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 .
Status of Claims
Claims 1-5, 7-8, 10-12 & 14-22 are amended. Claims 6, 9 & 13 are canceled. Claims 1-5, 7-8, 10-12 & 14-31 are currently pending.
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 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, 3-8, 10-11, 13, 16 & 21-31 are rejected under 35 U.S.C. 103 as being unpatentable over Sakamoto (US 2019/0006707 A1) in view of Chmiola (US 2020/0067128 A1).
Regarding claims 1, 3-7, 10-11, 13 & 21-25, Sakamoto teaches an electrochemical device ([0117]) comprising: a cathode comprising a cathode active material such as LiFePO4 or LiNi1/3Co1/3Mn1/3O2 ([0119] & [0140]), an anode comprising lithium metal ([0120]) and a hybrid electrolyte, wherein the hybrid electrolyte comprises: (i) a first electrolyte (514) having a first surface and an opposed second surface, the first electrolyte comprising a solid state electrolyte material including a garnet phase such as LLZO represented by Li7La3Zr2O12 (Fig. 9A; [0122]-[0132]); (ii) a second electrolyte (516) comprising a liquid electrolyte or a gel electrolyte, the second electrolyte comprising a solvent including propylene carbonate and a salt such as LiTFSI (Fig. 9A; [0078] & [0141]); wherein the cathode faces the first surface of the first electrolyte of the hybrid electrolyte, with the second electrolyte contacting the first surface of the first electrolyte, and wherein the anode contacts the second surface of the first electrolyte of the hybrid electrolyte (Fig. 9A). However, Sakamoto is silent as to a molar concentration of the salt in the solvent ranging from 2 M to 4 M and an interfacial resistance of an interface of the first electrolyte and the second electrolyte stabilizing when an electrochemical cell including the hybrid electrode is cycled. Chmiola teaches an electrochemical device comprising a cathode comprising a cathode active material such as lithium nickel-cobalt-manganese oxide (i.e LiNixCoyMnzO2 where x:y:z is 5:3:2, 6:2:2 or 8:1:1), an anode comprising lithium metal and a hybrid electrolyte; wherein the hybrid electrolyte comprises: a first electrolyte comprising a c-LLZO (i.e Li7La3Zr2O12) solid state electrolyte with a garnet phase and having a first surface facing the cathode and an opposed second surface facing the anode; and a second electrolyte contacting the first surface of the first electrolyte and comprising either i) a liquid electrolyte comprising a solvent such as dimethoxyethane (DME), sulfolane (i.e dimethyl sulfoxide) and carbonates; and a salt such as LiFSI and LiTFSI at a concentration of 0.1 M to 4 M; or a gel electrolyte comprising a polymer such as PEO and a solvent such as dimethoxyethane (DME), sulfolane, acetonitrile and carbonates ([0077]-[0084], [0099]-[0105], [0107], [0129], [0154]-[0162] & [0167]; Examples 1-2, 8 & 10-16).
It would have been obvious to one of ordinary skill in the art, before the effective filing date of the present invention, to use a liquid electrolyte with lithium salt concentration of 2 M to 4 M because such a concentration range is taught to be suitable for a liquid electrolyte used in a hybrid electrolyte composed of a solid-state electrolyte and a liquid electrolyte as taught by Chmiola. “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 MPEP 2144.07. While Sakamoto as modified by Chmiola does not explicitly teach an interfacial resistance of an interface of the first electrolyte and the second electrolyte stabilizing when an electrochemical cell including the hybrid electrolyte is cycled, it is noted that Sakamoto teaches the salt in the second electrolyte being selected from LiPF6, LiClO4, LiBF4, LiFSI, LiTFSI and LiTf ([0141]). However, the instant specification discloses that the interfacial resistance stabilizes for LiTFSI when the cell is cycled ([0068]). Since Sakamoto teaches LiTFSI as a salt which can be used for the second electrolyte in the hybrid electrolyte, the interfacial resistance in Sakamoto’s cell would be expected to similarly stabilize when the cell is cycled. “Where the claimed and prior art products are identical or substantially identical in structure or composition, or are produced by identical or substantially identical processes, a prima facie case of either anticipation or obviousness has been established. In re Best, 562 F.2d 1252, 1255, 195 USPQ 430, 433 (CCPA 1977)”. See MPEP 2112.01 I. Furthermore, the use of LiFTSI as a lithium salt in a liquid electrolyte component of a hybrid electrolyte is known in view of Chmiola as noted above.
Regarding claim 8, Chmiola teaches a salt concentration of 2 M in an exemplary embodiment using sulfolane (with a known density of 1.2 g/cm3) as a solvent such that a resulting concentration in the liquid electrolyte is 1.67 molal (Example 10).
Regarding claim 16, Sakamoto as modified by Chmiola teaches the hybrid electrolyte of claim 1. Sakamoto further teaches the solid-state electrolyte material being densified through conventional sintering ([0038] & [0056]).
Regarding claim 26-28, Sakamoto as modified by Chmiola teaches the device of claim 22 but is silent as to an interface of the first electrolyte and the second electrolyte being 100 mohm.cm2 or less (claim 26), 60 mohm.cm2 or less (claim 27), and 30 mohm.cm2 or less (claim 28). However, Sakamoto teaches the first electrolyte and the second electrolyte each having the same composition as that of the present invention (i.e LLZO as the first electrolyte and the second electrolyte including a lithium salt such as LiTFSI and an organic solvent such as propylene carbonate). Accordingly, an interfacial resistance of an interface of the first electrolyte and the second electrolyte would be expected to be inherently be 30 mohm.cm2 or less. “Where the claimed and prior art products are identical or substantially identical in structure or composition, or are produced by identical or substantially identical processes, a prima facie case of either anticipation or obviousness has been established. In re Best, 562 F.2d 1252, 1255, 195 USPQ 430, 433 (CCPA 1977)”. See MPEP 2112.01 I.
Regarding claims 29-31, Sakamoto as modified by Chmiola teaches the electrochemical device of claim 22 but is silent as to the electrochemical device having greater than 95% utilization upon cycling (claim 29) greater than 99% utilization upon cycling (claim 30) and greater than 95% capacity retention over 10 cycles (claim 31). However, modified Sakamoto teaches the electrochemical device having substantially the same composition as that of the present invention as it relates to the cathode, the anode and the hybrid electrolyte (see rejection of claims 1 & 22 above). Accordingly, modified Sakamoto’s device would be expected to inherently possess the presently claimed properties of claims 29-31. “Where the claimed and prior art products are identical or substantially identical in structure or composition, or are produced by identical or substantially identical processes, a prima facie case of either anticipation or obviousness has been established. In re Best, 562 F.2d 1252, 1255, 195 USPQ 430, 433 (CCPA 1977)”. See MPEP 2112.01 I.
Claims 2 & 20 are rejected under 35 U.S.C. 103 as being unpatentable over Sakamoto (US 2019/0006707 A1) and Chmiola (US 2020/0067128 A1), as applied to claims 1, 3-8, 10-11, 13, 16 & 21-31 above, and further in view of Ohta (US 2011/0244337 A1).
Regarding claims 2 & 20, Sakamoto as modified by Chmiola teaches the hybrid electrolyte of claim 1, wherein the salt is LiTFSI and the solvent is propylene carbonate. Sakamoto more broadly teaches the solid state electrolyte material being represented by LiwAxM2Re3-yOz, where w is 5-7.5; A is selected from B, Al, Ga, In, Zn, Cd, Y, Sc, Mg, Ca, Sr, Ba, and any combination thereof; x is 0-2; M is selected from Zr, Hf, Nb, Ta, Mo, W, Sn, Ge, Si, Sb, Se, Te, and any combination thereof; Re is selected from lanthanide elements, actinide elements, and any combination thereof; y is 0-0.75, and z is 10.875-13.125 ([0017]-[0024]) but does not explicitly teach Li6.5La3Zr1.5Ta0.5O12. Ohta teaches a solid state electrolyte material represented by Li5+XLa3ZrXA2-XO12, wherein A is preferably Nb or Ta and x is from 1.4 to 2 ([0037]) which reads on the presently claimed composition when x=1.5. It would have been obvious to one of ordinary skill in the art, before the effective filing date of the present invention, to use Ohta’s solid state electrolyte material described above because it has higher lithium ion conductivity and lower activation energy as compared to other known Garnet-type lithium ion-conducting oxide as taught by Ohta ([0037]).
Claims 12 & 14-15 are rejected under 35 U.S.C. 103 as being unpatentable over Sakamoto (US 2019/0006707 A1) and Chmiola (US 2020/0067128 A1), as applied to claims 1, 3-8, 10-11, 13, 16 & 21-31 above, and further in view of Christensen (US 2019/0036158 A1).
Regarding claims 12 & 14-15, Sakamoto as modified by Chmiola teaches the hybrid electrolyte of claim 1 but is silent as to the gel comprising a polymer selected from the group recited in instant claim 12 (claim 12), the gel comprising PVDF-HFP (claim 14) and the gel comprising PAN (claim 15). Christensen teaches a gel electrolyte comprising a liquid electrolyte including a salt and an organic solvent as well as a polymer such as PVDF-HFP or PAN ([0040]). It would have been obvious to one of ordinary skill in the art, before the effective filing date of the present invention, to use PAN or PVDF-HFP as the polymer for forming the gel electrolyte as suitable polymer materials for forming a gel electrolyte as taught by Christensen ([0040]).
Claims 17-19 are rejected under 35 U.S.C. 103 as being unpatentable over Sakamoto (US 2019/0006707 A1) and Chmiola (US 2020/0067128 A1), as applied to claims 1, 3-8, 10-11, 13, 16 & 21-31 above, and further in view of Zhu (US 2021/0249693 A1).
Regarding claims 12 & 14-15, Sakamoto as modified by Chmiola teaches the hybrid electrolyte of claim 1 but is silent as to the solid-state electrolyte material being heat treated under inert atmosphere to remove surface impurities (claim 17), wherein the heat-treatment temperature is in a range of 350°C to 700°C (claim 18) and in a range of 375°C to 425°C (claim 19). Zhu teaches heat-treating a solid-state electrolyte material such as LLZO at 400°C to 500°C in an inert atmosphere to remove surface impurities ([0041] & [0044]). It would have been obvious to one of ordinary skill in the art, before the effective filing date of the present invention, to perform a heat-treatment as described by Zhu above, on Sakamoto’s solid-state electrolyte material in order to remove surface impurities as taught by Zhu ([0044]).
Response to Arguments
Applicant's arguments filed 01/09/2026 have been fully considered but they are not persuasive. In response to Applicant’s arguments that the combination of Sakamoto and Chmiola does fairly teach or suggest the claimed subject matter, the examiner respectfully disagrees. Specifically, Applicant argues that Sakamoto as modified by Chmiola does not disclose an interfacial resistance of an interface of the first electrolyte and the second electrolyte stabilizing when an electrochemical cell including the hybrid electrolyte is cycled since Sakamoto is silent as to a molar concentration of the salt in the solvent ranging from 2M to 4M and as to the claimed interfacial resistance of an interface of the first electrolyte and the second electrolyte. Applicant further notes that Chmiola makes no mention of a cathode contacting the second electrolyte of the hybrid electrolyte, wherein the cathode comprises a lithium-based cathode active material and the electrolyte comprises a solvent and a salt including the claimed imide salts, wherein the solvent is selected from the presently claimed group. However, contrary to Applicant’s assertions, Chmiola, similarly to Sakamoto ([0140]-[0141]), discloses an exemplary embodiment in which a cathode active material such as LiNi0.6Mn0.2Co0.2O2 (i.e lithium-based cathode material) is in contact with the first electrolyte (i.e bulk composite scaffold made up of LLZO) after the cathode active material is infiltrated in the porous first electrolyte and also in contact with a catholyte including a lithium salt such as LiFSI dissolved in sulfolane ([0211]-[0212]). However, Chmiola more broadly teaches that the solvent used to form the catholyte can be “carbonates, esters, ethers, sulfones, ketones, amides, nitriles, imides and combinations thereof” ([0159]-[0160]) and the lithium salt can be LiFTSI ([0161]). Thus, while Sakamoto is silent as to the claimed concentration range of 2M to 4M for the lithium salt, the teachings of Chmiola render obvious the use of 2M to 4M of lithium salt in the catholyte because such a concentration range is taught to be suitable for a liquid electrolyte including the same salt as Sakamoto as well as the same carbonate solvents for the cathode side of the cell as described in Chmiola ([0162]). Since Sakamoto teaches the same lithium salt and solvent as the presently claimed second electrolyte composition, when Sakamoto’s second electrolyte is configured to have a lithium salt concentration of 2M to 4M (as would have been obvious from the teachings of Chmiola), the claimed interfacial resistance property at the interface of the first electrolyte and second electrolyte would be expected to be present in modified Sakamoto. While the examiner acknowledges that the use of a salt selected form the group consisting of imides-based salt recited in claim 1 would solve the problems of the prior art that have a solid liquid electrolyte interphase with a high resistance, it is noted that Sakamoto and Chmiola each disclose exemplary embodiments using a lithium (halosulfonyl)imide as a lithium salt for the catholyte. Moreover, one of ordinary skill in the art readily understands that the use of liquid electrolyte in conjunction with the first electrolyte can improve the lithium ion charge transfer kinetics and interfacial behavior of the ceramic electrolyte c-LLZO (i.e corresponding to the first electrolyte) by providing a liquid electrolyte comprising one or more solvents in which one or more conducting lithium salt is dissolved in appreciable molarities as taught by Chmiola ([0154]-[0156]). With regard to Applicant’s arguments that the properties recited in claim 26-28 would not have been inherent to Sakamoto’s invention as modified by Chmiola, the examiner respectfully disagrees. Applicant further argues that Sakamoto and Chmiola do not disclose any information about the efficacy of the claimed salts in achieving the interfacial resistance properties recited in claims 26-28. However, as noted above, Sakamoto and Chmiola’s exemplary embodiments for a catholyte composition each include LiFSI which reads on the claimed lithium (halosulfonyl)imide salt. In light of the instant specification’s disclosure that the claimed imide-based lithium salts can achieve the claimed resistance properties, one of ordinary skill in the art would expect Sakamoto and Chmiola’s LiFSI salt along with the LLZO-based first electrolyte used in both references to achieve the claimed interfacial resistance properties. Furthermore, the claimed concentration range of 2M to 4M for the lithium salt would have been obvious based on Chmiola’s disclosure that a liquid electrolyte comprising one or more solvents in which one or more conducting lithium salt is dissolved in appreciable molarities (0.1 M to 4 M with an exemplary embodiment using 2 M) can improve the interfacial behavior of the LLZO electrolyte (i.e first electrolyte) and the liquid electrolyte ([0154]-[0156] & [0162]).
Thus, in view of the foregoing, claims 1-5, 7-8, 10-12 & 14-31 stand rejected.
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure. Schleutker (“On the interfacial charge transfer between solid and liquid Li+ electrolytes”) teaches higher salt concentration resulting in lower interfacial resistance between solid electrolytes such as LLZO and liquid electrolytes including a lithium salt such as LiPF6 (Abstract; 5. Discussion; Fig. 5).
THIS ACTION IS MADE FINAL. Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a). A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
Contact Information
Any inquiry concerning this communication or earlier communications from the examiner should be directed to NATHANAEL T ZEMUI whose telephone number is (571)272-4894. The examiner can normally be reached M-F 8am-5pm (EST).
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/NATHANAEL T ZEMUI/Examiner, Art Unit 1727