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 .
Priority
Receipt is acknowledged of certified copies of papers required by 37 CFR 1.55.
Information Disclosure Statement
The information disclosure statement (IDS) submitted on 2/24/2025 has been considered by the examiner.
Claim Objection
Claims 2, 5, and 7 are objected to because of the following informalities:
Claim 2: please amend “the Prussian blue analog uniform to form an insertion material” to --the Prussian blue analog particles to form [[an]] the insertion material--.
Claims 5 and 7: please amend “Prussian blue analogue particles” to –the Prussian blue analogue particles--.
Appropriate correction is required.
Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claims 3-4 and 6 are rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as failing to set forth the subject matter which the inventor or a joint inventor, or for applications subject to pre-AIA 35 U.S.C. 112, the applicant regards as the invention.
Regarding claim 3, claim 3 recites “ further comprising producing the slurry, comprising oxidizing a monoclinic Prussian blue analogue to synthesize Prussian blue analogue particles having at least partially a cubic crystal structure”, and claim 2 recites “wherein the Prussian blue analogue particles have at least partially a monoclinic crystal structure”. Since the monoclinic Prussian blue analogue is oxidized to Prussian blue analogue particles having at least partially a cubic crystal structure, the Prussian blue analogue in the slurry applied to the conductor has at least partially a cubic crystal structure instead of a monoclinic crystal structure. But in the final product of the solid- state potassium ion-selective electrode, the Prussian blue analogue particles have at least partially a monoclinic crystal structure. Thus, it is unclear if the Prussian blue analogue in the solid- state potassium ion-selective electrode has at least partially a monoclinic crystal structure or at least partially a cubic crystal structure. Thus, the scope of claim 3 is indefinite. Claim 6 is further rejected by virtue of its dependence upon and because it fails to cure the deficiencies of indefinite claim 3.
Regarding claim 4, claim 4 recites “further comprising holding a potential of an electrode at an oxidation-reduction potential of K2FeFe in a K2SO4 aqueous solution after the immersing the ion-sensitive stock membrane”, and it is unclear if “an electrode” is the same as or different than the all-solid-state potassium ion-selective electrode to be manufactured. Thus, the scope of claim 4 is indefinite.
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.
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.
Claim 1 is rejected under 35 U.S.C. 103 as being unpatentable over Gabrielli et al. (An Electrogravimetric Study of an All-Solid-State Potassium Selective Electrode with Prussian Blue as the Electroactive Solid Internal Contact, Journal of the Electrochemical Society, 2005, 152(12), H219-H224), and further in view of Brant et al. (US20240429385A1).
Regarding claim 1, Gabrielli teaches an all-solid-state potassium ion-selective electrode (all-solid-state potassium ion-selective electrode with Prussian Blue [PB] as the electroactive solid internal contact [title]) comprising:
a conductor (gold electrode [Electrode preparation on Pg. H221]);
an insertion material formed on a surface of the conductor (One of the gold electrodes was immersed into 0.02 M FeCl3, 0.02 M K3[Fe(CN)6], and 0.01 M HCl aqueous solution. Electrodeposits of PB were galvanostatically carried out by applying a controlled cathodic current …” [Electrode preparation on Pg. H221]; PB is deemed as the insertion material); and
a potassium ion-sensitive membrane covering the insertion material (PVC membrane was deposited on the gold electrode by spin-coating. For this, 10 µL of the membrane solution was pipetted onto the electrode [Electrode preparation on Pg. H221]; the membrane solution is detailed in Membrane solution preparation on Pg. H221) ,
wherein the insertion material containing Prussian blue analogue particles (PB [Electrode preparation on Pg. H221]),
wherein the Prussian blue analogue particles are represented by a molecular formula KxFe[Fe(CN)6]y·nH2O, wherein x is a number equal to or greater than 1.5 and equal to or less than 2, y is a number greater than 0 and equal to or less than 1, and n is a number equal to or greater than 0 (At the PB/membrane interface a second ion-exchange phenomenon takes place KFeIIIFeII(CN)6 + K+ + e− ↔ K2FeIIFeII(CN)6” [ Theory on Pg. H219]. Note that the PBA will be further modified by Brant as the following).
Gabrielli is silent to: (1) wherein the insertion material further comprises conductive material particles; and (2) wherein the Prussian blue analogue particles have at least partially a monoclinic crystal structure.
Brant teaches potassium ion battery cell comprising a Prussian Blue analogue (PBA) as an active cathode material (claim 1), wherein the Prussian Blue analogue is Prussian white having the formula AaFe[Fe(CN)6], wherein A is potassium or sodium, and wherein 1.8<a≤2, preferably wherein 1.9<a≤2 [para. 0046]. Prussian white is associated with a high battery capacity and an enhanced capability in storing sodium (and potassium) ions. Prussian white is also environmentally friendly and can be produced at a low cost [para. 0047]. The step of providing a slurry may comprise mixing the Prussian Blue analogue in the form of a powder, with a conductive additive and a binder [para. 0052]. The cycling data in FIG. 3a shows that the electrode stack contains both the anhydrous phase of Prussian white and the hydrated phase of Prussian white i.e., both the rhombohedral and monoclinic structures [para. 0142]. The conductive additive may be any type of conductive additive known to the skilled person. For example, various types of carbon compounds, e.g. super P, C65, C45, carbon black, e.g. ketjen black may be utilized [para. 0083]. Thus, Brant teaches an electrode material comprising Prussian blue analogue particles (Prussian white having the formula KaFe[Fe(CN)6] with 1.8<a≤2) having at least partially a monoclinic crystal structure and conductive material particles.
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify the PBA material in Gabrielli to Prussian white having the formula KaFe[Fe(CN)6] with 1.8<a≤2 having at least partially a monoclinic crystal structure, and further adding conductive material particles into the insertion material, as taught by Brant, since it would enhance capacity in storing potassium ions and would be also environmentally friendly and could be produced at a low cost [para. 0047 in Brant].
Claims 2, 5 and 7 are rejected under 35 U.S.C. 103 as being unpatentable over Takayama et al. (JP 2020046364A, English translation), and in view of Gabrielli et al. (An Electrogravimetric Study of an All-Solid-State Potassium Selective Electrode with Prussian Blue as the Electroactive Solid Internal Contact, Journal of the Electrochemical Society, 2005, 152(12), H219-H224) and Brant et al. (US20240429385A1). Takayama was provided in IDS filed on 2/24/2025.
Regarding claim 2, Takayama teaches a method for manufacturing an all-solid-state magnesium ion-selective electrode (a method for manufacturing an all-solid-state magnesium ion-selective electrode [0009]),
wherein the all-solid-state magnesium ion-selective electrode comprises:
a conductor (supplying the slurry onto a conductor [para. 0009]);
an insertion material formed on a surface of the conductor (supplying the slurry containing PB represented by the structure formula KzFe [Fe(CN)6]y·n H2O onto a conductor, and drying the slurry to form a composite film on the surface of the conductor [para. 0009]; the slurry containing PB is deemed as the insertion material); and
a magnesium ion-sensitive membrane covering the insertion material (supplying a magnesium ion-sensitive film stock solution onto the surface of the insertion material and drying the magnesium ion-sensitive film stock solution to form an ion-sensitive film on the surface of the insertion material [para. 0009]),
wherein the insertion material containing Prussian blue analogue particles, wherein the Prussian blue analogue particles are represented by a molecular formula KxFe[Fe(CN)]y▪ nH20 (PB represented by the structure formula KzFe [Fe(CN)6]y·n H2O [para. 0009]), wherein x is a number equal to or greater than 0 and equal to or less than 2 ( z is 0 or more and 2 or less [para. 0009]), y is a number greater than 0 and equal to or less than 1 (y is a number greater than 0 and 1 or less [para. 0009]), and n is a number equal to or greater than 0 (n is a number greater than or equal to 0 [para. 0009]), and
wherein the method comprises:
applying a slurry onto the conductor and drying the slurry to form a compound membrane on the surface of the conductor (supplying the slurry containing PB represented by the structure formula KzFe [Fe(CN)6]y·n H2O onto a conductor, and drying the slurry to form a composite film on the surface of the conductor [para. 0009]);
immersing the compound membrane in a first magnesium chloride aqueous solution and making a distribution of K+ in the Prussian blue analog uniform to form an insertion material on the surface of the conductor (Forming an insertion material on the surface of the conductor by immersing the mixture film in a first aqueous solution of magnesium chloride and replacing K + of the Prussian blue with Mg2 + [para. 0009]);
applying a magnesium ion-sensitive membrane stock liquid onto the surface of the insertion material and drying the magnesium ion-sensitive membrane stock liquid to form an ion-sensitive stock membrane on the surface of the insertion material (supplying a magnesium ion-sensitive film stock solution onto the surface of the insertion material and drying the magnesium ion-sensitive film stock solution to form an ion-sensitive film on the surface of the insertion material [para. 0009]); and
immersing the ion-sensitive stock membrane in a second magnesium chloride aqueous solution to form a magnesium ion-sensitive membrane on the surface of the insertion material ( immersing the ion-sensitive film in a second magnesium chloride aqueous solution to form a magnesium ion-sensitive film on the surface of the insertion material).
Takayama further teaches the above method for manufacturing magnesium ion-sensitive electrode can be used to manufacture calcium ion selective electrode by replacing the first and second magnesium chloride aqueous solutions with the first and second calcium chloride solutions, and replacing the magnesium ion-sensitive film cock solution with a calcium ion-sensitive film cock solution [para. 0011].
Gabrielli teaches all solid-state potassium selective electrode with Prussian Blue as the electroactive solid internal contact (title), and use the potassium ion-selective membrane stock liquid to form the potassium ion-sensitive membrane on the surface of the insertion material (corresponding to the PB solid internal contact).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to take the method of Takayama to manufacture an all solid-state potassium ion-selective electrode by replacing the first and second magnesium chloride aqueous solutions with the first and second potassium chloride solutions, and replacing the magnesium ion-sensitive film cock solution with a potassium ion-sensitive film cock solution, in the same way for manufacturing the solid-state calcium ion selective electrode, as taught by Takayama and Gabrielli, since it would form all solid-state potassium ion-selective electrode (title in Gabrielli).
Takayama teaches wherein x is a number equal to or greater than 0 and equal to or less than 2, as outlined in the rejection above, thus is silent to wherein x is a number equal to or greater than 1.5 and equal to or less than 2. But the disclosed range of x overlaps with the claimed range of x.
It would have been obvious to have selected and utilized a Prussian blue analog represented by the structure formula KzFe [Fe(CN)6]y·n H2O with z within the disclosed range of 0 to 2, as taught by Takayama, including those amounts that overlap within the claimed range, since one of ordinary skill in the art would reasonably expect any value within the taught range to be suitable given that Takayama specifically teaches the range to be suitable for the Prussian blue analog. It has been held that obviousness exists where the claimed ranges overlap or lie inside ranges disclosed by the prior art. See MPEP 2144.05 (I).
Modified Takayama is silent to: (1) wherein insertion material further comprises
conductive material particles; and (2) wherein the Prussian blue analogue particles have at least partially a monoclinic crystal structure.
Brant teaches potassium ion battery cell comprising a Prussian Blue analogue (PBA) as an active cathode material (claim 1), wherein the Prussian Blue analogue is Prussian white having the formula AaFe[Fe(CN)6], wherein A is potassium or sodium, and wherein 1.8<a≤2, preferably wherein 1.9<a≤2 [para. 0046]. Prussian white is associated with a high battery capacity and an enhanced capability in storing sodium (and potassium) ions. Prussian white is also environmentally friendly and can be produced at a low cost [para. 0047]. The step of providing a slurry may comprise mixing the Prussian Blue analogue in the form of a powder, with a conductive additive and a binder [para. 0052]. The cycling data in FIG. 3a shows that the electrode stack contains both the anhydrous phase of Prussian white and the hydrated phase of Prussian white i.e., both the rhombohedral and monoclinic structures [para. 0142]. The conductive additive may be any type of conductive additive known to the skilled person. For example, various types of carbon compounds, e.g. super P, C65, C45, carbon black, e.g. ketjen black may be utilized [para. 0083]. Thus, Brant teaches an electrode material comprising Prussian blue analogue particles (Prussian white having the formula KaFe[Fe(CN)6] with 1.8<a≤2) having at least partially a monoclinic crystal structure and conductive material particles.
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify the PBA material in modified Takayama to Prussian white having the formula KaFe[Fe(CN)6] with 1.8<a≤2 having at least partially a monoclinic crystal structure, and further adding conductive material particles into the insertion material, as taught by Brant, since it would enhance capacity in storing potassium ions and would be also environmentally friendly and could be produced at a low cost [para. 0047 in Brant].
Regarding claims 5 and 7, Modified Takayama teaches the method according to claim 2, and Takayama is silent to comprising producing the slurry, comprising mixing: Prussian blue analogue particles; acetylene black, Ketjen black, or multi-wall carbon nanotubes; and polyvinylidene fluoride.
Brant does teach the step of providing a slurry may comprise mixing the Prussian Blue analogue in the form of a powder, with a conductive additive and a binder [para. 0052]. The conductive additive may be any type of conductive additive known to the skilled person. For example, various types of carbon compounds, e.g. super P, C65, C45, carbon black, e.g. ketjen black may be utilized [para. 0083]. The binder is not limited to a particular binder. For example, alginate, carboxymethyl cellulose (CMC), styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVdF) may be used [para. 0084].
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify the method by providing the step of producing the slurry, comprising mixing: Prussian blue analogue particles; conductive material particles of Ketjen black; and polyvinylidene fluoride, as taught by Brant, since it would provide the slurry of the electroactive solid internal contact of the electrode [para. 0052 in Brant].
Double Patenting
A rejection based on double patenting of the “same invention” type finds its support in the language of 35 U.S.C. 101 which states that “whoever invents or discovers any new and useful process... may obtain a patent therefor...” (Emphasis added). Thus, the term “same invention,” in this context, means an invention drawn to identical subject matter. See Miller v. Eagle Mfg. Co., 151 U.S. 186 (1894); In re Vogel, 422 F.2d 438, 164 USPQ 619 (CCPA 1970); In re Ockert, 245 F.2d 467, 114 USPQ 330 (CCPA 1957).
Applicant is advised that should claim 5 be found allowable, claim 7 will be objected to under 37 CFR 1.75 as being a substantial duplicate thereof. When two claims in an application are duplicates or else are so close in content that they both cover the same thing, despite a slight difference in wording, it is proper after allowing one claim to object to the other as being a substantial duplicate of the allowed claim. See MPEP § 608.01(m).
Allowable Subject Matter
Claims 3-4 and 6 would be allowable if they are rewritten or amended to overcome the rejection(s) under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), 2nd paragraph, set forth in this Office action.
The following is a statement of reasons for the indication of allowable subject matter.
Regarding claim 3, the prior art of the record does not teach and/or suggest “
producing the slurry, comprising oxidizing a monoclinic Prussian blue analogue to synthesize Prussian blue analogue particles having at least partially a cubic crystal structure”. As outlined in the rejection of claim 2 above, the Prussian blue analogue particles of the potassium ion-selective electrode having at least partially a monoclinic crystal structure, thus one of ordinary skill in the art would not be motivated to oxidize a monoclinic Prussian blue analogue to synthesize Prussian blue analogue particles having at least partially a cubic crystal structure. Note that claim 3 is further rejected under 112(b) above. Claim 6 further depends on claim 3.
Regarding claim 4, the prior art of the record does not teach and/or suggest “further comprising holding a potential of an electrode at an oxidation-reduction potential of K2FeFe in a K2SO4 aqueous solution after the immersing the ion-sensitive stock membrane”.
As allowable subject matter has been indicated, applicant's reply must either comply with all formal requirements or specifically traverse each requirement not complied with. See 37 CFR 1.111(b) and MPEP § 707.07(a).
Conclusion
The prior arts made of record and not relied upon are considered pertinent to applicant's disclosure: Ito et al. (JP2020092086A) teaches a positive electrode material for a potassium ion secondary battery including PBA having a monoclinic structure, conductive material particles and a binder. Uchiyama et al. (US20220334077A1) teaches a solid-state ion selective electrode comprising an internal layer containing metal oxide, a binder and a conductive agent. Speck (US20190195824A1) teaches an electrochemical sensor comprising a ion selective measuring electrode 13 comprising an ion-selective membrane, internal layer, and conductor. Ikejiri et al. (JP2018018578A) teaches an all-solid-state electrode [para. 0082].
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/SHIZHI QIAN/Primary Examiner, Art Unit 1795
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