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.
Information Disclosure Statement
The information disclosure statement filed April 5, 2024 has been placed in the application file and the information referred to therein has been considered as to the merits.
With respect to foreign language references with no translation of the document: “If no translation is submitted, the examiner will consider the information in view of the concise explanation and insofar as it is understood on its face, e.g., drawings, chemical formulas, English language abstracts, in the same manner that non-English language information in Office search files is considered by examiner in conducting searches.” See MPEP §609.04(a)(II) (D) and 37 CFR 1.98(a)(3)(ii).
Drawings
The drawings received April 5, 2024 are acceptable for examination purposes.
Specification
The specification received April 5, 2024 has been reviewed for examination purposes.
Claim Rejections - 35 USC § 103
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention(s) absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and effective filing dates of each claim that was not commonly owned as of the effective filing date of the later invention in order for the examiner to consider the applicability of 35 U.S.C. 102(b)(2)(C) for any potential 35 U.S.C. 102(a)(2) prior art against the later invention.
Claims 1, 3, 6, 11 and 14 are rejected under 35 U.S.C. 103 as being unpatentable over Yang et al. (CN 105186033A).
As to claim 1, Yang discloses a gel polymer electrolyte separator, which is prepared from raw materials comprising a masterbatch and an extractant; wherein
the masterbatch comprises the following components in mass percentage, based on a mass of the gel polymer electrolyte: 53% to 81% of an organic solvent, 10% to 21% of a polymer substrate, 6% to 19% of a pore-forming agent, and 1% to 8% of a nano-functional material (the mass ratio of polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP), titanium dioxide nanotubes (TiO2-NER8-NTs), pore forming agent, and organic solvent is 1.0–2.5:0.1–0.9:0.3–1:7.6–8.2 (para. [0015]). This teaches of a range of organic solvent from 76-82%, polymer substrate (PVdF-HFP) from 10-25%, pore forming agent from 3-17% and nano-functional material (titanium dioxide nanotubes) from 1-9%. A further review of the examples show:
Example 1 – 10g total sample (para. [0038]) organic solvent 7.9g (79%), PVdF-HFP polymer substrate 1.5g (15%), pore forming agent 0.3g (3%) and nano-functional material (titanium dioxide nanotubes) 0.3g (3%).
Example 2 – 10g total sample (para. [0044]) organic solvent 8.1g (81%), PVdF-HFP polymer substrate 1.5g (15%), pore forming agent 0.3g (3%) and nano-functional material (titanium dioxide nanotubes) 0.1g (1%).
Example 3 – 10g total sample (para. [0047]) organic solvent 7.7g (77%), PVdF-HFP polymer substrate 1.5g (15%), pore forming agent 0.3g (3%) and nano-functional material (titanium dioxide nanotubes) 0.3g (3%).
as discussed above, the polymer substrate is one or two selected from the group consisting of a polyvinylidene fluoride (PVDF) homopolymer and a PVdF-hexafluoropropylene (HFP) copolymer; and
as discussed above, the nano-functional material is one or more selected from the group consisting of Al₂O₃, SiO₂, TiO₂, and an oxide solid electrolyte.
As to an extractant, Yang teaches of rinsing with deionized water to remove the pore forming agent.
As to claim 3, the solvent is one of DMF, NMP and DMAc (para. [0015] and examples).
As to claim 6, the method includes dissolving the titanium oxide nanotubes, the PVdF-HFP polymer and the pore forming agent in the solvent (see examples) and forming the liquid into a film (coated onto a base and dried).
As to claim 11, the solvent is one of DMF, NMP and DMAc (para. [0015] and examples).
As to claim 14, the separator of claim 1 is used in a lithium ion battery (para. [0002] for example).
The difference between Yang and the raw materials of claim 1 are the specific ranges of each raw material.
As noted above, Yang teaches of organic solvent from 76-82%, polymer substrate PVdF-HFP) from 10-25%, pore forming agent from 3-17% and nano-functional material (titanium dioxide nanotubes) from 1-9%. A further review of the examples show: Example 1 – 10g total sample (para. [0038]) organic solvent 7.9g (79%), PVdF-HFP polymer substrate 1.5g (15%), pore forming agent 0.3g (3%) and nano-functional material (titanium dioxide nanotubes) 0.3g (3%). Example 2 – 10g total sample (para. [0044]) organic solvent 8.1g (81%), PVdF-HFP polymer substrate 1.5g (15%), pore forming agent 0.3g (3%) and nano-functional material (titanium dioxide nanotubes) 0.1g (1%). Example 3 – 10g total sample (para. [0047]) organic solvent 7.7g (77%), PVdF-HFP polymer substrate 1.5g (15%), pore forming agent 0.3g (3%) and nano-functional material (titanium dioxide nanotubes) 0.3g (3%).
The ranges of Yang either significantly overlap or encompass the ranges of claim 1. Furthermore, for each example, the only difference in ranges is that the amount of the pore former is 3% which is just outside the lower limit of claim 1. But Yang also recognized that the pore former mass can be effectively tuned to higher levels from 3-17 mass%, thus substantially overlapping in scope with the amount of pore former of claim 1.
Modifying the examples to tune the amount of pore forming agent, while maintaining sufficient amounts of organic solvent, polymer substrate and nano-functional material would have been reasonably within the teachings of Yang, amounts with sufficient encompass or effectively overlap in scope with the amounts of claim 1.
Therefore it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to select the amounts of organic solvent, polymer substrate, pore former and nano-functional material where the range of organic solvent from 76-82%, polymer substrate (PVdF-HFP) from 10-25%, pore forming agent from 3-17% and nano-functional material (titanium dioxide nanotubes) from 1-9% and values near such ranges with the understanding that the selection and tuning of the ranges would have effectively resulted in the formation of a suitable PVdF-HFP / nano-functional material gel polymer electrode. See MPEP § 2144.05, incorporated herein. "[A] prior art reference that discloses a range encompassing a somewhat narrower claimed range is sufficient to establish a prima facie case of obviousness." In re Peterson, 315 F.3d 1325, 1330, 65 USPQ2d 1379, 1382-83 (Fed. Cir. 2003). See also In re Harris, 409 F.3d 1339, 74 USPQ2d 1951 (Fed. Cir. 2005) (claimed alloy held obvious over prior art alloy that taught ranges of weight percentages overlapping, and in most instances completely encompassing, claimed ranges; furthermore, narrower ranges taught by reference overlapped all but one range in claimed invention).
Generally, differences in ranges will not support the patentability of subject matter encompassed by the prior art unless there is evidence indicating such ranges is critical. In re Boesch, 617 F.2d 272, 205 USPQ 215 (CCPA 1980). In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955). In re Hoeschele, 406 F.2d 1403, 160 USPQ 809 (CCPA 1969).
In the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976). “The law is replete with cases in which the difference between the claimed invention and the prior art is some range or other variable within the claims. . . . In such a situation, the applicant must show that the particular range is critical, generally by showing that the claimed range achieves unexpected results relative to the prior art range.” In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990) It has been held that when the difference between a claimed invention and the prior art is the range or value of a particular variable, then a prima facie rejection is properly established when the difference in the range or value is minor. Titanium Metals Corp. of Am. v. Banner, 778 F.2d 775, 783, 227 USPQ 773, 779 (Fed. Cir. 1985).
Claims 2, 4, 10 and 12 are rejected under 35 U.S.C. 103 as being unpatentable over Yang et al. (CN 105186033A) as applied to claims 1 and 6, respectively above, and further in view of Cao et al. “Structure and ionic conductivity of porous polymer electrolytes based on PVDF-HFP copolymer membranes”.
Yang does teach of the inclusion of pore forming agents. The disclosed agents are polyethylene glycol pore formers.
Yang does not teach of the pore former being one or two of dibutyl phthalate (DBP) and white oil (claims 4 and 12) or of the extractant being one or more of methanol, dichloromethane, ethanol, chloroform, trichloromethane, dichloromethane, carbon tetrachloride, toluene, ethyl acetate (claims 2 and 10).
PEG, DBP and white oil are all recognized polymer pore forming agents and it would have been of routine and predictable skill in the art to select any suitable pore forming agent that is recognized as a suitable pore forming agent.
Cao is directed to PVdF-HFP based electrolytes whereby the membrane is formed using pore forming agents such as DBP or PEG (abstract, Sections 2.1 and 2.2). These additives are removed to render the PVdF-HFP effectively porous (applied to claims 4 and 12).
Therefore it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify the teachings of Yang whereby the pore forming agent is BDP as taught by Cao since it would have provided a suitable alternative to PEG for effectively forming pores in a PVdF-HFP gel electrolyte.
The selection of a known material based on its suitability for its intended use supported a prima facie obviousness determination in Sinclair & Carroll Co. v. Interchemical Corp., 325 U.S. 327, 65 USPQ 297 (1945) See also In re Leshin, 227 F.2d 197, 125 USPQ 416 (CCPA 1960). MPEP § 2144.07.
Cao further disclosed that extraction used methanol to extract the additive at room temperature (section 2.2, applied to claims 2 and 10). The use of other extractants such as methanol to effectively remove DBP or PEG pore forming additives would have been obvious for the predictable and expected result of sufficient additive extraction from the membrane, thereby providing the same desired porous PVdF-HFP membrane.
Therefore it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify the extractant of Yang to be methanol as taught by Cao since it would have predictably and effectively removed the pore-forming additive from the PVdF-HFP membrane.
Claims 4 and 12 are rejected under 35 U.S.C. 103 as being unpatentable over Yang et al. (CN 105186033A) as applied to claims 1 and 6, respectively above, and further in view of Walkowiak et al. (PL240557).
Yang does teach of the inclusion of pore forming agents. The disclosed agents are polyethylene glycol pore formers.
Yang does not teach of the pore former being one or two of dibutyl phthalate (DBP) and white oil (claims 4 and 12).
PEG, DBP and white oil are all recognized polymer pore forming agents and it would have been of routine and predictable skill in the art to select any suitable pore forming agent that is recognized as a suitable pore forming agent.
Walkowiak is directed to PVdF-HFP based electrolytes whereby the membrane is formed using pore forming agents such as DBP (claims 4 and 14), which is effectively removed using diethyl ether to render the PVdF-HFP effectively porous (see Examples on pages 3-4 of the machine translation).
Therefore it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify the teachings of Yang whereby the pore forming agent is BDP as taught by Cao since it would have provided a suitable alternative to PEG for effectively forming pores in a PVdF-HFP gel electrolyte.
The selection of a known material based on its suitability for its intended use supported a prima facie obviousness determination in Sinclair & Carroll Co. v. Interchemical Corp., 325 U.S. 327, 65 USPQ 297 (1945) See also In re Leshin, 227 F.2d 197, 125 USPQ 416 (CCPA 1960). MPEP § 2144.07.
Claims 2 and 10 are rejected under 35 U.S.C. 103 as being unpatentable over Yang et al. (CN 105186033A) as applied to claims 1 and 6, respectively above, and further in view of Walkowiak et al. (PL240557) and Mitchell (U.S. Patent No. 6,007,588).
Yang does not teach of the extractant being one or more of methanol, dichloromethane, ethanol, chloroform, trichloromethane, dichloromethane, carbon tetrachloride, toluene, ethyl acetate (claims 2 and 10).
Walkowiak is directed to PVdF-HFP based electrolytes whereby the membrane is formed using pore forming agents such as DBP (claims 4 and 14), which is effectively removed using diethyl ether to render the PVdF-HFP effectively porous (see Examples on pages 3-4 of the machine translation).
Therefore it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify the teachings of Yang whereby the pore forming agent is BDP as taught by Walkowiak since it would have provided a suitable alternative to PEG for effectively forming pores in a PVdF-HFP gel electrolyte. The selection of a known material based on its suitability for its intended use supported a prima facie obviousness determination in Sinclair & Carroll Co. v. Interchemical Corp., 325 U.S. 327, 65 USPQ 297 (1945) See also In re Leshin, 227 F.2d 197, 125 USPQ 416 (CCPA 1960). MPEP § 2144.07.
Upon using DBP, it would have been of routine and predictable skill in the art to select the extractant to be one or more of methanol, dichloromethane, ethanol, chloroform, trichloromethane, dichloromethane, carbon tetrachloride, toluene, ethyl acetate.
While Yang uses water to remove polyethylene glycol (PEG) pore formers, it was of routine skill in the art to select the extractant to be water given the compatibility between water and PEG since PEG is well known to be water soluble.
It is further well known in the art to generate pores in PVdF-HFP using other pore-former/extractant combinations, including using DBP and diethyl ether as taught by Walkowiak (as discussed above). DBP is a hydrophobic ester that readily dissolves in many organic solvents. Thus upon selecting DBP as a pore former as discussed above, in order to effectively remove DBP, Walkowiak uses an organic solvent of diethyl ether. While Walkowiak does not teach of the extractant being one or more of methanol, dichloromethane, ethanol, chloroform, trichloromethane, dichloromethane, carbon tetrachloride, toluene, ethyl acetate, these alternative organic solvents would have been predictable alternatives for extracting DBP.
Mitchell for example, recognized plasticizers such as DBP as pore forming agents whereby effective removal of such is facilitated by a number of organic based extractants including diethyl ether and methanol (col. 5, ll. 13-33). The substitution of diethyl ether (Walkowiak) with other extractants such as methanol (Mitchell) in PVdF based polymers for the purpose of removing DBP to form pores in the PVdF would have been of routine and predictable skill in the art for the same effective result.
Therefore it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify the extractant of modified Yang by using any number of suitable conventional organic extractants such as methanol as taught by Mitchell since it would have predictably and effectively removed DBP from PVDF to render the PVDF porous. The selection of a known material based on its suitability for its intended use supported a prima facie obviousness determination in Sinclair & Carroll Co. v. Interchemical Corp., 325 U.S. 327, 65 USPQ 297 (1945) See also In re Leshin, 227 F.2d 197, 125 USPQ 416 (CCPA 1960). MPEP § 2144.07. See also KSR International Co. v. Teleflex Inc., 82 USPQ2d 1385 (U.S. 2007).
Claims 8-9 are rejected under 35 U.S.C. 103 as being unpatentable over Yang et al. (CN 105186033A) as applied to claim 6 above, and further in view of either Lin et al. (CN 111224154A), Woo et al. (KR10-2018-0031355) or Bai et al. (U.S. Patent Application Publication No. 2023/0246297).
As to claims 8 and 9, Yang teaches of drying the film at 50-70oC (see examples).
Yang does not explicitly teach of molding the gel electrolyte (claim 8).
Lin, drawn to the same field of manufacturing gel polymer electrolytes, wherein Lin recognized that a method of preparing a gel electrolyte can readily include a molding of the casted material to form an effective gel electrolyte film (paras. [0028], [0031], for example). Woo, drawn to the same field of manufacturing gel polymer electrolytes, wherein Woo also recognized that a method of preparing a gel electrolyte can readily include a molding of the casted material to form an effective gel electrolyte film (see page 3 of the machine translation). Bai, drawn to the same field of manufacturing gel polymer ion conducting gel coatings to a base layer, wherein Bai also recognized that a method of preparing a gel layer can readily include a molding of the casted material to form an effective gel film (para. [0047]). Molding provides control of the thickness and shape of the film as desired and it would have been of routine and predictable skill in the art to modify the method of Yang to include drying and molding to obtain a gel polymer electrolyte separator having a desired shape and thickness.
Therefore it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify the method of Yang to include a molding step as taught by Lin, Woo or Bai since it would have provided a predictable method step for forming the PVdF-HFP film to a desired shape and thickness by containing the casted solution within a desired mold as needed.
Allowable Subject Matter
Claims 5, 7 and 13 are objected to as being dependent upon a rejected base claim but would be allowable if rewritten in independent form including all of the limitations of the base claim and any intervening claims.
The following is a statement of reasons for the indication of allowable subject matter:
With respect to claims 5 and 13, none of the cited prior art of record, alone or in combination, are held to reasonably teach, suggest or render obvious the pore forming agent having a mass fraction of DBP in a range from 7% to 18% and a mass fraction of white oil in the range of 1% to 2%.
According to the disclosure of the instant application (para. [0021]): Owing to the introduction of nano-functional materials, the dosage of pore-forming agent is reduced to ensure the mechanical strength of the gel polymer electrolyte, which is easy to cause a problem that one side of the separator has pores while the other side is non-porous during the manufacturing. However, in the present disclosure, by introducing a mixed pore-forming agent of white oil and DBP, the ion transmission problem that one side of the gel polymer electrolyte separator has pores while the other side is non-porous could be effectively solved, interface resistance could be reduced, and ionic conductivity could be increased.
The cited prior art of record, alone or in combination, fails to reasonably teach or suggest the particular combination of white oil and DBP in the specified amounts in claims 5 and 13.
With respect to claim 7, none of the cited prior art of record, alone or in combination, are held to reasonably teach, suggest or render obvious the method further comprising in step (1), subjecting the pore-forming agent to filtration and iron removal in sequence before the dissolving.
The cited prior art of record, alone or in combination, fails to reasonably teach or suggest subjecting the pore-forming agent to filtration and iron removal in sequence before the dissolving as recited in claim 7.
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure. KR10-1881211 discloses a gel polymer electrolyte membrane comprising PVdF-HFP, LLTO/SiO2 nanomaterial, and DBP but does not sufficiently teach the mass percentages of the components.
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/GREGG CANTELMO/Primary Examiner, Art Unit 1725
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