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 .
Claim Objections
Claim 3 is objected to because of the following informalities: L12 should recite “wherein said lithium battery” in order to have consistent antecedent basis.
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 2-3, 8, 11-12, and 33 are rejected under 35 U.S.C. 103 as being unpatentable over Kim et al. (US PGPub 2014/0087255 A1) and further in view of Zhamu et al. (US PGPub 2017/0098856 A1, which has a publication date of Apr. 6, 2017 and is cited on the IDS dated July 30, 2020), Kung et al. (US PGPub 2012/0288750 A1), Lee et al. (US PGPub 2014/0377643 A1), Hwang et al. (US PGPub 2017/0047584 A1), and Nakagawa et al. (US PGPub 2017/0005369 A1).
Regarding Claims 2-3 and 8, Kim discloses in Figs. 1 and 8 an anode electrode for a lithium battery (1) ([0003], [0031]), said anode electrode comprising multiple particulates of an anode active material (10) ([0031], e.g. [0082]), wherein at least a particulate comprises a core (15) and a thin encapsulating layer (11) encapsulating said core (15) ([0031]), wherein said core (15) comprises a plurality of primary particles of said anode active material (12) having a volume Va, an electron-conducting material (13) as a filler material, and pores having a volume Vp ([0042]-[0043]) and wherein said thin encapsulating layer (11) comprises an electrically conducting material comprising a carbonaceous material ([0031], hollow carbon fiber) and has a thickness from about 50 nm to about 500 nm ([0037]), which falls within and therefore reads on the instantly claimed range of 1 nm to 10 µm.
The Examiner notes that while Kim does not explicitly disclose wherein the electrically conducting material has an electric conductivity from 10-6 S/cm to 20,000 S/cm and a lithium ion conductivity from 10-8 S/cm to 5 x 10-2 S/cm, Kim discloses wherein said thin encapsulating layer comprises a carbonaceous material ([0031], hollow carbon fiber) having a thickness in the range of about 50 nm to about 500 nm ([0037]) and therefore the thin encapsulating layer of Kim necessarily and inherently has an electric conductivity from 10-6 S/cm to 20,000 S/cm and a lithium ion conductivity from 10-8 S/cm to 5 x 10-2 S/cm, as evidenced by P19, L16-26 of the instant specification.
Kim further discloses wherein said electron-conducting material (13) may contain graphene ([0042]-[0043]).
Though, Kim is not particular regarding the type of graphene of said electron-conducting material and consequently does not disclose wherein said graphene is functionalized graphene, and said graphene comprises single-layer graphene or few-layer graphene, wherein said few-layer graphene is defined as a graphene platelet formed of less than 10 graphene planes.
However, Kim discloses wherein the electron-conducting material (13) is not particularly limited and may be any variety available in the art ([0043]).
Zhamu teaches graphene materials that are good conductive additives for an electrode for a lithium battery ([0085]).
Specifically, Zhamu teaches wherein the graphene material may be functionalized graphene, and said graphene comprise single-layer graphene or few-layer graphene, wherein said few-layer graphene is defined as a graphene platelet formed of less than 10 graphene planes ([0085], [0092]).
It would have been obvious to one of ordinary skill in the art to utilize functionalized graphene, wherein said graphene comprises single-layer graphene or few-layer graphene, wherein said few-layer graphene is defined as a graphene platelet formed of less than 10 graphene planes, as the electron-conducing material of Kim, as taught by Zhamu, as such is not particularly limited and may be any variety available in the art, wherein the skilled artisan would have reasonable expectation that such would successfully function as the electron-conducting material and thereby form the anode electrode desired by Kim.
Modified Kim further discloses wherein said anode active material is preferably silicon (Si) ([0031], [0039] of Kim) and wherein said electron-conducting material (13 of Kim) may occupy 5 to 25% by weight of the said core (15 of Kim), but is not particularly limited thereto ([0045] of Kim).
However, modified Kim does not disclose wherein said electron-conducting material occupies 50% by weight of said particulate weight.
Kung teaches an anode electrode for a lithium battery having reduced resistance for Li ion transport relative to other graphene-based electrode materials ([0015]).
Specifically, Kung teaches wherein said anode electrode comprises at least a particulate comprising a plurality of primary particles of said anode active material and an electron-conducting material containing graphene ([0015], [0020]).
Kung further teaches that when said anode active material is silicon, such may occupy about 30% by weight to 80% by weight ([0024]) and therefore Kung teaches wherein said electron-conducting material may occupy from about 20% by weight to about 70% by weight of said particulate weight, which encompasses the instantly claimed value of 50% by weight.
It would have been obvious to one of ordinary skill in the art to utilize said anode active material of modified Kim in the range taught by Kung, such that said electron-conducting material of modified Kim occupies 50% by weight of said particulate weight, in order to form an anode electrode for a lithium battery having reduced resistance for Li ion transport relative to other graphene-based electrode materials, wherein the amount of said electron-conducting material in said core of modified is not particularly limited and therefore the skilled artisan would have reasonable expectation that such would successfully form said anode electrode desired by modified Kim.
Modified Kim discloses wherein said core (15 of Kim) comprises a plurality of primary particles of said anode active material (12 of Kim) having a volume Va and pores having a volume Vp ([0042]-[0043] of Kim).
The Examiner notes that porosity = (pore volume)/(total volume) and therefore the porosity of said core = Vp/(Va+Vp).
In light of the above, the Examiner notes that a volume ratio Vp/Va of 5.0/1.0 mathematically equates to a porosity of about 83%.
Specifically, modified Kim discloses wherein a porosity of said core (15 of Kim) of said particulate is not particularly limited and may be controlled within a certain range, such as from about 1% to about 80%, in order to further improve the discharge capacity, high-rate characteristics, and lifetime characteristics of the lithium battery ([0034] of Kim), which reads on about 83%.
It would have been obvious to one of ordinary skill in the art to form the core of said particulate to have a porosity of about 80%, as disclosed by modified Kim, such that a volume ratio Vp/Va is 5.0/1.0, wherein the skilled artisan would have reasonable expectation that such would successfully improve the discharge capacity, high-rate characteristics, and lifetime characteristics of the lithium battery of modified Kim.
Assuming for the sake of argument that the range of about 1% to about 80% does not read on the value of about 83%, the following is relied upon.
Lee teaches an anode electrode for a lithium battery comprising multiple particulates of silicon as an anode active material having a volume Va and pores having a volume Vp ([0001], [0054]).
Specifically, Lee teaches wherein the multiple particulates have a porosity in the range of 5% to 90% in order to suppress volume expansion of the anode active material during charging and discharging while maintaining mechanical strength ([0054]-[0057]), which encompasses the value of 83%.
It would have been obvious to one of ordinary skill in the art to form the core of said particulate to have a porosity in the encompassing portion of the range taught by Lee, such that a volume ratio Vp/Va is 5.0/1.0, in order to suppress volume expansion of the anode active material of modified Kim during charging and discharging while maintaining mechanical strength, as porosity of modified Kim is not particularly limited and may be controlled within a certain range and therefore the skilled artisan would have reasonable expectation that such would successfully form the core desired by modified Kim.
Modified Kim does not explicitly disclose wherein, if a single primary particle is encapsulated, the single primary particle is itself porous having a free space to expand into without straining said thin encapsulating layer when said battery is charged.
However, the Examiner notes that the limitation “wherein, if a single primary particle is encapsulated, the single primary particle is itself porous having a free space to expand into without straining said thin encapsulating layer when said battery is charged” is a contingent limitation.
Thus, because modified Kim discloses wherein said core (15 of Kim) comprises a plurality of primary particles of said anode active material (12 of Kim) ([0042]-[0043] of Kim), the limitation is not required to be met.
Modified Kim further discloses wherein said thin encapsulating layer (11 of Kim) comprising the electrically conducting material comprises a carbonaceous material ([0031] of Kim, hollow carbon fiber).
However, modified Kim does not disclose wherein the thin encapsulating layer further comprises a polymer wherein the carbonaceous or graphitic material is dispersed in or bonded by this polymer containing an elastomer or rubber selected from natural polyisoprene, synthetic polyisoprene, polybutadiene, chloroprene rubber, butyl rubber, ethylene propylene rubber, ethylene propylene diene rubber, metallocene-based poly(ethylene-co-octene) elastomer, poly(ethylene-co-butene) elastomer, styrene-ethylene- butadiene-styrene elastomer, epichlorohydrin rubber, polyacrylic rubber, silicone rubber, fluorosilicone rubber, perfluoroelastomers, polyether block amides, chlorosulfonated polyethylene, ethylene-vinyl acetate, thermoplastic elastomer, protein resilin, protein elastin, ethylene oxide-epichlorohydrin copolymer, polyurethane, urethane-urea copolymer, a sulfonated version thereof, or a combination thereof.
Hwang teaches an anode electrode for a lithium battery ([0015]) comprising multiple particulates of an anode active material, wherein at least a particulate comprises a core comprising silicon as the anode active material and an electron-conducting material ([0036]) and a thin encapsulating layer encapsulating said core ([0070]-[0071], second shell).
Specifically, Hwang teaches wherein the thin encapsulating layer may further comprise a carbonaceous material and a polymer, wherein the carbonaceous material is dispersed in or bonded by this polymer containing a rubber in order to further increase the mechanical strength of the particulate ([0070]-[0071]), wherein the rubber is not particularly limited and may be selected from the group of polychloroprene, styrene butadiene rubber, nitrile rubber, or a combination thereof ([0102]).
It would have been obvious to one of ordinary skill in the art to utilize a polymer in the thin encapsulating layer of modified Kim, such that a carbonaceous is dispersed in or bonded by this polymer containing a rubber, as further taught by Hwang, in order to further increase the mechanical strength of the particulate of modified Kim.
However, Hwang does not teach wherein the rubber is chloroprene rubber.
Nakagawa teaches suitable polymers for use in an anode electrode ([0023]). Specifically, Nakagawa teaches wherein the anode electrode comprises an anode active material comprising a carbonaceous material and a polymer ([0023]), wherein the polymer is not particularly limited and may be selected from the group of styrene butadiene rubber and chloroprene rubber ([0026]).
It would have been obvious to one of ordinary skill in the art to utilize chloroprene rubber as the polymer of modified Kim, as taught by Nakagawa, as the polymer is not particularly limited, wherein the skilled artisan would have reasonable expectation that such would successfully function as the polymer desired by modified Kim, thereby forming a thin encapsulating layer that increases the mechanical strength of the particulate of modified Kim, as desired by modified Kim.
Modified Kim further discloses wherein said particulate of the multiple particulates comprises pores having a volume Vp ([0034] of Kim).
However, modified Kim does not explicitly disclose wherein said particulate increases its volume by 50% when said lithium battery is charged.
Though, the Examiner notes that the instant specification discloses that when the volume ratio Vp/Va is from 0.5/1.0 to 5.0/1.0, empty space is provided to accommodate the volume change of said anode active material so that said particulate does not increase its volume by more than 50% when said lithium battery is charged ([0072], [0074]-[0075] of corresponding US PGPub 2020/011937 A1), which encompasses the instantly claimed limitation of increasing its volume by 50% when said lithium battery is charged.
Thus, because modified Kim discloses wherein the volume ratio Vp/Va is 5.0/1.0 ([0034] of Kim, [0054] of Lee), said particulate of modified Kim necessarily and inherently increases its volume by 50% when said lithium battery is charged, as evidenced by [0072], [0074]-[0075] of the instant specification, see corresponding US PGPub 2020/0119337 A1, absent any persuasive evidence provided by the Applicant.
Regarding Claim 11, modified Kim discloses all of the limitations as set forth above. Modified Kim further discloses wherein said anode active material is in the form of a nanoparticle having a diameter from about 25 nm to about 75 nm in order to further improve the discharge capacity, high-rate characteristics, and lifetime characteristics of the lithium battery ([0040]-[0041] of Kim), which falls within and therefore reads on the instantly claimed range from 0.5 nm to 100 nm.
Regarding Claim 12, modified Kim discloses all of the limitations as set forth above. However, modified Kim does not disclose wherein at least one of said anode active material particles is coated with a layer of carbon or graphene prior to being encapsulated.
Hwang teaches an anode electrode for a lithium battery ([0015]) comprising multiple particulates of an anode active material, wherein at least a particulate comprises a core comprising silicon as the anode active material and an electron-conducting material ([0036]) and a thin encapsulating layer encapsulating said core ([0070]-[0071], second shell).
Hwang further teaches wherein at least one of said anode active material particulates is coated with a layer of graphene prior to being encapsulated in order to improve the movement of lithium ions and the electrical conductivity ([0064]-[0066], first shell).
It would have been obvious to one of ordinary skill in the art to coat at least one of said anode active material particulates of modified Kim with graphene prior to being encapsulated by said thin encapsulating layer of modified Kim, as taught by Hwang, in order to improve the movement of lithium ions and the electrical conductivity.
Regarding Claim 33, modified Kim discloses in Fig. 8 of Kim a lithium battery (1 of Kim) containing an anode current collector, the anode electrode (2 of Kim) as set forth above, a cathode active material layer (see a cathode active material layer of cathode electrode 3 of Kim), a cathode current collector, an electrolyte in ionic contact with said anode electrode (2 of Kim) and said cathode active material layer (see a cathode active material layer of cathode electrode 3 of Kim), a porous separator (4 of Kim) disposed between said anode electrode (2 of Kim) and said cathode active material layer (see a cathode active material layer of cathode electrode 3 of Kim) ([0043], [0055], [0063], [0071] of Kim).
Claims 13-16 are rejected under 35 U.S.C. 103 as being unpatentable over Kim et al. (US PGPub 2014/0087255 A1) in view of Zhamu et al. (US PGPub 2017/0098856 A1, which has a publication date of Apr. 6, 2017 and is cited on the IDS dated July 30, 2020), Kung et al. (US PGPub 2012/0288750 A1), Lee et al. (US PGPub 2014/0377643 A1), Hwang et al. (US PGPub 2017/0047584 A1), and Nakagawa et al. (US PGPub 2017/0005369 A1), as applied to Claim 3 above, and further in view of Zhamu et al. (US PGPub 2017/0288211 A1, which has a publication date of Oct. 5, 2017), hereinafter referred to as Zhamu ‘211.
Regarding Claims 13-16, modified Kim discloses all of the limitations as set forth above. Modified Kim further discloses a desire to improve conductivity and charge/discharge efficiency ([0032] of Kim).
Specifically, modified Kim discloses wherein the lithium battery is a lithium-ion battery ([0071] of Kim) and therefore modified Kim discloses wherein the anode electrode must have sufficient conductivity in order to successfully perform charging and discharging, as required for a lithium-ion battery.
However, modified Kim does not disclose does not disclose wherein at least one of said particulates further comprises from 0.1% to 40% by weight of a lithium ion-conducting additive dispersed in said thin encapsulating layer or in ionic contact with said anode active material particles encapsulated therein, wherein said lithium ion-conducting additive is selected from Li2CO3, Li2O, Li2C2O4, LiOH, LiX, ROCO2Li, HCOLi, ROLi, (ROCO2Li)2, (CH2OCO2Li)2, Li2S, LixSOy, wherein X = F, Cl, I, or Br, R = a hydrocarbon group, 0 < x < 1, and 1 < y < 4, or contains a lithium salt selected from lithium perchlorate (LiClO4), lithium hexafluorophosphate (LiPF6), lithium borofluoride (LiBF4), lithium hexafluoroarsenide (LiAsF6), lithium trifluoro-methanesulfonate (LiCF3SO3), bis-trifluoromethyl sulfonylimide lithium (LiN(CF3SO2)2), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF2C2O4), lithium nitrate (LiNO3), Li-fluoroalkyl-phosphate (LiPF3(CF2CF3)3), lithium bisperfluoro-ethylsulfonylimide (LiBETI), lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), an ionic liquid-based lithium salt, a combination thereof, or a lithium ion-conducting polymer selected from poly(ethylene oxide) (PEO), Polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVdF), Poly bis-methoxy ethoxyethoxide-phosphazenex, Polyvinyl chloride, Polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP), a sulfonated derivative thereof, or a combination thereof.
Zhamu ‘211 teaches an anode electrode for a lithium battery having a high capacity ([0015]), said electrode comprising a particulate comprising a core and a thin encapsulating layer encapsulating said core ([0016]), wherein said thin encapsulating layer has a lithium ion conductivity no less than 10-7 S/cm ([0016]).
Zhamu ‘211 further teaches wherein said thin encapsulating layer comprises a lithium-ion conducting additive such as Li2CO3, Li2O, Li2C2O4, LiOH, LiX, ROCO2Li, HCOLi, ROLi, (ROCO2Li)2, (CH2OCO2Li)2, Li2S, LixSOy, wherein X = F, Cl, I, or Br, R = a hydrocarbon group, 0 < x < 1, and 1 < y < 4, lithium perchlorate (LiClO4), lithium hexafluorophosphate (LiPF6), lithium borofluoride (LiBF4), lithium hexafluoroarsenide (LiAsF6), lithium trifluoro-methanesulfonate (LiCF3SO3), bis-trifluoromethyl sulfonylimide lithium (LiN(CF3SO2)2), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF2C2O4), lithium nitrate (LiNO3), Li-fluoroalkyl-phosphate (LiPF3(CF2CF3)3), lithium bisperfluoro-ethylsulfonylimide (LiBETI), lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), an ionic liquid-based lithium salt, poly(ethylene oxide) (PEO), Polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVdF), Poly bis-methoxy ethoxyethoxide-phosphazenex, Polyvinyl chloride, Polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP), a sulfonated derivative thereof, or a combination thereof ([0063]-[0066]), wherein the lithium ion-conducting additive is preferably included in the range of 1% to 35% ([0060]), which falls within and therefore reads on the instantly claimed range of 0.1% to 40% by weight.
It would have been obvious to one of ordinary skill in the art to utilize as Li2CO3, Li2O, Li2C2O4, LiOH, LiX, ROCO2Li, HCOLi, ROLi, (ROCO2Li)2, (CH2OCO2Li)2, Li2S, LixSOy, wherein X = F, Cl, I, or Br, R = a hydrocarbon group, 0 < x < 1, and 1 < y < 4, lithium perchlorate (LiClO4), lithium hexafluorophosphate (LiPF6), lithium borofluoride (LiBF4), lithium hexafluoroarsenide (LiAsF6), lithium trifluoro-methanesulfonate (LiCF3SO3), bis-trifluoromethyl sulfonylimide lithium (LiN(CF3SO2)2), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF2C2O4), lithium nitrate (LiNO3), Li-fluoroalkyl-phosphate (LiPF3(CF2CF3)3), lithium bisperfluoro-ethylsulfonylimide (LiBETI), lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), an ionic liquid-based lithium salt, poly(ethylene oxide) (PEO), Polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVdF), Poly bis-methoxy ethoxyethoxide-phosphazenex, Polyvinyl chloride, Polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP), a sulfonated derivative thereof, or a combination thereof, in the range of 1% to 35% by weight, as taught by Zhamu ‘211, in the thin encapsulating layer of modified Kim, with reasonable expectation that such would successfully improve the conductivity and charge/discharge efficiency of the anode electrode of modified Kim, as desired by modified Kim in order to successfully perform charging and discharging, as required for the lithium-ion battery of modified Kim.
Response to Arguments
Applicant’s arguments filed January 21, 2026 have been fully considered but they are not persuasive.
Regarding amended Claim 3, the Applicant argues that the combination of the prior references does not show or suggest the remaining claim limitations with -- wherein said electron-conducting material is selected from a nanocarbon particle, metal nanoparticle, metal nanowire, electron-conducting polymer, graphene, or a combination thereof, wherein said graphene is selected from functionalized graphene. All of the claims that are dependent on claim 3 are patentable for the same reason.
The Examiner respectfully disagrees and notes that, upon further consideration of the cited prior art, Zhamu teaches graphene materials that are good conductive additives for an electrode for a lithium battery ([0085]), wherein the graphene material may be functionalized graphene, and said graphene comprise single-layer graphene or few-layer graphene, wherein said few-layer graphene is defined as a graphene platelet formed of less than 10 graphene planes ([0085], [0092]).
It would have been obvious to one of ordinary skill in the art to utilize functionalized graphene, wherein said graphene comprises single-layer graphene or few-layer graphene, wherein said few-layer graphene is defined as a graphene platelet formed of less than 10 graphene planes, as the electron-conducing material of Kim, as taught by Zhamu, as such is not particularly limited and may be any variety available in the art, wherein the skilled artisan would have reasonable expectation that such would successfully function as the electron-conducting material and thereby form the anode electrode desired by Kim.
Thus, the arguments are not found to be persuasive.
Conclusion
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). 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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/KIMBERLY WYLUDA/Examiner, Art Unit 1725
/BASIA A RIDLEY/Supervisory Patent Examiner, Art Unit 1725