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 .
Election/Restrictions
Claims 5-6 are withdrawn from further consideration pursuant to 37 CFR 1.142(b), as being drawn to a nonelected Invention II, there being no allowable generic or linking claim. Applicant timely traversed the restriction (election) requirement in the reply filed on 06/25/2026.
The restriction requirement between Invention I and III is withdrawn as Invention III, an air electrode, comprises Invention I, the layered double hydroxide. Claims 1-4 and 7-9 are rejoined.
However, the restriction requirement between the rejoined group of Invention I/III (claims 1-4 and 7-9) and Invention II (claims 5-6) is maintained. The traversal is on the grounds that the subject matter of claims 1-9 is sufficiently related that a thorough and complete search for a subject matter of the elected claims would necessarily encompass a complete search for the subject matter of the non-elected claims. This is not found persuasive because Invention. Furthermore, issues relevant to one invention are not necessarily relevant to the other invention (e.g. broadest reasonable interpretation of product claims vs. method claims is different), establishing examination burden.
The requirement is still deemed proper and is therefore made FINAL.
Claim Objections
Claim 7 objected to because of the following informalities:
The claim limitation, “a catalyst layer containing the layered double hydroxide of any one of claim 1” should read “a catalyst layer containing the layered double hydroxide of claim 1”.
Appropriate correction is required.
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 and 3 are rejected under 35 U.S.C. 103 as being unpatentable over Mizuno (US 20130143132 A1) in view of Sumboja et al. ("NiMn layered double hydroxides… "), Koshikawa et al. (JP2020200232A, refer to US PG Pub US20210346879A1 for citations, cited in IDS filed 11/28/2023), Goncalves et al. (Vanadium-containing electro and photocatalysts…), and Jiang et al. (“Nickel–cobalt layered double hydroxide nanosheets…”).
Mizuno teaches a metal air battery comprising an air electrode ([0021]) which comprises an air electrode catalyst containing a layered double hydroxide (LDH) ([0017]). Mizuno further discloses the composition of the LDH is represented by the formula: [M2+ 1-xM3+ x(OH)2] [An− x/n.yH2O], where, M2+ represents a divalent metal ion selected from the group consisting of Mg2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+and Zn2+, and M3+represents a trivalent metal ion selected from the group consisting of Al3+, Cr3+, Fe3+, Co3+and In3+ ([0015]).
While Mizuno discloses the LDH is provided with a positively charged cation layer which contains preferably at least two or more types of metal cations composed of mutually different valences ([0024]), Mizuno does not explicitly disclose a layered double hydroxide comprising four elements of Ni, Fe, V, and Co, and further comprising Mn as a fifth element.
Sumboja teaches NiMn-LDHs as oxidation evolution reaction (OER) catalysts (pg. 775, col. 1, first full paragraph) for zinc-air batteries (pg. 774, col. 1). Sumboja teaches that the nanosheets of NiMn LDHs with optimized Ni:Mn molar feeding ration exhibit good crystallinity, big layer spacing, and large surface area, and are highly active and stable during the OER (pg. 775, col. 1, 1st full para.).
Therefore, it would have been obvious to one of ordinary skill in the art, before the effective filing date, to have selected Ni2+ and Mn2+ from the finite list of cations provided by Mizuno for the benefit of an active and stable LDH, as taught by Sumboja.
Koshikawa teaches a layered double hydroxide as a catalyst in a water electrolysis cell ([0001]), where the LDH is used as catalyst material for an anode reaction of water electrolysis (i.e. oxygen evolution reaction that proceeds at the anode in water electrolysis, [0003]-[0004]). Koshikawa teaches that among transition metals, Ni and Fe have particularly high catalytic activity for the OER ([0030];[0003]) and additionally are elements that exist in abundance allowing for reduced material costs ([0030]).
A skilled artisan would recognize that the oxygen evolution reaction (OER) is a half reaction of electrochemical water splitting and is utilized in many key renewable energy systems such as metal air batteries and regenerative fuel cells, and that the OER in Koshikawa’s taught water electrolysis cell is the same OER in the metal-air battery disclosed by Mizuno, as evidenced by Jiang (pg. 445). Furthermore, a skilled artisan would recognize that the OER is kinetically slow and thus requires a catalyst (Jiang 1, pg. 445-446, bridging paragraph), such that a LDH catalyst used in a metal-air battery could be used in a water electrolysis cell, and vice versa, as the catalyst is catalyzing the same OER reaction.
Therefore, it would have been obvious to one of ordinary skill in the art, to have further selected Fe2+ and/or Fe3+ from the finite list of cations provided by Mizuno, for the benefit of high catalytic activity and lower material costs, as taught by Koshikawa.
Goncalves teaches vanadium containing electrocatalysts for the OER including vanadium-containing LDHs (pg. 2183, col. 2, 1st full para.). Goncalves further teaches strong electronic interactions of V ions with other transition metals (Fe and Ni) are responsible for synergistic effects (pg. 2187, col. 1, 1st full para.) and furthermore, that V atoms have an enhanced capability of binding oxygen intermediates compared to Ni and Fe-sites, thus exhibiting higher OER activity (pg. 2187, col. 1, 2nd full para.).
Therefore, it would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to have further included V, for the benefit of enhanced capability of binding oxygen intermediates and higher OER activity, and with reasonable expectation of achieving a successful LDH.
Jiang teaches NiCo-LDHs (pg. 446, col. 1, 2nd full para.), as cobalt- and nickel- containing materials as OER catalysts are versatile candidates for the replacement of precious catalysts due to their abundance, low cost, environmentally friendly, multiple valence state, and high theoretical activity (pg. 446, col. 1, 1st full para.). Jiang further teaches Co and Ni exist as multiple valence state in NiCo-LDH nanosheets, and the solid-state redox couples Ni2+/Ni3+ and Co2+/Co3+ in NiCo-LDHs may provide a notable electrochemical performance since Ni3+ and Co3+ are regarded has catalytically active centers for OER (pg. 448, col. 1-2, bridging para.).
Therefore, it would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to have further selected Co2+ and/or Co3+ from the finite list of cations provided by Mizuno, for the benefit of catalytically active centers for OER, as taught by Jiang, and with a reasonable expectation of achieving a working LDH.
Regarding claim 3, modified Mizuno discloses all limitations as set forth above.
Modified Mizuno discloses a layered double hydroxide (LDH) comprising Ni, Fe, V, Co, and Mn, as rendered obvious above, but does not explicitly disclose wherein the LDH has an atomic ratio Mn/Ni of 0.2 or more or 0.8 or less, which is determined by energy dispersive X-ray spectroscopy (EDS).
Sumboja teaches a NiMn layered double hydroxide catalyst as a more economically attractive catalyst utilized in zinc-air batteries for the oxygen evolution reaction (OER) (pg. 774).
Sumboja further teaches the compositions of LDHs can be easily turned, resulting in the unique redox characteristics and notable catalytic activity during the OER (pg. 774, right col. 1st full para.). Furthermore, Sumboja teaches controlling the Ni:Mn feeding ratio, comparing Ni:Mn ratios of 1:1, 3:1, and 5:1 (pg. 775, 2nd full para.).
Sumboja teaches that with increasing Ni:Mn ratio, the diffraction peaks of NiMn LDHs shifted to a smaller angle, suggesting an expansion of the interlayer spacing, where a large interlayer spacing leads to improved OER activity due to the exposure of more active sites during the catalytic reaction (pg. 775, right col., 2nd full para.).
Furthermore, Sumboja teaches a high crystallinity of the catalyst is desirable for a robust and stable OER (pg. 776, left col., first para.). However, a lower full-width half maximum (FWHM) of the (003) plane was observed with a lower Ni:Mn ratio, suggesting low crystallinity of a sample with a high Ni content (pg. 775-776, bridging para.).
Ni1Mn1 (Ni:Mn ratio is 1:1) exhibited an aggregate of large-sized nanosheets which could lead to its limited catalytically active surface area (pg. 776, left col., first full para.), while Ni3Mn1 (Ni:Mn ratio is 3:1) had a high surface area and large pore volume, indicating its favorably open structure which benefits its catalytic performance due to enlarged catalytically active surface area and good accessibility of electrolyte ions (pg. 776, right. Col., first full para.). This is evidenced by the early onset and large anodic current in Ni3Mn1 (Fig. 3a, pg. 777, right col., first para.), and the peak separation of Ni3Mn1 is smaller relative to that of Ni5Mn1, implying fast reaction kinetics of Ni3Mn1 (Fig. 3a, pg. 777, right col., first para), which is desired by an electrochemical catalyst.
Thus, Sumboja teaches that a balance between a large interlayer spacing and good crystallinity of NiMn LDHs is needed to achieve an optimum catalytic performance during the OER.
Therefore, it would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to have arrived within the claimed range for the Mn:Ni ratio, in order to achieve the desired balance between crystallinity and interlayer spacing to achieve optimum catalytic performance for the LDH, as taught by Sumboja.
Claims 7-9 is rejected under 35 U.S.C. 103 as being unpatentable over Hattori et al. (US20170104254A1) in view of Mizuno (US 20130143132 A1), Sumboja et al. ("NiMn layered double hydroxides… "), Koshikawa et al. (JP2020200232A, refer to US PG Pub US20210346879A1 for citations, cited in IDS filed 11/28/2023), Goncalves et al. (Vanadium-containing electro and photocatalysts…), and Jiang et al. (“Nickel–cobalt layered double hydroxide nanosheets…”).
Regarding claims 7 and 8, Hattori discloses a metal air secondary battery ([0056]-[0057]) comprising an air electrode ([0057]), a separator ([0057]), an electrolytic solution ([0057]) and a negative metal electrode ([0057]).
Hattori further discloses wherein the air electrode comprises a current collector (i.e. positive electrode current collector, [0043]) is porous (i.e. has air permeability to enable supply of air to the air electrode, [0043]).
Furthermore, Hattori discloses wherein the mixture of the air-electrode catalyst, electron conductive material, and hydroxide-ion conductive material (i.e. catalyst layer, [0038]) are press-bonded to a current collector ([0038]). Thus, Hattori satisfies the claim limitation “a catalyst layer covering at least part of the porous current collector”, of claim 7.
Hattori further discloses wherein a hydroxide-ion-conductive material is included in the catalyst layer (i.e. air electrode layer, [0034]) wherein the hydroxide-ion-conductive material comprises a layered double hydroxide having a fundamental composition represented by the formula: M2+ 1-xM3+ x(OH)2An− x/n.mH2O, where M2+ represents at least one divalent cation, M3+ represents at least one trivalent cation, An− represents an n-valent anion, n is an integer of 1 or more, and x is 0.1 to 0.4 ([0036]).
Hattori does not disclose wherein the layered double hydroxide comprises four elements of Ni, Fe, V, and Co, and further comprises the fifth element, Mn, as claimed in claim 1.
Mizuno teaches a similar metal air battery comprising an air electrode ([0021]) which comprises an air electrode catalyst containing a layered double hydroxide (LDH) ([0017]). Mizuno further teaches the composition of the LDH is represented by the formula: [M2+ 1-xM3+ x(OH)2] [An− x/n.yH2O], where, M2+ represents a divalent metal ion selected from the group consisting of Mg2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+and Zn2+, and M3+represents a trivalent metal ion selected from the group consisting of Al3+, Cr3+, Fe3+, Co3+and In3+ ([0015]). Mizuno further teaches the LDH is provided with a positively charged cation layer which contains preferably at least two or more types of metal cations composed of mutually different valences ([0024]).
Sumboja teaches NiMn-LDHs as oxidation evolution reaction (OER) catalysts (pg. 775, col. 1, first full paragraph) for zinc-air batteries (pg. 774, col. 1). Sumboja teaches that the nanosheets of NiMn LDHs with optimized Ni:Mn molar feeding ration exhibit good crystallinity, big layer spacing, and large surface area, and are highly active and stable during the OER (pg. 775, col. 1, 1st full para.).
Therefore, it would have been obvious to one of ordinary skill in the art, before the effective filing date, to have selected Ni2+ and Mn2+ from the finite list of cations provided by Mizuno for the benefit of an active and stable LDH, as taught by Sumboja.
Koshikawa teaches a layered double hydroxide as a catalyst in a water electrolysis cell ([0001]), where the LDH is used as catalyst material for an anode reaction of water electrolysis (i.e. oxygen evolution reaction that proceeds at the anode in water electrolysis, [0003]-[0004]). Koshikawa teaches that among transition metals, Ni and Fe have particularly high catalytic activity for the OER ([0030];[0003]) and additionally are elements that exist in abundance allowing for reduced material costs ([0030]).
A skilled artisan would recognize that the oxygen evolution reaction (OER) is a half reaction of electrochemical water splitting and is utilized in many key renewable energy systems such as metal air batteries and regenerative fuel cells, and that the OER in Koshikawa’s taught water electrolysis cell is the same OER in the metal-air battery disclosed by Mizuno, as evidenced by Jiang (pg. 445). Furthermore, a skilled artisan would recognize that the OER is kinetically slow and thus requires a catalyst (Jiang 1, pg. 445-446, bridging paragraph), such that a LDH catalyst used in a metal-air battery could be used in a water electrolysis cell, and vice versa, as the catalyst is catalyzing the same OER reaction.
Therefore, it would have been obvious to one of ordinary skill in the art, to have further selected Fe2+ and/or Fe3+ from the finite list of cations provided by Mizuno, for the benefit of high catalytic activity and lower material costs, as taught by Koshikawa.
Goncalves teaches vanadium containing electrocatalysts for the OER including vanadium-containing LDHs (pg. 2183, col. 2, 1st full para.). Goncalves further teaches strong electronic interactions of V ions with other transition metals (Fe and Ni) are responsible for synergistic effects (pg. 2187, col. 1, 1st full para.) and furthermore, that V atoms have an enhanced capability of binding oxygen intermediates compared to Ni and Fe-sites, thus exhibiting higher OER activity (pg. 2187, col. 1, 2nd full para.).
Therefore, it would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to have further included V, for the benefit of enhanced capability of binding oxygen intermediates and higher OER activity, and with reasonable expectation of achieving a successful LDH.
Jiang teaches NiCo-LDHs (pg. 446, col. 1, 2nd full para.), as cobalt- and nickel- containing materials as OER catalysts are versatile candidates for the replacement of precious catalysts due to their abundance, low cost, environmentally friendly, multiple valence state, and high theoretical activity (pg. 446, col. 1, 1st full para.). Jiang further teaches Co and Ni exist as multiple valence state in NiCo-LDH nanosheets, and the solid-state redox couples Ni2+/Ni3+ and Co2+/Co3+ in NiCo-LDHs may provide a notable electrochemical performance since Ni3+ and Co3+ are regarded has catalytically active centers for OER (pg. 448, col. 1-2, bridging para.).
Therefore, it would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to have further selected Co2+ and/or Co3+ from the finite list of cations provided by Mizuno, for the benefit of catalytically active centers for OER, as taught by Jiang, and with a reasonable expectation of achieving a working LDH.
Regarding claim 9, modified Hattori discloses all limitations as set forth above.
Modified Hattori further discloses wherein the separator is composed of a hydroxide-ion conductive inorganic electrolyte being a dense ceramic material capable of selective permeation of hydroxide ions generated at the air electrode layer to the electrolytic solution (Hattori, [0045]). Thus, modified Hattori satisfies the claim limitation, “wherein the separator is a hydroxide ion conductive dense separator”.
Modified Hattori further discloses wherein the electrolytic solution is separated from the air electrode layer (i.e. air electrode) by the separator (Hattori, [0057]).
Allowable Subject Matter
Claims 2 and 4 remain objected to as being dependent upon a rejected base claim.1
The following is a statement of reasons for the indication of allowable subject matter:
Claim 2 would be allowable for disclosing the layered double hydroxide having an atomic ratio (Ni+Mn)/(Ni+Fe+V+Co+Mn) of 0.6 or more and 0.8 or less, which is determined by energy-dispersive X-ray spectroscopy (EDS).
Claim 4 would be allowable for disclosing the layered double hydroxide having an atomic ratio Mn/(Ni+Fe+V+Co+Mn) of more than 0 and 0.4 or less, which is determined by energy-dispersive X-ray spectroscopy (EDS).
Mizuno is silent regarding controlling the atomic ratios of the transition metals of the layered double hydroxide and does not explicitly disclose a layered double hydroxide containing five elements, Ni, Fe, V, Co and Mn, nor a desire to control the atomic ratios of the five transition metals.
Sumboja discloses controlling the Ni:Mn ratio in a NiMn-LDH to control interlayer spacing, crystallinity, and in turn, catalytic activity (pg. 775, right col., 2nd full para, and pg. 776, left col., first para.). However, as Sumboja only discloses a NiMn-LDH—an LDH only having two transition metals—Sumboja neither teaches nor suggests controlling the atomic ratio of Ni and Mn in a five-transition metal or element LDH system. Thus, there appears no reason for a skilled artisan to pursue such.
Koshikawa discloses an LDH which may include two or more transition metals from the group consisting of V, Cr, Mn, Fe, Co, Ni, Cu, W, and Ru and suggests a preference for Ni and/or Fe ([0028]-[0030]). However, Koshikawa provides no motivation or teaching for why one of ordinary skill in the art, would specifically choose Ni, Fe, V, Co, and Mn to form a layered double hydroxide comprising those five transition metal elements, or why a skilled artisan would desire to control or optimize the atomic ratio of Ni and Mn with respect to the other transition metals.
Jiang discloses a NiCo-LDH as potential OER catalysts and how Ni and Co contribute as catalytically active centers for OER (pg. 448, col 1-2, bridging paragraph). However, Jiang does not disclose or suggest adding additional transition metals to improve the catalytic activity of the NiCo-LDH, and therefore provides no reason for a skilled artisan to pursue an LDH with five-transition metals, nor how controlling the atomic ratio of Ni and/or Co would affect the catalytic activity of the LDH, specifically in a system with Ni, Fe, V, Co, and Mn.
Goncalves, while disclosing vanadium-containing LDHs (pg. 2183, col. 2, 1st full para.), teaches specifically how V ions interact with Fe and Ni in NiFeV-LDHs (pg. 2187, col. 1, 1st full para.). Goncalves is silent regarding additional transition metals such as Mn and Co, and neither teaches nor suggests reasons for controlling the atomic ratios of V, Fe, and Ni.
In contrast, Applicant’s layered double hydroxide comprising Ni, Fe, V, Co, and Mn with a specific ratio of (Ni+Mn)/(Ni+Fe+V+Co+Mn) of 0.6 or more and 0.8 or less, and Mn/(Ni+Fe+V+Co+Mn) of more than 0 and or 0.4 or less, which is determined by energy-dispersive X-ray spectroscopy (EDS), allows for a more excellent catalytic function (see [0012] of instant specifications).
As none of the prior art discussed above alone or in combination teaches/suggests such atomic ratios of a layered double hydroxide comprising five elements, one with ordinary skill in the art would not find it obvious/be motivated to achieve such atomic ratios as claimed and disclosed by the applicant (see [0012]-[0015] of the instant specification).
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to ESTHER J TAN whose telephone number is (571)272-3479. The examiner can normally be reached M-F 7:30 AM-4:00 PM.
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.
/E.J.T./Examiner, Art Unit 1751
/Haroon S. Sheikh/Primary Examiner, Art Unit 1751
Prosecution Insights