COMPOSITE SOLID ELECTROLYTE USING ZEOLITE AND FLUORINE-BASED LITHIUM SALT

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 Acknowledgment is made of applicant’s claim for foreign priority under 35 U.S.C. 119 (a)-(d). The certified copy has been filed in parent Application No. KR10-2021-0139559, filed on 10/19/2021. Claim Rejections - 35 USC § 103 In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status. The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action: A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made. The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows: 1. Determining the scope and contents of the prior art. 2. Ascertaining the differences between the prior art and the claims at issue. 3. Resolving the level of ordinary skill in the pertinent art. 4. Considering objective evidence present in the application indicating obviousness or nonobviousness. This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention(s) absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and effective filing dates of each claim that was not commonly owned as of the effective filing date of the later invention in order for the examiner to consider the applicability of 35 U.S.C. 102(b)(2)(C) for any potential 35 U.S.C. 102(a)(2) prior art against the later invention. Claim(s) 1-2 and 8-17 is/are rejected under 35 U.S.C. 103 as being unpatentable over Munichandraiah (“Influence of zeolite on electrochemical and physicochemical properties of polyethylene oxide solid electrolyte” – 1995) in view of Kim et al. (US 2021/0066751 A1). Regarding Claim 1, Munichandraiah discloses a composite solid electrolyte film comprising: zeolite (fine zeolite particles dispersed at 8, 14, 20, 24, 29, and 38 wt%) [Section 2, Section 3.1], an ion-conductive polymer (polyethylene oxide, PEO, Mw 300,000) [Section 2], and a fluorine-based lithium salt (lithium tetrafluoroborate, LiBF4) [Section 2]. Munichandraiah discloses that the base complex (PEO)8LiBF4 maintains an O:Li ratio of 8:1 [Section 2], which, upon addition of 8 to 38 wt% zeolite, provides a salt concentration in the total composite film of approximately 13 to 19.3 wt%. Munichandraiah does not explicitly disclose that the content of the fluorine-based lithium salt is within the claimed range of 20 to 45 wt%. However, Kim, from the same field of endeavor, teaches solid polymer electrolytes for all-solid-state lithium secondary batteries comprising an ion-conductive polyalkylene oxide (PEO) and a fluorine-based lithium salt [pars. 0015,0020,0050–56]. Kim explicitly discloses that the fluorine-based lithium salt (e.g., LiTFSI, LiFSI) is present in an amount of 10 to 50 parts by weight based on 100 parts by weight of the electrolyte [Claim 7; par. 0057], and specifically provides working examples containing 20.8 wt% (Example 2), 23.7 wt% (Example 1), 29.6 wt% (Example 3), and 46.9 wt% (Examples 4 and 5) of the fluorine-based lithium salt in solid PEO-based electrolyte films [Table 4]. Kim teaches that utilizing a high concentration of the fluorine-based lithium salt (~20 to 47 wt%) provides increased polymer chain fluidity, dissociates more lithium cations, compensates for the loss of ionic conductivity caused by high solid contents, and provides voltage stability exceeding 5.0 V [pars. 0051,0057,0114,0117]. Therefore, before the effective filing date of the claimed invention, it would have been obvious for an ordinary skilled artisan to modify the composite solid electrolyte of Munichandraiah by incorporating the fluorine-based lithium salt in an amount of 20 to 45 wt% (e.g., 20.8 to 29.6 wt%), as taught by Kim, in order to increase polymer chain mobility, enhance salt dissociation, overcome conductivity decreases resulting from inorganic filler loading, and improve high-voltage electrochemical stability in all-solid-state batteries. Furthermore, the claimed range of 20 to 45 wt% represents a routine optimization of a result-effective variable that directly overlaps and abuts the ranges taught by Munichandraiah (~15-19.3 wt%) and Kim (10 to 50 wt%, specifically 20.8 to 46.9 wt%), establishing a prima facie case of obviousness, without undue experimentation and with a reasonable expectation of success [MPEP 2144.05(II)]. Regarding Claim 2, modified Munichandraiah discloses the composite the solid electrolyte of claim 1, wherein the zeolite further includes an alkali metal ion [Section 3.2]. Regarding Claim 8, modified Munichandraiah discloses the composite the solid electrolyte of claim 1, wherein the ion conductive polymer is a polyalkylene oxide-based polymer (i.e., PEO) [Section 2]. Regarding Claim 9, modified Munichandraiah discloses the composite solid electrolyte of claim 1, wherein the fluorine-based lithium salt is LiBF4 [Section 2]. Moreoever, Kim explicitly teaches utilizing LiN(SO2CF3)2 (LiTFSI), across all working Examples [Table 2, Table 4] and discloses Li(FSO2)2N (LiFSI) as a preferred fluorinated salt [par. 0056]. It would have been obvious to an ordinary skilled artisan to select LiTFSI or LiFSI in the composite of Munichandraiah to achieve higher dissociation and ionic conductivity, as taught by Kim. Regarding Claim 10, modified Munichandraiah discloses the composite solid electrolyte of claim 1. Kim explicitly teaches utilizing LiN(SO2CF3)2 (LiTFSI), across all working Examples [Table 2, Table 4] and discloses Li(FSO2)2N (LiFSI) as a preferred fluorinated salt [par. 0056]. It would have been obvious to an ordinary skilled artisan to select LiFSI in the composite of Munichandraiah to achieve higher dissociation and ionic conductivity, as taught by Kim. Regarding Claim 11, modified Munichandraiah discloses the composite solid electrolyte of claim 1. Kim's broad disclosure of 10 to 50 parts by weight of salt, along with Example 3 (29.6 wt% LiTFSI) and Examples 4–5 (46.9 wt% LiTFSI), directly encompasses the narrower range of 30 to 40 wt%. Selecting 30 to 40 wt% is a matter of routine optimization of a known result-effective variable to maximize lithium transport without causing salt crystallization [MPEP 2144.05(II)] Regarding Claim 12, modified Munichandraiah discloses the composite solid electrolyte of claim 1, wherein the composite solid electrolyte is a freestanding film [Munichandraiah – Section 2; Kim – pars. 0025,0115,0117]. Regarding Claim 13, modified Munichandraiah discloses the composite solid electrolyte of claim 1, but fails to explicitly teach wherein the composite solid electrolyte has an elongation of 1.5 times or more that of a composite solid electrolyte including 10 wt % of the fluorine-based lithium salt. However, an increase in elongation at break of 1.5 times or more is the natural, inherent physical consequence of plasticizing a semicrystalline PEO matrix with 20 to 45 wt% of a bulky fluorinated imide/borate lithium salt (such as LiTFSI). Because the prior art combination renders obvious the identical composite formulation, this claimed functional mechanical property is inherently present under 35 U.S.C. 102/103 [MPEP § 2112]. Regarding Claim 14, modified Munichandraiah discloses the composite solid electrolyte of claim 1, but fails to explicitly teach wherein the composite solid electrolyte has a work function of 3.5 eV or more. However, the work function is an inherent physical and electronic property of a solid composite electrolyte comprising PEO, zeolite, and 20 to 45 wt% of a fluorinated lithium salt. Because the prior art combination renders the claimed chemical composition and physical structure obvious, the resulting material inherently possesses the claimed work function [MPEP 2112]. Regarding Claim 15, Munichandraiah discloses a method for producing a composite solid electrolyte, the method comprising: mixing zeolite, an ion conductive polymer, and a fluorine-based lithium salt to produce a mixture; and producing a composite solid electrolyte using the mixture {Munichandraiah teaches preparing the composite solid electrolyte by dissolving PEO and lithium salt in an organic solvent (acetonitrile), adding and uniformly dispersing fine zeolite particles under stirring, casting the solution onto a substrate (PTFE-covered glass), and evaporating the solvent under vacuum drying at 80°C for 24 hours to form a solid film [Section 2]}. Munichandraiah fails to disclose wherein a content of the fluorine-based lithium salt is 20 to 45 wt %. However, Kim, from the same field of endeavor, teaches solid polymer electrolytes for all-solid-state lithium secondary batteries comprising an ion-conductive polyalkylene oxide (PEO) and a fluorine-based lithium salt [pars. 0015,0020,0050–56]. Kim explicitly discloses that the fluorine-based lithium salt (e.g., LiTFSI, LiFSI) is present in an amount of 10 to 50 parts by weight based on 100 parts by weight of the electrolyte [Claim 7; par. 0057], and specifically provides working examples containing 20.8 wt% (Example 2), 23.7 wt% (Example 1), 29.6 wt% (Example 3), and 46.9 wt% (Examples 4 and 5) of the fluorine-based lithium salt in solid PEO-based electrolyte films [Table 4]. Kim teaches that utilizing a high concentration of the fluorine-based lithium salt (~20 to 47 wt%) provides increased polymer chain fluidity, dissociates more lithium cations, compensates for the loss of ionic conductivity caused by high solid contents, and provides voltage stability exceeding 5.0 V [pars. 0051,0057,0114,0117]. Therefore, before the effective filing date of the claimed invention, it would have been obvious for an ordinary skilled artisan to modify method of Munichandraiah wherein a content of the fluorine-based lithium salt in the composite solid electrolyte is in an amount of 20 to 45 wt% (e.g., 20.8 to 29.6 wt%), as taught by Kim, in order to increase polymer chain mobility, enhance salt dissociation, overcome conductivity decreases resulting from inorganic filler loading, and improve high-voltage electrochemical stability in all-solid-state batteries. Furthermore, the claimed range of 20 to 45 wt% represents a routine optimization of a result-effective variable that directly overlaps and abuts the ranges taught by Munichandraiah (~15-19.3 wt%) and Kim (10 to 50 wt%, specifically 20.8 to 46.9 wt%), establishing a prima facie case of obviousness, without undue experimentation and with a reasonable expectation of success [MPEP 2144.05(II)]. Regarding Claim 16, modified Munichandraiah discloses the method of claim 15, wherein the mixture further includes acetonitrile (CAN) to dissolve the PEO and lithium salt and to disperse the zeolite [Munichandraiah – Section 2]. Regarding Claim 17, modified Munichandraiah discloses a lithium secondary battery comprising: a positive electrode; the composite solid electrolyte of claim 1; and a negative electrode {Munichandraiah discloses constructing and cycling electrochemical cells comprising the composite solid electrolyte disposed between lithium metal electrodes (Li/SPE/Li) [Section 2, Section 3.2]. Kim further teaches all-solid-state secondary batteries comprising positive and negative electrodes with the solid polymer electrolyte disposed therebetween [Claim 17; pars. 0083-101]}. Claim 3 is rejected under 35 U.S.C. 103 as being unpatentable over Munichandraiah and Kim, as applied to Claim 1, and further in view of Xiao (US20190229318A1), or alternatively, in view of Hatta (US20160240887A1). Regarding Claim 3, modified Munichandraiah discloses the composite solid electrolyte of claim 1, but fails to explicitly teach wherein zeolite particles have an average particle diameter of 200 to 1,000 nm. Xiao, from the same field of endeavor, teaches lithium battery electrolyte and separator membranes comprising lithium-containing zeolite particles (specifically zeolite Y and ZSM-5). Xiao explicitly teaches that the zeolite particles have an average particle diameter of 10 nm to 20 μm, specifically 10 nm to 1 μm (i.e., 1000 nm), and exemplifies zeolite nanoparticles having an average particle diameter of 100 nm [pars. 0009,0067,0076]. Xiao further teaches that reducing the zeolite particle size to the sub-micron/nanoscale enables the formation of a more uniform active layer, improves interfacial contact, and provides efficient entrapment of contaminants without inhibiting lithium-ion transport [pars. 0045,0067,0072]. Alternatively, Hatta explicitly teaches in Example 1-47 and Table 1 an electrolyte containing zeolite particles having a D50 particle size of 1000 nm, and establishes that particle sizes between 50 and 450 nm or 750 and 1,000 nm maintain transparency, prevent slurry viscosity spikes, and suppress short circuits [pars. 0010,0075-76,0138]. Therefore, before the effective filing date of the claimed invention, it would have been obvious for an ordinary skilled artisan to modify the size of the zeolite particles of Munichandraiah to be an average diameter of 200 to 1,000 nm, as taught by Xiao or Hatta, in order to form a smoother, more uniform composite film, increase filler surface contact with the polymer matrix, and prevent pinhole defects or short circuits. Furthermore, adjusting particle size within a known functional range is a matter of routine optimization of a result-effective variable, without undue experimentation and with a reasonable expectation of success [MPEP 2144.05(II)]. Claims 4-7 are rejected under 35 U.S.C. 103 as being unpatentable over Munichandraiah and Kim, as applied to Claim 1, and further in view of Xiao (US20190229318A1). Regarding Claims 4 and 6, modified Munichandraiah discloses the composite solid electrolyte of claim 1, but does not explicitly teach wherein the zeolite is Y-type zeolite, or wherein the zeolite has a specific surface area by a BET measurement method of 100 to 2,000 m2/g. Xiao, from the same field of endeavor, teaches lithium battery electrolyte and separator membranes comprising lithium-containing zeolite particles including zeolite Y allows for effective entrapment of undesirable contaminants and decomposition products while facilitating unobstructed lithium-ion transport through the open, three-dimensional pore channels of the framework [pars. 0011-12,0045,0065,0068,0071,0074]. Therefore, before the effective filing date of the claimed invention, it would have been obvious for an ordinary skilled artisan to modify the zeolite of Munichandraiah to include zeolite Y, as taught by Xiao, in order to provide for effective entrapment of undesirable contaminants and decomposition products while facilitating unobstructed lithium-ion transport through the open, three-dimensional pore channels of the framework. To the extent that the specific surface area is not expressly quantified in Xiao, this property is an inherent physical characteristic of Y-type zeolite disclosed by the prior art [MPEP 2112]. There the prior art combination renders obvious the identical material (i.e., zeolite Y), it inherently possesses the claimed physical characteristics. Regarding Claim 5, modified Munichandraiah discloses the composite solid electrolyte of claim 1, but does not explicitly teach wherein zeolite pores have an average diameter of 1 to 10 nm. Xiao, from the same field of endeavor, teaches lithium battery electrolyte and separator membranes comprising lithium-containing zeolite particles including zeolite Y allows, wherein the zeolite particles may have an average pore size diameter of less than or equal to about 1.5 nm for effective entrapment of undesirable contaminants and decomposition products while facilitating unobstructed lithium-ion transport through the open, three-dimensional pore channels of the framework [pars. 0011-12,0045,0065,0068,0071,0074]. Therefore, before the effective filing date of the claimed invention, it would have been obvious for an ordinary skilled artisan to modify the zeolite of Munichandraiah, as taught by Xiao, wherein the zeolite pores have an average diameter of up to 1.5 nm in order to provide for effective entrapment of undesirable contaminants and decomposition products while facilitating unobstructed lithium-ion transport through the open, three-dimensional pore channels of the framework. Regarding Claim 7, modified Munichandraiah discloses the composite solid electrolyte of claim 1, but does not explicitly teach wherein the zeolite has a mole ratio between silica (SiO2) and alumina (Al2O3) of 1:1 to 10:1. Xiao, from the same field of endeavor, teaches lithium battery electrolyte and separator membranes comprising lithium-containing zeolite particles which, in particular embodiments, having a SiO2:Al2O3 ratio less than about 10 for an increased hydrofluoric acid (HF) scavenger function of the porous separator to protect the positive electrode [par. 0070]. Therefore, before the effective filing date of the claimed invention, it would have been obvious for an ordinary skilled artisan to modify the zeolite of Munichandraiah, as taught by Xiao, to have a molar ratio between silica and alumina of less than 10 in order to provide for an increased hydrofluoric acid (HF) scavenger function of the porous separator to protect the positive electrode. Furthermore, adjusting molar ratio between silica and alumina within a known functional range is a matter of routine optimization of a result-effective variable, without undue experimentation and with a reasonable expectation of success [MPEP 2144.05(II)]. Conclusion Any inquiry concerning this communication or earlier communications from the examiner should be directed to HAROON S SHEIKH whose telephone number is (571)270-0302. The examiner can normally be reached 9-6. Examiner interviews are available via telephone, in-person, and video conferencing using a USPTO supplied web-based collaboration tool. To schedule an interview, applicant is encouraged to use the USPTO Automated Interview Request (AIR) at http://www.uspto.gov/interviewpractice. If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, JONATHAN LEONG can be reached at (571) 270-1292. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300. Information regarding the status of published or unpublished applications may be obtained from Patent Center. Unpublished application information in Patent Center is available to registered users. To file and manage patent submissions in Patent Center, visit: https://patentcenter.uspto.gov. Visit https://www.uspto.gov/patents/apply/patent-center for more information about Patent Center and https://www.uspto.gov/patents/docx for information about filing in DOCX format. For additional questions, contact the Electronic Business Center (EBC) at 866-217-9197 (toll-free). If you would like assistance from a USPTO Customer Service Representative, call 800-786-9199 (IN USA OR CANADA) or 571-272-1000. HAROON S. SHEIKH Primary Examiner Art Unit 1751 /Haroon S. Sheikh/ Primary Examiner, Art Unit 1751