches analogous art of an electrolyte composition comprising SiO2 particles in a polymer electrolyte material intended for a lithium-ion battery (page 1). The achieved SiO2/PEO composite is taught as being a polymer microporous membrane, wherein the achieved polymer electrolyte membrane has a high tensile strength (page 1).
Therefore, it would have been obvious to one having ordinary skill in the art at the effective filing date of the invention to configure the solid electrolyte of Zhao that is a PEO material to be a microporous PEO composition given Zhou teaches such a material is suitable for the intended use (MPEP 2144.07), and provides the predictable result of achieving a polymer electrolyte membrane having a high tensile strength (page 1).
17. Claim 14 is rejected under 35 U.S.C. 103 as being unpatentable over Zhao et al., “Fumed Silica-Based Single-Ion Nanocomposite Electrolyte for Lithium Batteries,” ACS Appl. Mater. Interfaces 2015, 7, 19335-19341 (copy provided) as applied to at least claims 10 and 11 above2, and further in view of Deng, “Li-ion batteries: basics, progress, and challenge,” Energy Science & Engineering 2015; 3(5): 385-418 (copy provided).
Regarding claim 14, Zhao fails to explicitly teach wherein the solid electrolyte medium comprises a lithium-containing salt. Deng teaches it is a known technique, and would be immediately recognized by one having ordinary skill in the art, to incorporate a lithium-containing salt into the PEO material to provide the predictable result of improved lithium ion conductivity (p. 407).
Therefore, it would have been obvious to one having ordinary skill in the art at the effective filing date of the invention to provide the PEO of Zhao/Deng with a lithium-containing salt given Deng teaches that it is a known technique to provide PEO with a lithium-containing salt, thereby providing the predictable result of improving lithium ion conductivity (p. 407).
18. Claim 18 is rejected under 35 U.S.C. 103 as being unpatentable over Zhao et al., “Fumed Silica-Based Single-Ion Nanocomposite Electrolyte for Lithium Batteries,” ACS Appl. Mater. Interfaces 2015, 7, 19335-19341 (copy provided) as applied to at least claims 10 and 17 above, and further in view of Gao et al., “Single-ion conducting polymer electrolytes as a key jigsaw piece for next-generation battery applications,” Chem. Sci. 2021, 12 (13248-13272) (copy provided by Applicant)
Regarding claim 18, Zhao fails to disclose wherein anions in the polyanionic polymer are selected from the group consisting of bis(fluorosulfonyl)imide and borate as claimed; however, Zhao teaches that other polyelectrolyte and anion structures that give better dissociation of ions could further improve conductivity (Conclusions section).
In the same field of endeavor of polymer electrolytes intended for lithium rechargeable batteries, Gao teaches a summary review of single ion conducting (SIC) polymer electrolytes and known techniques to optimize ionic conductivity. Gao teaches the same technique taught in Zhao of adding building blocks of immobilized anionic groups on a polymer backbone allowing for mobilized Li+ cations and teaches suitable examples thereof include:
carboxylate (-CO2-) anionic groups (section 2.1.1) (as taught by Zhao);
sulfonate (-SO3-) anionic groups (section 2.1.2) (as taught by Zhao);
sulfonylimide (-SO2N(-)SO2-) anionic groups including bis(fluorosulfonyl)imide ((section 2.1.3; see Figs. 4 & 6 also) ; and
borate (-B-) anionic groups (section 2.1.4; see Figs. 5 & 7 also).
Therefore, it would have been obvious to one having ordinary skill in the art at the effective filing date of the invention to look to known building blocks of immobilized anionic groups on a polymer backbone allowing for mobilized Li+ cations and to substitute sulfonylimide (-SO2N(-)SO2-) anionic groups including bis(fluorosulfonyl)imide and/or borate anionic groups for the taught anionic groups of Zhao (carboxylate and sulfonate) given Gao teaches their functional equivalency in terms of achieving the predictable result of immobilized anionic groups on a polymer backbone allowing for mobilized Li+ cations and increased ionic conductivity of the resulting polymer.
19. Claims 21, 22, 24, and 26-27 are rejected under 35 U.S.C. 103 as being unpatentable over Zhao et al., “Fumed Silica-Based Single-Ion Nanocomposite Electrolyte for Lithium Batteries,” ACS Appl. Mater. Interfaces 2015, 7, 19335-19341 (copy provided), and optionally in view of Deng, “Li-ion batteries: basics, progress, and challenge,” Energy Science & Engineering 2015; 3(5): 385-418 (copy provided).
Regarding claims 21 and 24, Zhao teaches an electrolyte composition [either Si-PSSLi-PEGMA/ PEGDME electrolyte (Fig. 5) or Si-PSSLi-PEGMA/PEO oligomer] (see p. 19338-19339) comprising hairy nanoparticles (Si-PSSLi-PEGMA) incorporated into an ionically conductive electrolyte medium (either PEGDME or PEO oligomer), wherein the \hairy nanoparticles (Si-PSSLi-PEGMA) each comprise:
a nanoparticle core of silica (SiO2) (7-10 nm) (Experimental section, p. 19336) (“Si” in Si-PSSLi-PEGMA); and
co-polymerized lithium 4-styrenesulfonate (“PSSLi”) and poly(ethylene oxide) methacrylate (“PEGMA”) (i.e., “PSSLi-PEGMA” – illustrated in Fig. 4) (“an ion-conductive polymer”) chemically attached to the nanoparticle core, wherein the ion- conductive polymer (“PSSLi-PEGMA”) is polyanionic [see Fig. 4 illustrating both sulfonate (SO3-) and carboxylate (CO2-) anionic groups; abstract] with mobile Li+ cations (p.19338-39; entire disclosure relied upon; see also Figs 1, 4, and 6 reproduced above).
Zhao teaches the composite lithium electrolyte is intended to suppress lithium dendrite growth and enable the use of lithium metal anode in rechargeable batteries (abstract; title). Zhao discusses that lithium metal is the most promising anode for a rechargeable battery (p. 19335) and discusses the desire to achieve a solid-state polymer electrolyte (SPE) for use therewith as it can address safety issues related to the use of liquid electrolytes. Zhao describes the use of polymer electrolyte materials and that an effective approach of increasing the lithium transference number and ionic conductivity of the SPE is to chemically attach anions on the polymer electrolyte backbone (p. 19335).
Zhao does not explicitly teach the composite lithium electrolyte intended as a solid-state polymer electrolyte (SPE) material within a metal-ion battery; however, it would be immediately understood reading the disclosure of Zhao that this is the intended end use of the described materials, such that the incorporation thereof into a standard rechargeable lithium-ion metal battery is considered prima facie obvious. Moreover, the claim recites the basic, foundational constituents of any known metal-ion battery (i.e., an anode; a cathode; and an electrolyte composition in contact with said anode and cathode), wherein one of ordinary skill in the art would immediately recognize these three components claimed as the foundation of an metal-ion battery such that the incorporation of the materials taught by Zhao into a metal-ion battery comprising an anode, a cathode, and an electrolyte composition in contact with said anode and cathode would be prima facie obvious.
Optional Reference to Deng
To avoid any doubt, the optional reference to Deng is also cited which teaches lithium-ion battery basics and the known, foundational entities of an anode and applicable materials (pp. 395-406), a cathode and applicable materials (pp. 390-395), an electrolyte and applicable materials (pp.406-408), and the basic construct thereof (see Fig. 4; pp. 385-390) in which the electrolyte composition is in contact with said anode and cathode.
Accordingly, it would have been obvious to one having ordinary skill in the art to look to known lithium ion rechargeable battery constructs as taught by Deng for the intended implementation of Zhao’s taught material for lithium batteries (title; abstract).
Regarding claim 22, Zhao teaches lithium metal is the most promising anode for a rechargeable battery (p. 19335) and discusses the desire to achieve a solid-state polymer electrolyte (SPE) for use therewith as it can address safety issues related to the use of liquid electrolytes. The PEGDME and PEO oligomer utilized in the composite electrolyte composition would be understood to be liquid based electrolytes, which are used for testing purposes given Zhao teaches that solid PEO, the most widely used polymer electrolyte host, featured for its high crystallization degree in the solid state is not used to avoid in the influence of the PEO crystal structure in the material (p. 19338). Accordingly, the use of solid PEO, taught as the most widely used polymer electrolyte host for the final electrolyte composition is considered an obvious expedient in view of the teachings of Zhao which are aimed at providing a solid-state polymer electrolyte (SPE) (p. 19335).
Optional Reference to Deng
Deng also teaches that benefits of utilizing solid electrolytes over liquid electrolytes including polymer solid electrolytes, and the PEO is the most widely studied polymer which is coupled with various lithium salts such as LiCF3SO3 and LiClO4 (p. 407).
Therefore, it would have been obvious to one having ordinary skill in the art at the effective filing date of the invention to select and implement solid PEO as the solid-state polymer electrolyte (SPE) desired by Zhao (p. 199335) given Deng teaches it is the most widely studied and used polymer electrolyte material for solid state polymer electrolytes (p. 407), the court holding the selection of a known material suitable for its intended use supports a prima facie case of obviousness (MPEP 2144.07).
Regarding claims 26 and 27, Zhao teaches wherein the nanoparticle core is silica (SiO2) (i.e., “has an inorganic composition that is an oxide composition”) (pp. 19936-37; Figs. 1, 4-6).
20. Claim 25 is rejected under 35 U.S.C. 103 as being unpatentable over Zhao et al., “Fumed Silica-Based Single-Ion Nanocomposite Electrolyte for Lithium Batteries,” ACS Appl. Mater. Interfaces 2015, 7, 19335-19341 (copy provided) and optionally in view of Deng, “Li-ion batteries: basics, progress, and challenge,” Energy Science & Engineering 2015; 3(5): 385-418 (copy provided) as applied to at least claims 21 and 24, and further in view of Gao et al., “Single-ion conducting polymer electrolytes as a key jigsaw piece for next-generation battery applications,” Chem. Sci. 2021, 12 (13248-13272) (copy provided by Applicant)
Regarding claim 25, Zhao fails to disclose wherein anions in the polyanionic polymer are selected from the group consisting of bis(fluorosulfonyl)imide and borate as claimed; however, Zhao teaches that other polyelectrolyte and anion structures that give better dissociation of ions could further improve conductivity (Conclusions section).
In the same field of endeavor of polymer electrolytes intended for lithium rechargeable batteries, Gao teaches a summary review of single ion conducting (SIC) polymer electrolytes and known techniques to optimize ionic conductivity. Gao teaches the same technique taught in Zhao of adding building blocks of immobilized anionic groups on a polymer backbone allowing for mobilized Li+ cations and teaches suitable examples thereof include:
carboxylate (-CO2-) anionic groups (section 2.1.1) (as taught by Zhao);
sulfonate (-SO3-) anionic groups (section 2.1.2) (as taught by Zhao);
sulfonylimide (-SO2N(-)SO2-) anionic groups including bis(fluorosulfonyl)imide ((section 2.1.3; see Figs. 4 & 6 also) ; and
borate (-B-) anionic groups (section 2.1.4; see Figs. 5 & 7 also).
Therefore, it would have been obvious to one having ordinary skill in the art at the effective filing date of the invention to look to known building blocks of immobilized anionic groups on a polymer backbone allowing for mobilized Li+ cations and to substitute sulfonylimide (-SO2N(-)SO2-) anionic groups including bis(fluorosulfonyl)imide and/or borate anionic groups for the taught anionic groups of Zhao (carboxylate and sulfonate) given Gao teaches their functional equivalency in terms of achieving the predictable result of immobilized anionic groups on a polymer backbone allowing for mobilized Li+ cations and increased ionic conductivity of the resulting polymer.
Conclusion
20. The following reference (not presently relied upon in a formal rejection) is an anticipatory reference to at least claims 1 and 10:
Porcarelli et al., “Single-Ion Conducting Polymer Nanoparticles as Functional Fillers for Solid Electrolytes in Lithium Metal Batteries,” ACS Appl. Mater. Interfaces, 2021, 13, 54354-54362, published Nov. 3, 2021 (copy provided by Applicant with IDS filed 6/4/2024).3 Porcarelli teaches the exact ion-conductive polymer species disclosed in the instant application attached to a nanoparticle (polymer) core (Fig. 1(a) reproduced below):
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21. Additional prior art made of record and not relied upon is considered pertinent to applicant's disclosure:
Lu et al, “Ionic-Liquid-Nanoparticle Hybrid Electrolytes: Applications in Lithium Batteries,” Angew. Chem. Int. Ed. 2014, 53, 488-592, DOI: 10.1002/anie.201307137 (copy provided) teaches the following hairy nanoparticle construct (i.e., SiO2 nanoparticle with an ion-conductive polymer with a cationic group (imaidazolium or piperdidium) with mobile anions of TFSI- (partial Fig. 1):
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Schaefer et al., “Nanoprous hybrid electrolytes,” J. Mater. Chem., 2011, 21, 10094, DOI: 10.1039/c0jm0417h (copy provided) teaches hairy nanoparticles comprising a SiO2 nanoparticle core and the following ion-conductive polymer with a cationic group and mobile anion (reproduced partial Fig. 1 (1A) and partial Fig. 2 (2A)):
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Lago et al., “All-Solid-State Lithium-Ion Batteries with Grafted Ceramic Nanoparticles Dispersed in Solid Polymer Electrolytes, ChemSusChem 2015, 8, 3039-3043, DOI: 10.1002/cssc.201500783 (copy provided) teaches a hairy nanoparticle comprising comprising SiO2 or Al2O3 nanoparticles with a grafted ion-conductive polymer having anionic group and mobile cations (Li+):
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Schaefer et al., “High Lithium Transference Number Electrolytes via Creation of 3-Dimensional, Charged, Nanoporous Networks from Dense Functionalized Nanonparticle Composites, J. Chem. Mater. 2013, 25, 834-839, (copy provided) teaches a hairy nanoparticle composition comprising SiO2 nanoparticles with the following lithium-ion conducting polymer having polyanionic groups (-SO3BF3-) and mobile cations (Li+):
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Chen et al., “Synthesis and aqueous solution of polyelectrolyte-grafted silica particles prepared by surface-iniated atom transfer radical polymerization, J. Colloid & Interface Science 257 (2003) 56-64 (copy provided) teaches:
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Liu et al., “Composite solid electrolytes containing single-ion lithium polymer grafted garnet for dendrite free, long-life all-solid-state lithium metal batteries,” Chemical Engineering Journal 445 (2022), 136436, pages 1-12, available Online 16 April 2022 (copy provided) teaches a LLZTO particle (microsized) graphited with polyanionic ion-conductive polymer with mobile lithium ions:
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22. Any inquiry concerning this communication or earlier communications from the examiner should be directed to AMANDA J BILLIET, NEE BARROW, whose telephone number is (571)270-7867. The examiner can normally be reached Monday-Friday 9am - 6pm CST.
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/AMANDA J BILLIET/Primary Examiner, Art Unit 1729
1 See Priority section analysis above (section 3).
2 It is assumed for compact prosecution purposes that claim 14 depends from claim 11 (see rejection under 35 U.S.C. 112(b)/second paragraph).
3 It is noted that the present effective filing date of the claims is 10/10/2023 (see Priority section); accordingly, there is no grace period for this reference at the present time, wherein the presence and absence of different authors/inventors in the article and the instant application also does not allow for any assumption as to an inventor-originated disclosure for a hypothetical future claim that achieves the effective filing date of the priority application.
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