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 .
file provisions of the AIA .
Election/Restrictions
Claims 12-20 are withdrawn from further consideration pursuant to 37 CFR 1.142(b), as being drawn to a nonelected invention, there being no allowable generic or linking claim. Applicant timely traversed the restriction (election) requirement in the reply filed on 02/11/2025.
Drawings
The drawings are objected to as failing to comply with 37 CFR 1.84(p)(5) because they include the following reference character(s) not mentioned in the description: FIG. 4D has “435” in the drawing, but “435” is not in the specification. Corrected drawing sheets in compliance with 37 CFR 1.121(d), or amendment to the specification to add the reference character(s) in the description in compliance with 37 CFR 1.121(b) are required in reply to the Office action to avoid abandonment of the application. Any amended replacement drawing sheet should include all of the figures appearing on the immediate prior version of the sheet, even if only one figure is being amended. Each drawing sheet submitted after the filing date of an application must be labeled in the top margin as either “Replacement Sheet” or “New Sheet” pursuant to 37 CFR 1.121(d). If the changes are not accepted by the examiner, the applicant will be notified and informed of any required corrective action in the next Office action. The objection to the drawings will not be held in abeyance.
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.
Claims 1, 3-10 are rejected under 35 U.S.C. 103 as being unpatentable over Platt et al. (WO 2020153973 A1, “Platt”) in view of Katori et al. (US 20200194825 A1, “Katori”) and Makino et al. (US 20190198919 A1, “Makino”).
Regarding claim 1, Platt discloses a method for making a solid-state argyrodite electrolyte (see title “solid electrolyte material synthesis method”; see [0022] “Li6PS5Br argyrodite” and see [0027] “Li6PS5Cl argyrodite”) the method comprising: contacting a first suspension and a first solution to form a precursor (see [0023] “precursors to generate the solid electrolyte”; see [0014] “These two solutions require a very short stirring time to produce two homogenous solutions that may be mixed and stirred again to form a final homogenous mixture of the solid electrolyte solution”; see [0022] 1st line disclosed mixing of two different solutions/suspension generated in step 120 (generates suspension) and step 130 (generates solution); see [0023] describes “homogenization and reaction of precursors to generate the solid electrolyte”), the first suspension comprising Li3PS4 (see [0018] “step 120” & “PS43- backbone” & “approximately 1 mole of Li2S is used for every 1 mole of P2S5 to achieve the desired solution”; see [0020] describes “reactants are Li2S and P2S5, Li3PS4”) and an ester solvent (see [0017] describes “solvents for use in step 120” and “ester molecules”). Platt discloses the first solution comprising Li2S, LiX (where X is selected from chloride (Cl), bromide (Br), iodine (I), or a combination thereof), and an alcohol solvent (see [0022] describes “second reactants Li2S and LiBr, and second solvent” & “to form a Li6PS5Br argyrodite composed of PS43- units”; see [0021] describes “multiple solvents” for step 130 & [0020] describes “second solvents” & “alcohols”). Platt discloses and removing the ester solvent and the alcohol solvent from the precursor to form the solid-state argyrodite electrolyte represented by the formula Li6PS5X, where X is selected from chloride (Cl), bromide (Br), iodine (I), or any combination thereof (see [0014] describes “the solvents may be removed from the solution by a technique such as vacuum drying to form the final solid electrolyte”; see [0022] describes “Li6PS5Br argyrodite”) and the solid-state argyrodite electrolyte has an ionic conductivity greater than or equal to about 1.0 x 10-4 S/cm to less than or equal to about 10 x 10-3 S/cm at about 25 °C (see P7 line 30 through P8 line 6 “Example 3 (Dual solution Method) ionic conductivity of the sample was 1.6 mS/cm.”; see P8 line 5 “ambient temperature”).
Platt discloses 1.6 mS/cm which is equivalent to 0.0016 S/cm, which lies within the claimed range of about 1.0 x 10-4 S/cm to less than or equal to about 10 x 10-3 S/cm.
Platt does not explicitly disclose ester solvent selected from the group consisting of: methyl formate, methyl propionate, methyl butyrate, methyl pentanoate, ethyl formate, ethyl propionate, ethyl butyrate, ethyl pentanoate, ethyl hexanoate, ethyl heptanoate, ethyl octanoate, ethyl decanoate, propyl acetate, propyl propanoate, isopropyl acetate, isopropyl palmitate, butyl acetate, butyl butyrate, isobutyl acetate, amyl acetate, pentyl propanoate, pentyl butyrate, pentyl pentanoate, pentyl hexanoate, isoamyl acetate, sec-amyl acetate, and combinations thereof.
Katori teaches butyl acetate as an organic solvent (see [0047]) and “the organic solvent is not particularly limited as long as it does not react with Li2S or P2S5” (see [0047]).
Platt and Katori are analogous to the current invention because they are related to the same filed of endeavor, namely method for producing solid electrolyte (see Katori abstract).
Therefore, it would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to incorporate “butyl acetate”, suggested by Katori into the method for making the solid-state electrolyte of Platt, because Katori teaches the organic solvent butyl acetate does not react with Li2S or P2S5 (see Katori [0047]).
Platt does not explicitly disclose an alcohol solvent selected from the group consisting of: 1-butanol, 2-butanol, isobutanol, 1-pentanol, 3-pentanol, isopentanol, neopentanol, cyclopentanol, hexanol, cyclohexanol, methylcyclohexanol, heptanol, nonanol, and combinations thereof.
Makino teaches method for manufacturing solid electrolyte (see title). Makino teaches alcohol solvent is isobutanol (see [0164] alcohol compound solvent includes & “isobutanol”).
Platt and Makino are analogous to the current invention because they are related to the same field of endeavor, namely methods for manufacturing solid electrolytes.
Makino teaches isobutanol amongst a list of other alcohol compound solvents. KSR Rationale E states that it is obvious to choose "from a finite number of identified, predictable solutions, with a reasonable expectation of success".
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 isobutanol from the list of possible alcohol compound solvents taught in Makino.
Regarding claim 3, modified Platt discloses the method of claim 1 and further discloses wherein contacting the first suspension and the first solution to form a precursor comprises forming a mixture comprising the first suspension and the first solution and mixing and stirring the mixture (see [0023] “precursors to generate the solid electrolyte”; see [0014] “These two solutions require a very short stirring time to produce two homogenous solutions that may be mixed and stirred again to form a final homogeneous mixture of the solid electrolyte solution.”; see [0022] “the two different solutions/suspensions” & “typically, reaction/stir time for each step 120 or step 130 may be between a few minutes and a few hours. Specific reaction/stirring time depend upon the details of the reactants and solvent used including parameters such as initial powder size, total volume, and total solids loading.”; see [0023] “Next, in step 140 the first and second combinations may be mixed for a predetermined period of time and temperature in order to create a solid electrolyte solution. Mixing time is not specifically limited as long as it allows for appropriate homogenization and reaction of precursors to generate the solid electrolyte.”).
Regarding claim 4, modified Platt discloses the method of claim 1 and further discloses wherein the mixture is mixed and stirred for a time greater than or equal to about 30 minutes to less than or equal to about 24 hours (see [0022] “Example processes described below indicated various reaction/stirring time.”; see [0023] “Next, in step 140 the first and second combinations may be mixed for a predetermined period of time and temperature in order to create a solid electrolyte solution” & “typically, reaction/stirring time for step 140 may be between a few minutes and a few hours.”; see [0027] Example 3 “stirred for 30 min.”; “stirred for 30 min”; combined and further stirred for 15 mins”).
Regarding claim 5, modified Platt discloses the method of claim 1 and further discloses wherein the precursor has a molar ratio of 1:1 of Li2S:P2S5 and Platt also discloses Li3PS4 (see [0018] “approximately 1 mole of Li2S is used for every 1 mole of P2S5 to achieve the desired solution.”; see [0020] “reactants are Li2S and P2S5, Li3PS4”; see [0027] “it should be understood that the present method may include electrolytes with other phases with and without halogen such as compounds: Li3PS4”; see Example 4 “0.615 g of P2S5 was mixed with 0.127 g Li2S in 25 mL ethyl acetate (EA) and stirred for 5 h” & “0.223 g LiCl was mixed with 0.478 g Li2S in 25 mL ethanol and stirred for 5 h” & “Li6PS5Cl argyrodite was the primary phase observed”). Platt does not explicitly disclose wherein the precursor has a 1:1:1 molar ratio of Li3PS4: Li2S: LiX.
However, Platt does disclose that ratios and amounts of the various reactions are not limited and may be changed to obtain the appropriate final material stoichiometry (see [0021] “For step 130, the ratios and amounts of the various reactants are not specifically limited, and may be chosen to obtain the appropriate final material stoichiometry.”).
Therefore, it would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to include the precursor has a ratio to obtain the appropriate final material stoichiometry, as suggested by Platt. Doing so would obtain the final material stoichiometry of the Li6PS5CL argyrodite (see P8 Example 4 line 15 “Li6PS5Cl argyrodite was the primary phase observed”), as suggested by Platt.
Regarding claim 6, modified Platt teaches the method of claim 1 and further discloses wherein the method further comprises preparing the first suspension, wherein preparing the first suspension comprises: contacting Li2S and P2S5 in the ester solvent to form a mixture (see [0018] “step 120” & “PS43- backbone, in one embodiment, approximately 1 mole of Li2S is used for every 1 mole of P2S5 to achieve the desired solution. The amount of solvent added to the combination is not limited as long as the amount of solvent supports synthesis of the desired composition of solid” & “multiple solvents may be mixed together with the noted reactants” & see [0017] “solvents for use in step 120” & “ester molecules”); and mixing and stirring the mixture (see [0022] “the two different solution/suspensions” & “Typically, reaction/stir time for each step 120 or step 130 may be between a few minutes and a few hours. Specific reaction/stirring time depend upon the details of the reactants and solvent used including parameters such as initial powder size, total volume, and total solids loading”; see P8 Example 4 (Dual Solution Method) “0.615 g of P2S5 was mixed with 0.127 g Li2S in 25 mL ethyl acetate (EA) and stirred for 5 h.”). Platt does not explicitly disclose a time greater than or equal to about 8 hours to less than or equal to about 96 hours.
However, Platt does disclose mixing time is not limited as long as it allows for appropriate homogenization and reaction of precursors (see [0023] “in step 140 the first and second combinations may be mixed for a predetermined period of time and temperature in order to create a solid electrolyte solution. Mixing time is not specifically limited as long as it allows for appropriate homogenization and reaction of precursors to generate the solid electrolyte.”).
Therefore, it would have been prima facie obvious to one of ordinary skill in the art to include mixing and stirring and a time in order to allow for homogenization, as suggested by Platt. Doing so allows for appropriate reaction of precursors to generate the solid electrolyte, as suggested by Platt.
Regarding claim 7, modified Platt discloses the method of claim 1 and further discloses a molar ratio of 1:1 for Li2S:P2S5 (see [0018] and P8 Example 4). Platt discloses a total concentration of the Li2S and the P2S5 in the mixture is greater than or equal to about 0.5 wt. % (see P8 line 20 through line 27 “Example 4 (Dual Solution Method) 0.615 g of P2S5 was mixed with 0.127 g Li2S in 25 mL ethyl acetate (EA) and stirred for 5 h. The Li2S particles were approximately 0.5 mm diameter. 0.223 g LiCl was mixed with 0.478 g Li2S in 25 mL ethanol and stirred for 5 h. The EA and ethanol mixtures were combined and further stirred for 15 min, and then the final mixture was heated at 150 °C under vacuum for 1.5 h to form a ceramic powder. The powder was further heated at 550 °C under flowing argon for 2h. X-ray diffraction analysis was carried out on the powders. Li6PS5Cl argyrodite was the primary phase observed.”). Platt does not explicitly disclose wherein the mixture has a molar ratio of the Li2S and P2S5 greater than or equal to about 2.9 to less than or equal to about 3.1.
However, Platt does disclose the ratios and amounts of the various reactants are not limited and may be chosen to obtain the appropriate final material stoichiometry (see [0021] “For step 130, the ratios and amounts of the various reactants are not specifically limited, and may be chosen to obtain the appropriate final material stoichiometry.”).
Therefore, it would have been prima facie obvious to one of ordinary skill int the art before the effective filing date of the claimed invention to incorporate ratios and amounts to obtain the appropriate final material stoichiometry, as suggested by Platt.
Regarding claim 8, modified Platt discloses the method of claim 1 and further discloses wherein the method further comprises; preparing the first solution, the preparing of the first solution comprising: contacting Li2S and LiX in the alcohol solvent to form a mixture; and mixing and stirring the mixture for a time greater than or equal to about 0.1 hours to less than or equal to about 24 hours (see [0019] “ step 130” & “second reactants may include, for example, Li2S and LiX (X = F, Cl, Br, or I).”; see P8 lines 20-27 “Example 4 (Dual Solution Method) 0.615 g of P2S5 was mixed with 0.127 g Li2S in 25 mL ethyl acetate (EA) and stirred for 5 h. The Li2S particles were approximately 0.5 mm diameter. 0.223 g LiCl was mixed with 0.478 g Li2S in 25 mL ethanol and stirred for 5 h. The EA and ethanol mixtures were combined and further stirred for 15 min, and then the final mixture was heated at 150° C. under vacuum for 1.5 h to form a ceramic powder.”).
Platt discloses mixing and stirring for 5 hours which lies within the claimed range of a time greater than or equal to about 0.1 hours to less than or equal to about 24 hours, which renders this claim obvious.
Regarding claim 9, modified Platt discloses the method of claim 1 and discloses a molar ratio of 1:1 for Li2S:P2S5 (see P8 lines 20-27 & [0018]). Platt does not explicitly disclose wherein the mixture has a molar ratio of the Li2S and the LiX of greater than or equal to about 0.9 to less than or equal to about 1.1, and a total concentration of the Li2S and the LiX in the mixture is greater than or equal to about 0.1 wt.% to less than or equal to about 20 wt.%.
However, Platt does disclose concentration of Li2S and the LiX (see P8 lines 20-27 “Example 4” & “0.615 g of P2S5” & “0.127 g Li2S” & “0.223 g LiCl” & “0.478 g Li2S”; see [0021] “ratios and amounts of the various reactants are not specifically limited, and may be chosen to obtain the appropriate final material stoichiometry”).
Therefore, it would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to incorporate ratios and amounts of various reactants to obtain the appropriate final material stoichiometry, as suggested by Platt.
Regarding claim 10, modified Platt discloses the method of claim 1 and further discloses wherein the removing the ester solvent and the alcohol solvent form the precursor solution to form the solid-state argyrodite electrolyte further comprises (see [0014] “The solvents may be removed from the solution by a technique such as vacuum drying to form the final solid electrolyte”; see [0022] “Li6PS5Br argyrodite”; see [0018] “multiple solvents”; see [0017] “ester molecules”; see [0021] “multiple solvents”; see [0020] “second solvents” & “alcohols”) heating the precursor to a temperature greater than or equal to about 80 °C to less than or equal to about 700 °C for a time greater than or equal to about 30 minutes to less than or equal to about 48 hours (see P8 lines 20-27 “Example 4 (Dual Solution Method)” & “and then the final mixture was heated at 150 °C under vacuum for 1.5 h to form a ceramic powder. The powder was further heated at 550 °C. under flowing argon for 2 h.” & “Li6PS5Cl argyrodite was the primary phase observed”).
Platt discloses temperature 150 °C and 550 °C which lie within the temperature range of temperature greater than or equal to about 80 °C to less than or equal to about 700 °C, which renders this claim limitation obvious.
Platt discloses a time 1.5 h and 2 h which lie within the claimed range of greater than or equal to about 30 minutes to less than or equal to about 48 hours, which renders this claim limitation obvious.
Claim 2 is rejected under 35 U.S.C. 103 as being unpatentable over Platt et al. (WO 2020153973 A1, “Platt”) in view of Katori et al. (US 20200194825 A1, “Katori”) and Makino et al. (US 20190198919 A1, “Makino”) as applied to claim 1 above, and further in view of Yubuchi et al. (Yubuchi, So et al.; “Lithium-Ion-Conducting Argyrodite-Type Li6PS5X (X = Cl, Br, 1) Solid Electrolytes Prepared by a Liquid-Phase Technique Using Ethanol as a Solvent”; American Chemical Society, Applied Energy Materials; July 11, 2018; pages 3622 – 3629).
Regarding claim 2, modified Platt discloses the method of claim 1 and further discloses wherein the ester solvent further comprises ethyl acetate (see [0017] “ethyl acetate” & see [0018] “for step 120” & “multiple solvents may be mixed together with the noted reactants”), and the alcohol solvent (see [0021] describes “multiple solvents”; see [0020] describes “second solvents” & “alcohols” & “the typical action of the second solvent upon the second reactants is to reduce the particle size or completely dissolve the reactants”). Platt does not explicitly disclose the alcohol solvent further comprises tert-butanol.
Yubuchi teaches tert-butanol alcohol solvent (see P3623, par. 3, line 5, “To find favorable synthesis conditions such as appropriate halogen species, alcohol solvents”; see P3623, 2. Experimental Section, 2.1. Preparation of Materials “tert-butyl alcohol” & “were used as the alcohol solvents”).
It would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to incorporate tert-butyl alcohol as the alcohol solvent, as suggested by Yubuchi. Because doing so reduces the particle size or completely dissolves the reactants, as disclosed by Platt (see [0020] “the typical action of the second solvent upon the second reactants is to reduce the particle size or completely dissolve the reactants”).
Claim 11 is rejected under 35 U.S.C. 103 as being unpatentable over (WO 2020153973 A1, “Platt”) in view of Katori et al. (US 20200194825 A1, “Katori”) and Makino et al. (US 20190198919 A1, “Makino”) as applied to claim 1 above, and further in view of Zhang et al. (Zhixia Zhang, Long Zhang, Yanyan Liu, Chuang Yu, Xinlin Yan, Bo Xu, Li-min Wang, Synthesis and characterization of argyrodite solid electrolytes for all-solid-state Li-ion batteries, Journal of Alloys and Compounds, Volume 747, 2018, Pages 227-235).
Regarding claim 11, modified Platt discloses the method of claim 1 and further Platt discloses wherein the solid-state argyrodite electrolyte comprises a plurality of Li6PS5X particles (see [0022] “to form a Li6PS5Br argyrodite”; see [0019] “step 130” & “second reactants may include, for example, Li2S and LiX (X = F, Cl, Br, or I).”; see P8 line 7 “Example 4 (Dual Solution Method)” & P8 line 15 “Li6PS5Cl argyrodite was the primary phase observed”; see [0014] “Described herein are novel soft chemical processes relying upon synthesis methods using multipart solvent/solution based approaches employing selective solvation and/or particle size reduction for different reactants used to form the solid electrolytes”). Platt does not explicitly disclose having an average particle size greater than or equal to about 0.1 micrometer to less than or equal to about 100 micrometers.
However, Platt does disclose on P8 line 18 “ionic conductivity of the sample was 1.3 mS/cm.” Platt also discloses “particle size reduction for different reactants used to form the solid electrolyte” in [0014].
Zhang teaches average particle size of Li6PS5Cl is 12 µm (see P230, FIG. 2 “SEM images of the Li6PS5Cl morphology are displayed in Fig. 2” & “the average particle size is 12 µm for the former and 8 µm for the latter sample, thus leading to higher ionic conductivity of the sintered sample than that of the mechanically alloyed sample”).
A result effective variable is a variable which achieves a recognized result. The determination of the optimum or workable ranges of a result-effective variable is routine experimentation and therefore obvious. MPEP § 2144.05.
Thus, the average particle size is a variable that achieves the recognized result of improved ionic conductivity. That makes the average particle size a result-effective variable. Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to routinely experiment with the average particle size and come up with greater than or equal to about 0.1 micrometer to less than or equal to about 100 micrometers.
Response to Arguments
Applicant’s arguments, see P11-P12, filed 12, with respect to the rejection of claim 1 under 35 U.S.C. § 103 as being unpatentable over Platt et al. (WO 2020153973 A1, “Platt”) in view of Yamamoto et al. (US 20180062200 A1, “Yamamoto”), Katori et al. (US 20200194825 A1, “Katori”) and Makino et al. (US 20190198919 A1, “Makino”) have been fully considered and are persuasive. Therefore, the rejection has been withdrawn. However, upon further consideration, a new ground(s) of rejection is made in view of Platt et al. (WO 2020153973 A1, “Platt”) in view of Katori et al. (US 20200194825 A1, “Katori”) and Makino et al. (US 20190198919 A1, “Makino”).
As previously stated in the rejection above, Katori teaches butyl acetate as an organic solvent (see [0047]) and “the organic solvent is not particularly limited as long as it does not react with Li2S or P2S5” (see [0047]).
Therefore, it would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to incorporate “butyl acetate”, suggested by Katori into the method for making the solid-state electrolyte of Platt, because Katori teaches the organic solvent butyl acetate does not react with Li2S or P2S5 (see Katori [0047]).
As previously stated in the rejection above, Makino teaches method for manufacturing solid electrolyte (see title). Makino teaches alcohol solvent is isobutanol (see [0164] alcohol compound solvent includes & “isobutanol”).
Makino teaches isobutanol amongst a list of other alcohol compound solvents. KSR Rationale E states that it is obvious to choose "from a finite number of identified, predictable solutions, with a reasonable expectation of success".
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 isobutanol from the list of possible alcohol compound solvents taught in Makino.
Conclusion
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/S.A.A./Examiner, Art Unit 1725
/JAMES M ERWIN/Primary Examiner, Art Unit 1725 02/17/2026