Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Claim Objections
Claim 8 is objected to because of the following informalities:
Claim 8 recites the additional limitation “wherein the organic solvent is selected from a combination of the ester solvent and the ether solvent.”
Applicant’s recitation of the term “is selected from” lends itself to interpretation as a Markush group; however, the claim lacks transitional language indicating whether the group is closed. If the group applicant denotes as “a combination of the ester solvent and the ether solvent” is closed, the claim should also recite “consisting of.” If the group is not closed, other words of transition (“comprising” / “comprises” or “consisting essentially of” / “consists essentially of”) should be used as appropriate and the “is selected from” language should be removed. Appropriate correction is required.
For purposes of examination, the examiner has interpreted the organic solvent recited in Claim 8 to mean a mixture in any volume proportion of one or more esters with one or more ethers not also including any other class of solvent [the ester(s) and ether(s) together represent 100% of the organic solvent].
Claim Rejections - 35 USC § 102
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of the appropriate paragraphs of 35 U.S.C. 102 that form the basis for the rejections under this section made in this Office action:
A person shall be entitled to a patent unless –
(a)(1) the claimed invention was patented, described in a printed publication, or in public use, on sale, or otherwise available to the public before the effective filing date of the claimed invention.
(a)(2) the claimed invention was described in a patent issued under section 151, or in an application for patent published or deemed published under section 122(b), in which the patent or application, as the case may be, names another inventor and was effectively filed before the effective filing date of the claimed invention.
Claim(s) 1 through 7 and 10 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Park
et al. (WO 2018/190559 A1), cited via US equivalent US 10,858,749 B2 (“Park”).
Regarding Claim 1, Park discloses:
A manufacturing method of a lithium battery negative electrode, comprising:
providing a copper foil (“A lithium metal electrode was prepared by plating lithium metal on a Cu current collector through electroplating” Col. 7, Lines 32-33); and
performing an electroplating process to form a lithium deposition layer on the copper foil, wherein an electrolyte solution used in the electroplating process comprises an organic solvent and fluorine-containing lithium salt [See Example 1, Col. 7, Lines 32-48 , indicating electroplating using the fluorine-containing lithium salt LiFSI (1M) dissolved in the organic solvent dimethyl ether (DME); see also the solvents disclosed at Col. 4 Lines 24-31 and the fluorinated lithium salts disclosed at Col. 2, Lines 43-48 and Col. 4, Lines 9-15 and 32-40];
wherein the organic solvent comprises an ester solvent [See Comparative Example 1, Col. 8 Lines 5-15 using 25:50:25 v/v ethylene carbonate (EC): diethylene carbonate (DEC): dimethylene carbonate (DMC)], an ether solvent [See Examples 1-4 and Comparative Examples 2-4, Col. 7, Line 30 – Col. 8, Line 45 using dimethyl ether (DME)], an alcohol solvent, or a combination thereof, and
the fluorine-containing lithium salt comprises lithium hexafluorophosphate [See Col. 4, Line 34], lithium bis(fluorosulfonyl)imide [See Col. 4, Line 34], lithium trifluoromethanesulfonate [See Col. 4, Line 36], lithium difluoro(oxalato)borate, lithium bis(trifluoromethanesulfonyl)imide [See Col. 4, Line 37], or a combination thereof.
Regarding Claim 2, Park discloses the manufacturing method of Claim 1, and also discloses:
wherein the electrolyte solution at least comprises the ester solvent, and a volume ratio thereof accounts for more than 50%. [See Comparative Example 1, Col. 8 Lines 5-15 using 25:50:25 v/v ethylene carbonate (EC): diethylene carbonate (DEC): dimethylene carbonate (DMC)]
Regarding Claim 3, Park discloses the manufacturing method of Claim 1, and also discloses:
wherein a usage ratio of the fluorine-containing lithium salt in the electrolyte solution is between 0.1 mol/L and 5 mol/L. [See Col. 4, Lines 41-44 indicating concentration of lithium salt is preferably from 1 M to 4 M; See also Examples 1-4 and Comparative Examples 1-4, Col.7, Line 30 – Col. 8, Line 45 using fluorinated lithium salts at 1 M or 3 M]
Regarding Claim 4, Park discloses the manufacturing method of Claim 1, and also discloses:
wherein a current density in the electroplating process is between 1mA/cm2 and 5mA/cm2. [See Col. 7, Lines 47-48 indicating that electroplating in Example 1 was carried out using a current density of 3 mA/cm2.]
Regarding Claim 5, Park discloses the manufacturing method of Claim 1, and also discloses:
wherein a thickness of the lithium deposition layer is between 1 micron and 20 microns. [See Col. 3, Lines 29-31, “…a lithium metal electrode having a thickness level of 20 µm or less…can be prepared.”]
Regarding Claim 6, Park discloses the manufacturing method of Claim 1, and also discloses:
wherein the electrolyte solution further comprises an additive (corresponding to “a lithium nitrogen oxide; and an additive represented by … MNOx … M is Cs, Rb, K, Ba, Sr, Ca, Na or Mg and x is 2 or 3” [See Col. 2, Lines 16-25]), and the additive comprises lithium nitrate [See Examples 1-4 and Comparative Examples 2 and 3, Col. 7, Line 30 – Col. 8, Line 35, each employing lithium nitrate; See also Col. 4, Lines 61-63].
Regarding Claim 7, Park discloses the manufacturing method of Claim 6, and also discloses:
wherein a usage ratio of the additive in the electrolyte solution is between 1 wt% and 10 wt%. [See Col. 2, Lines 32-35, “The lithium nitrogen oxide may be included in the electroplating solution in a content of 1% by weight to 5% by weight based upon the total weight of the electroplating solution.”; See also Examples 1-4 and Comparative Examples 2 and 3, Col. 7, Line 30 – Col. 8, Line 35, each employing 2% by weight lithium nitrate].
Regarding Claim 10, Park discloses the manufacturing method of Claim 1, and also discloses:
wherein a surface of the lithium deposition layer comprises a fluorine-containing compound. [See Col. 4, Lines 38-40, “…and particularly, using LiFSI may be advantageous in electroplating lithium metal on a current collector.”; See also Col. 4, Lines 52-53, “…the electroplating solution may form a stable film on a lithium metal electrode…” and Col. 3, Lines 19-22, “…surface properties of a prepared lithium metal electrode can be controlled depending on a composition of the electroplating solution.”]
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 8 and 9 are rejected under 35 U.S.C. 103 as being unpatentable over Park et al. (WO 2018/190559 A1), cited via US equivalent US 10,858,749 B2 (“Park”), in view of Hasegawa (WO 2018/212027 A1), cited via US equivalent US2020/0106134 A1 (“Hasegawa”).
Regarding Claim 8, Park discloses the manufacturing method of Claim 1. Park does not disclose:
wherein the organic solvent is selected from a combination of the ester solvent and the ether solvent.
Hasegawa discloses:
wherein the organic solvent is selected from a combination of the ester solvent and the ether solvent. [See, e.g., “Electrolyte Solution” Par. 18 “The electrolyte solution of the present example embodiment comprises a fluorinated ether as an electrolyte solvent and a cyclic dicarboxylic acid ester as an additive.”; Pars. 19-25 listing fluorinated ethers, functional advantages and preferred proportions thereof; and Pars. 26-64 listing cyclic dicarboxylic acid esters and functional advantages thereof.]
Park and Hasegawa are each in the same field of endeavor as the present invention, specifically, battery technology and more particularly solvent systems for use as electrolytes advantageous in passivation of anodes in lithium batteries. Accordingly, these references constitute analogous art as required by MPEP §2141.01(a).
One of ordinary skill in the art would have been motivated to combine the electroplating teachings of Park with the electrolyte solvent systems taught by Hasegawa, given Hasegawa’s mention at Par. 25 of improvements from the ether component in ion conductivity and resistance to oxidation of the electrolyte and at Par. 26 of the protective film-forming function of the cyclic dicarboxylic acid ester component resulting in the extension of battery life, to arrive at the manufacturing method of Claim 8 before the effective filing date thereof. Additionally, as such mixed solvent systems have been employed before [See the references cited at the conclusion of this Action], one of ordinary skill in the battery art would have had a reasonable expectation of success in modifying the teachings of Park with those of Hasegawa to arrive at the manufacturing method of Claim 8.
Regarding Claim 9, Park in view of Hasegawa discloses the manufacturing method of Claim 8. Hasegawa also discloses:
wherein a volume ratio of the ester solvent and the ether solvent is between 3:1 and 1:1. [See, e.g., “Preparation of electrolyte solution”, Par. 143 “PC [propylene carbonate] (70% by volume) and FE-1 [a fluorinated ether] (30% by volume) were mixed to prepare a nonaqueous solvent.” and permutations of the electrolyte listed in Table 2.]
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant’s disclosure.
Yamashita, et al. (US 6,270,926) discloses a non-aqueous electrolyte solution for a lithium secondary battery prepared by dissolving an electrolyte of a lithium salt (including fluorinated salts) in a mixed solvent comprising propylene carbonate or ethylene carbonate and diethoxyethane or dimethoxyethane. [See Col. 3, Lines 20-24].
Okano, et al. (US 2011/0020711 A1) discloses exemplary solvents for a non-aqueous electrolyte for a lithium battery, including “chain carbonic esters…cyclic carbonic esters…chain ethers…cyclic ethers…and cyclic carboxylic acid esters… . These components can be used singly or in combination of two or more kinds.” [Par 42] Okano also discloses “…since chain carbonic esters and cyclic carbonic esters (including ethylene carbonate, the ester used in applicant’s examples) have a high boiling point and high viscosity, the battery characteristics at a low temperature lowers when these solvents are used. Therefore, the above solvents are preferably a mixed solvent including chain ethers and cyclic ethers having a low boiling point and low viscosity.” [Par 43]
Takami, et al. (US 5,079,109) discloses a nonaqueous electrolyte solvent mixture for a secondary battery consisting of ethylene carbonate, 2-methyltetrahydrofuran, and butylene carbonate in a volume ratio of 50:25:25, corresponding to a 3:1 volume ratio of esters to ether. [See Example 5, Col. 12, Lines 25-30]
Xu, Kang, Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries. Chem. Rev., 2004, 104, 4303-4417 discloses at Section 2.1 (“Solvents”) (p. 4307) five basic requirements for ideal electrolyte solvents, and that for applications in lithium batteries, aprotic solvents with polar group such as carbonyls [esters] and ether-linkages merit consideration. Also disclosed at p. 4310, first column, first paragraph, is that ethylene carbonate was adopted as an electrolyte cosolvent in a number of electrolyte systems, including those containing ethers, after that cyclic ester was found to improve bulk ion conductivity and interfacial properties.
Dudley, J.T. et al., Conductivity of electrolytes for rechargeable lithium batteries. Journal of Power Sources, 35 (1991) 59-82 (“Dudley”) discloses conductivity data for multiple ester - ether solvent combinations. [See, e.g., 2-Methyl Tetrahydrofuran : Dimethoxyethane : Ethylene Carbonate : Propylene Carbonate 25:25:25:25, a 1:1 mixture of ethers and esters [Table 3, Line 4, Page 65], Dimethoxyethane : Ethylene Carbonate 50:50 [Table 3, Line 22, Page 66], and Dimethoxyethane : Ethylene Carbonate : Propylene Carbonate 50:25:25 [Table 3, Lines 23 and 24 for two different lithium hexafluoroarsenate concentrations, Page 66]. Dudley also discloses at page 59, second paragraph, that “Quite commonly, high dielectric constant solvents such as ethylene carbonate (EC) or propylene carbonate (PC) are mixed with low-viscosity, low-dielectric-constant solvents such as 2-methyl tetrahydrofuran (2-MeTHF) to obtain improved conductivity.”
Li, X. et al., Dendrite-Free and Performance-Enhanced Lithium Metal Batteries through Optimizing Solvent Compositions and Adding Combinational Additives. Adv. Energy Mater., 2018, 8, 1703022 discloses that the average coulombic efficiency (CE) of a lithium metal anode improves as the proportion of EC (the cyclic ester, ethylene carbonate) rises in a mixed solvent system of EC and EMC (the linear ester, ethyl methyl carbonate) and that “This is because EC can be reduced to form lithium alkylcarbonates and also conduct ring-opening polymerization to form polycarbonates in the passivation film on Li anode surface. More EC content in the electrolyte could generate more such components in the surface film so the protection of Li metal anode would be enhanced.” [Li, Page 2 Col. 2]
Sun, X. et al., Revisiting the Electroplating Process for Lithium-Metal Anodes for Lithium-Metal Batteries, Angew. Chem. Int. Ed. 2020, 99, 6665-6674 discloses at page 6672, first column, that “additives may affect the diffusion barrier of the interface layer through regulating the composition of the SEI film. For instance, fluoroethylene carbonate (FEC) was extensively used in commercial lithium-ion batteries because a dense LiF-rich SEI can be preferentially formed on the graphite-anode surface.”
Any inquiry concerning this communication or earlier communications from the examiner should be directed to CHRISTOPHER G IZZO whose telephone number is (571)270-0705. The examiner can normally be reached Monday-Friday 8AM-5PM.
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If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Michael N. Orlando can be reached at 571-270-5038. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
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/CHRISTOPHER G. IZZO/ Examiner, Art Unit 1746
/CARSON GROSS/ Primary Examiner, Art Unit 1746
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