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 .
Response to Amendments
This is a final office action in response to applicant's arguments and remarks filed on 07/30/2025.
Status of Rejections
All previous rejections are maintained.
Claims 1-2, 5-12 and 21-24 are pending and under consideration for this Office Action.
Claim Rejections - 35 USC § 103
The text of those sections of Title 35, U.S. Code not included in this action can be found in a prior Office action.
Claims 1-2 and 21-22 are rejected under 35 U.S.C. 103 as being unpatentable over Yousefi et al. (“Template-free synthesis of MnO2 nanowires with secondary flower like structure: Characterization and supercapacitor behavior studies”, Current Applied Physics, 2012) in view of Suetsugu et al. (U.S. 2012/0141361); claim 2 evidenced by Zheng et al. (“Three-dimensional radial α-MnO2 synthesized from different redox potential for bifunctional oxygen electrocatalytic activities”, J Power Sources, 2017).
Regarding claim 1, Yousefi teaches an electrolytic manganese oxide (see e.g. Page 194, Col. 1, lines 8-9, electrodeposited, i.e. electrolytic, MnO2),
which is an electrolytic manganese oxide having a manganese metallic valence of 4.0 (see e.g. Page 194, Col. 1, lines 8-9, electrodeposited, i.e. electrolytic, MnO2, which has an Mn valence of +4), having an average primary particle size of 30 to 70 nm (see e.g. Page 196, Col. 1, lines 12-14, diameters of 30-70 nm) and an average secondary particle size of about 5.5 to 12.3 µm (see e.g. Figs. 2a/c and 3a/c, secondary flowerlike structures shown with diameters of about 5.5 to 12.3 microns; Page 196, Col. 1, lines 4-6 and 9-11), and having a crustal structure of γ manganese dioxide and α manganese dioxide (see e.g. Page 196, Col. 2, lines 1-4).
Yousefi does not explicitly teach the potential measured in a 40 wt% KOH solution based on a mercury/mercury oxide reference electrode being at least 200 mV and at most 320 mV. Yousefi does however teach the electrolytic manganese oxide being suitable for use as an electrode in lithium secondary batteries (see e.g. Page 193, Col. 1, lines 15-17).
Suetsugu teaches an electrolytic manganese dioxide (see e.g. Abstract), having an alkali potential measuring in a 40 wt% KOH solution based on a mercury/mercury oxide reference electrode of at least 280 mV and less than 310 mV (see e.g. Paragraph 0041, lines 1-6), this alkali potential increasing open circuit voltage and prolonging discharge time until the lower limit of useful discharge voltage when the material is used as a cathode material in an alkali-manganese dry cell (see e.g. Paragraph 0040, lines 1-3).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the electrolytic manganese oxide of Yousefi to have an alkali potential measured in a 40 wt% KOH solution based on a mercury/mercury oxide reference electrode of at least 200 mV and at most 320 mV as taught by Suetsugu to increase open circuit voltage and prolong discharge time until the lower limit of useful discharge voltage when the material is used as a cathode material in an alkaline manganese dioxide battery.
Modified Yousefi does not explicitly teach the manganese oxide being for an oxygen evolution anode catalyst, however, this limitation is a statement of intended use. MPEP § 2114 states “"[A]pparatus claims cover what a device is, not what a device does."…A claim containing a "recitation with respect to the manner in which a claimed apparatus is intended to be employed does not differentiate the claimed apparatus from a prior art apparatus" if the prior art apparatus teaches all the structural limitations of the claim.”. Modified Yousefi teaches all the structural limitations of the claimed electrolytic manganese oxide and would therefore be capable of being used for an oxygen evolution anode catalyst.
Regarding claim 2, though Yousefi does not explicitly provide a BET measurement, it does describe the manganese oxide having a high surface area resulting from its porous morphology of nanowires with diameters of 30-70 nm and lengths of 100-200 nm arranged into secondary micrometer-scale flowerlike structures (see e.g. Yousefi Figs. 2-3 and Page 196, Col. 1, lines 4-14), such structures being evidenced by Zheng to have BET specific surface areas on the order of 27.7 or 18.2 m2/g (see e.g. Zheng Fig. 2, micron-scale dandelionlike and urchinlike secondary structures formed of aggregated MnO2 nanorods having the respective BETs; Page 334, Col. 2, lines 1-10, and Page 338, Col. 2, lines 2-4), indicating that the BET specific surface area of the manganese oxide of modified Yousefi would similarly be within the claimed range.
Regarding claim 21, modified Yousefi teaches an electrode active material comprising the electrolytic manganese oxide as defined in claim 1 (see e.g. Yousefi Page 197, Col. 1, lines 1-9, the prepared MnO2 as active material for working electrode).
Modified Yousefi does not explicitly teach this being electrode active material being for oxygen evolution in water electrolysis, however, this limitation is a statement of intended use. MPEP § 2114 states “"[A]pparatus claims cover what a device is, not what a device does."…A claim containing a "recitation with respect to the manner in which a claimed apparatus is intended to be employed does not differentiate the claimed apparatus from a prior art apparatus" if the prior art apparatus teaches all the structural limitations of the claim.”. Modified Yousefi teaches all the structural limitations of the claimed electrode active material, as stated above, and would therefore be capable of being used for oxygen evolution.
Regarding claim 22, modified Yousefi teaches an electrode, which comprises the electrode active material as defined in claim 21 (see e.g. Yousefi Page 197, Col. 1, lines 1-9, working electrode comprising the prepared MnO2 active material).
Modified Yousefi does not explicitly teach this electrode being for oxygen evolution, however, this limitation is a statement of intended use. MPEP § 2114 states “"[A]pparatus claims cover what a device is, not what a device does."…A claim containing a "recitation with respect to the manner in which a claimed apparatus is intended to be employed does not differentiate the claimed apparatus from a prior art apparatus" if the prior art apparatus teaches all the structural limitations of the claim.”. Modified Yousefi teaches all the structural limitations of the claimed electrode, as stated above, and would therefore be capable of being used for oxygen evolution.
Claims 5-11 and 24 are rejected under 35 U.S.C. 103 as being unpatentable over Yousefi in view of Suetsugu, as applied to claim 1 above, and further in view of Gyenge et al. (U.S. 2017/0207464); claim 11 evidenced by Zhang et al. (“Smart Janus titanium mesh used as a diode for both liquid droplet and air bubble transport”, New J. Chem., 2021) and claim 24 evidenced by Quiroga (“Cyclic Voltammetry”, LibreTexts Chemistry, 2022).
Regarding claim 5, modified Yousefi teaches all the elements of the electrolytic manganese of claim 1 as stated above. Modified Yousefi further teaches an electrolytic manganese oxide/carbon mixture, which is a mixture of the electrolytic manganese oxide as defined in claim 1 and electrically conductive carbon (see e.g. Yousefi Page 197, Col. 1, lines 1-9, MnO2 active material mixed with acetylene black as conductive filler).
Modified Yousefi does not teach the proportion of the electrolytic manganese oxide to the total of the electrolytic manganese oxide and the electrically conductive carbon being at least 0.5 wt% and at most 40 wt%, instead teaching a larger proportion of 84.2 wt% (see e.g. Yousefi Page 197, Col. 1, lines 7-8, 80 wt% MnO2 active material and 15 wt% acetylene black). Yousefi does however teach the electrolytic manganese oxide being suitable for use as an electrode in lithium secondary batteries (see e.g. Page 193, Col. 1, lines 15-17).
Gyenge teaches an electrode (see e.g. Abstract) comprising an electrocatalyst including manganese dioxide and carbon mixture (see e.g. Paragraph 0062, lines 1-3, and Paragraph 0067), which is used for electrochemical cells including primary and secondary batteries at which ORR and OER are performed (see e.g. Paragraph 0055, lines 1-2, Paragraph 0060 and Paragraph 0072, lines 1-4), wherein supporting 30 wt% MnO2 on carbon black provides a high ORR current density (see e.g. Paragraph 0072, lines 12-15).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the electrolytic manganese oxide of modified Yousefi to be provided in a composition with an electrically conductive carbon such as carbon black at a proportion of 30 wt% of the total of the electrolytic manganese oxide and electrically conductive carbon as taught by Gyenge as a composition which provides a high ORR current density for a battery cell including manganese dioxide. MPEP § 2143(I)(A) states that “combining prior art elements according to known methods to yield predictable results” may be obvious. The claimed elements were known in the prior art and one skilled in the art could have combined the elements as claimed by known methods with no change in their respective functions, and the combination would yield nothing more than predictable results.
Modified Yousefi does not explicitly teach this mixture being for oxygen evolution anode catalyst in water electrolysis, however, this limitation is a statement of intended use. MPEP § 2114 states “"[A]pparatus claims cover what a device is, not what a device does."…A claim containing a "recitation with respect to the manner in which a claimed apparatus is intended to be employed does not differentiate the claimed apparatus from a prior art apparatus" if the prior art apparatus teaches all the structural limitations of the claim.”. Modified Yousefi teaches all the structural limitations of the claimed mixture, as stated above, and would therefore be capable of being used as an oxygen evolution anode catalyst in water electrolysis.
Regarding claim 6, modified Yousefi teaches the electrolytic manganese oxide/carbon mixture having interplanar spacings of at least 0.347, 0.268, 0.246, 0.239, 0.221, 0.211, 0.169 and 0.143 nm (see e.g. Yousefi Fig. 4, XRD peaks, shown marked below, at 2θ values of 25.6, 33.4, 36.5, 37.5, 40.9, 42.9, 54.1 and 65.1, which equate to the stated interplanar spacings calculated as d in the nλ=2dsinθ, n=1 equation in Paragraph 0061, lines 17-18, of the instant specification).
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Regarding claim 7, modified Yousefi teaches all the elements of the electrolytic manganese oxide of claim 1 as stated above. Modified Yousefi further teaches a manganese oxide composite electrode material which comprises an electrically conductive substrate at least part of which is covered with the electrolytic manganese oxide as defined in claim 1 (see e.g. Yousefi Page 197, Col. 1, lines 1-11, working electrode comprising mixture including active MnO2 provided on a glassy carbon electrode). Modified Yousefi does not teach the substrate being constituted by fibers, instead teaching it being glassy carbon (see e.g. Yousefi Page 197, Col. 1, lines 9-11), but does the manganese oxide being suitable for use as an electrode in lithium secondary batteries (see e.g. Yousefi Page 193, Col. 1, lines 15-17).
Gyenge teaches an electrode (see e.g. Abstract) comprising a catalyst such as manganese dioxide (see e.g. Paragraph 0062, lines 1-3) which is used for electrochemical cells including primary and secondary batteries at which ORR and OER are performed (see e.g. Paragraph 0055, lines 1-2, Paragraph 0060 and Paragraph 0072, lines 1-4), wherein the electrode comprises an electrically conductive substrate with a high surface area, such as carbon cloth, carbon fiber paper, graphite felt and a metal mesh such as nickel or titanium mesh (see e.g. Paragraph 0061, lines 6-10).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the electrically conductive substrate of modified Yousefi to be a substrate constituted by fibers, such as carbon cloth, carbon fiber paper, graphite felt and a metal mesh such as nickel or titanium mesh, as taught by Gyenge as an alternate suitable substrate for forming an electrode for a battery cell including manganese dioxide which also provides a high surface area. MPEP § 2143(I)(B) states that “simple substitution of one known element for another to obtain predictable results” may be obvious.
Regarding claim 8, modified Yousefi teaches the electrolytic manganese oxide covering the fibers in an amount per geometrical area of the electrically conductive susbtrate of 0.1 mg/cm2 (see e.g. Yousefi Page 197, Col. 1, lines 11-12).
Regarding claim 9, Yousefi as modified by Gyenge teaches the electrically conductive substrate being formed of carbon or titanium (see e.g. Gyenge Paragraph 0061, lines 6-9, carbon cloth, carbon fiber paper, graphite felt, or titanium mesh).
Regarding claim 10, modified Yousefi teaches the manganese oxide composite electrode material having interplanar spacings of at least 0.405, 0.347, 0.308, 0.246, 0.211, 0.169, 0.162 and 0.141 nm (see e.g. Yousefi Fig. 4, XRD peaks, shown marked below, at 2θ values of 21.9, 25.6, 29.0, 36.5, 42.9, 54.1, 56.7 and 66.3, which equate to the stated interplanar spacings calculated as d in the nλ=2dsinθ, n=1 equation in Paragraph 0061, lines 17-18, of the instant specification).
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Regarding claim 11, modified Yousefi further teaches the manganese oxide composite electrode material having interplanar spacings of at least 0.405, 0.246, 0.234, 0.221, 0.211, 0.162 and 0.141 nm (see e.g. Yousefi Fig. 4, XRD peaks, shown marked below, at 2θ values of 21.9, 36.5, 38.5, 40.9, 42.9, 56.7 and 66.3, which equate to the stated interplanar spacings calculated as d in the nλ=2dsinθ, n=1 equation in Paragraph 0061, lines 17-18, of the instant specification).
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Though modified Yousefi does not explicitly teach the manganese oxide composite electrode material having an interplanar spacing of 0.256±0.005 nm, Gyenge further teaches titanium mesh as one of the fiber-constituted substrate materials (see e.g. Gyenge Paragraph 0061, lines 6-9). Titanium mesh is evidenced by Zhang to exhibit an interplanar spacing of 0.255 nm (see e.g. Zhang Fig. 3f and Page 17865, Col. 2, lines 6-11, XRD line for Ti Mesh at 35.1°, equating to 0.255 calculated as above).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the composite electrode of modified Yousefi to comprise titanium mesh as the fiber-constituted substrate, which exhibits an interplanar spacing of 0.255 nm, as taught by Gyenge as one of a finite number of exemplary suitable electrode substrates providing high surface area. MPEP § 2143(I)(E) states that it may be obvious to choose “from a finite number of identified, predictable solutions, with a reasonable expectation of success”. Further, MPEP § 2144.07 states “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)”.
Regarding claim 24, modified Yousefi teaches an apparatus, which comprises the manganese oxide composite electrode material as defined in claim 7 (see e.g. Yousefi Page 194, Col. 2, bottom paragraph, and Page 197, lines 7-14, electrochemical workstation of three-electrode cell configuration under applied potential comprising MnO2 as working electrode with aqueous electrolyte). Modified Yousefi does not explicitly teach this electrochemical apparatus being for water electrolysis, however, this limitation is a statement of intended use. MPEP § 2114 states “"[A]pparatus claims cover what a device is, not what a device does."…A claim containing a "recitation with respect to the manner in which a claimed apparatus is intended to be employed does not differentiate the claimed apparatus from a prior art apparatus" if the prior art apparatus teaches all the structural limitations of the claim.”. Modified Yousefi teaches all the structural limitations of the claimed apparatus as stated above, and would therefore be capable of being used for water electrolysis. Furthermore, Yousefi teaches the apparatus being used for cyclic voltammetry (CV) with an aqueous, i.e. water-containing, Na2SO4 solution (see e.g. Yousefi Page 194, Col. 2, bottom paragraph), which would be subjected to electrolysis, as evidenced by Quiroga (see e.g. Quiroga connecting paragraph of Pages 2-3).
Claim 12 is rejected under 35 U.S.C. 103 as being unpatentable over Yousefi, Suetsugu and Gyenge, as applied to claim 7 above, and further in view of Staiti et al. (“Investigation of polymer electrolyte hybrid supercapacitor based on manganese oxide–carbon electrodes”, Electrochimica Acta, 2010).
Regarding claim 12, modified Yousefi teaches all the elements of the electrode material of claim 7 as stated above. Modified Yousefi does not teach a laminate comprising the electrode material as defined in claim 7 and a polymer electrolyte membrane. Yousefi does however teach the electrode material being used in a supercapacitor (see e.g. Yousefi Page 197, Col. 1, lines 1-6) with a liquid electrolyte (see e.g. Yousefi Page 194, Col. 2, bottom paragraph).
Staiti teaches a supercapacitor (see e.g. Abstract) comprising a manganese oxide electrode assembled, i.e. laminated, with a polymer electrolyte membrane (see e.g. Page 7437, Col. 1, lines 6-10, and connecting paragraph of Cols. 1-2, lines 3-13), the polymer electrolyte membrane providing similar capacitive performance as liquid electrolyte, while providing a lightweight and flexible supercapacitor design (see e.g. Page 7441, Col. 2, lines 18-21, and under “Conclusions”, lines 12-16).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the electrode material of modified Yousefi to be laminated with a polymer electrolyte membrane as taught by Staiti to provide a lightweight and flexible supercapacitor device which maintains similar capacitive performance as a liquid electrolyte.
Claim 23 is rejected under 35 U.S.C. 103 as being unpatentable over Yousefi in view of Suetsugu, as applied to claim 1 above, and further in view of Staiti.
Regarding claim 23, modified Yousefi teaches all the elements of the electrode of claim 22 as stated above. Modified Yousefi does not teach a laminate comprising the electrode as defined in claim 22 and a polymer electrolyte membrane. Yousefi does however teach the electrode material being used in a supercapacitor (see e.g. Yousefi Page 197, Col. 1, lines 1-6) with a liquid electrolyte (see e.g. Yousefi Page 194, Col. 2, bottom paragraph).
Staiti teaches a supercapacitor (see e.g. Abstract) comprising a manganese oxide electrode assembled, i.e. laminated, with a polymer electrolyte membrane (see e.g. Page 7437, Col. 1, lines 6-10, and connecting paragraph of Cols. 1-2, lines 3-13), the polymer electrolyte membrane providing similar capacitive performance as liquid electrolyte, while providing a lightweight and flexible supercapacitor design (see e.g. Page 7441, Col. 2, lines 18-21, and under “Conclusions”, lines 12-16).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the electrode of modified Yousefi to be laminated with a polymer electrolyte membrane as taught by Staiti to provide a lightweight and flexible supercapacitor device which maintains similar capacitive performance as a liquid electrolyte.
Response to Arguments
Applicant's arguments filed 07/30/2025 have been fully considered but they are not persuasive.
On pages 9-10, Applicant argues that the manganese dioxide of Yousefi would not be able to have the alkali potential in claimed range because it is produced by a heat treatment, which is evidenced by Ruetschi to result in a markedly decreased alkali potential. This is not considered persuasive. Upon further consideration, the Ruetschi reference alone is not sufficient to show that Yousefi would not be capable of having the claimed alkali potential. For one, Ruetschi describes heat treatment of an already formed MnO2 showing the decreased alkali potential (see e.g. Ruetschi Page 2659, Col. 2, paragraph starting with “The theoretical…”), whereas Yousefi describes the heat treatment being used to form the MnO2 from Mn(OH)2 (see e.g. Yousefi Page 195, 3.1), which would not necessarily produce the same decreased alkali potential. Furthermore, the MnO2 of Ruetschi even without heat treatment starts at a lower alkali potential than the claimed range of around 150 mV (see e.g. Ruetschi Fig. 6). Iwamoto et al. (U.S. 2009/0047578) discloses a manganese oxide with a potential of 260-340 mV (see e.g. Iwamoto Paragraph 0016) being formed by heat treating a manganese oxide of higher initial alkali potential (see e.g. Iwamoto Paragraphs 0026 and 0029), showing evidence that a manganese dioxide with an alkali potential in the claimed range can be formed even with heat treatment.
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure.
Guo et al. (“Effects of current density on preparation of grainy electrolytic manganese dioxide”, J. CENT. SOUTH UNIV. TECHNOL., 2005) discloses an electrolytic manganese dioxide consisting of γ-MnO2 with primary particle sizes of 20 nm to 100 nm and secondary particles sizes of 1-3 µm.
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.
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/M.S.J./Examiner, Art Unit 1795
/LUAN V VAN/Supervisory Patent Examiner, Art Unit 1795