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.
Election/Restrictions
Applicant’s election without traverse of Group I (claims 1-7 and 16-21) in the reply filed on 04/27/2026 is acknowledged.
Claims 8-15 and 22-29 were withdrawn from further consideration pursuant to 37 CFR 1.142(b) as being drawn to nonelected Groups II and III, there being no allowable generic or linking claim. Election was made without traverse in the reply filed on 04/27/2026.
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.
Claim 1 is rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim 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.
Claim 1 recites the limitation "the electrolyte" in line 2. There is insufficient antecedent basis for this limitation in the claim.
Claims 3, 16, 17, and 18 are rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim 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.
A broad range or limitation together with a narrow range or limitation that falls within the broad range or limitation (in the same claim) may be considered indefinite if the resulting claim does not clearly set forth the metes and bounds of the patent protection desired. See MPEP § 2173.05(c). In the present instance:
claim 3 recites the broad recitation "comprises", and the claim also recites "consists of" which is the narrower statement of the range/limitation.
claim 16 recites the broad recitation "a thickness in the range of 1-15 nm", and the claim also recites "or in the range of 5-10 nm" which is the narrower statement of the range/limitation.
claim 16 recites the broad recitation “an areal porosity in the range of at least 15%”, and the claim also recites "or of at least 20% or at least 25% or at least 30% or at least 40%" which are narrower statements of the range/limitation.
claim 17 recites the broad recitation "comprises", and the claim also recites "consists of" which is the narrower statement of the range/limitation.
Claim 18 recites the broad recitation "a thickness in the range of 0.34-5 nm", and the claim also recites "or in the range of 0.34-1 nm" which is the narrower statement of the range/limitation.
The claim(s) are considered indefinite because there is a question or doubt as to whether the feature introduced by such narrower language is (a) merely exemplary of the remainder of the claim, and therefore not required, or (b) a required feature of the claims.
Claim Interpretation
The phrases “or” and “and/or” are recited throughout the claim set. These recitations are interpreted as “exclusive or” statements which are satisfied if any of the listed options are met by the prior art.
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.
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(s) 1-5, 7, and 16-19 is/are rejected under 35 U.S.C. 103 as being unpatentable over Zhamu1 et al. (US 2016/0301075 A1, as cited in the 07/20/2023 IDS) in view of Zhamu2 (US 2013/0059174 A1).
Regarding claim 1, Zhamu1 teaches a Li or Na based battery (a rechargeable alkali metal battery: lithium metal battery or sodium metal battery, [0014-0015]) comprising
an anode (an anode comprising an alkali metal layer, [0015]) at least partially covered on its side facing the electrolyte by at least one artificial solid-electrolyte interphase layer (dendrite penetration-resistant layer, [0015]; a separator and electrolyte component in contact with the anode and the cathode, wherein the dendrite penetration-resistant layer is disposed between the alkali metal layer and the separator, [0015]) with at least one layer of porous graphene (dendrite-stopping layer is made from an integral layer of porous graphene structure, [0041]) of a thickness of less than 25 nm (multi-layer graphene can have a thickness typically less than 10 nm, commonly referred to as few-layer graphene, [0061])
wherein said layer of porous graphene is a contiguous layer (these graphene sheets are preferably interconnected, i.e. overlapped with one another, [0017]; the continuous-length porous graphene structure, e.g. graphene paper, [0023]; integral layer per [0041] – interconnected, continuous, and integral read on “contiguous”) having passage openings in the form of said pores (multiple graphene sheets may be made into a sheet of NGP paper, which is an example of the porous graphene structure layer, [0061]) and which porous graphene is a two-dimensional planar layer (constituent graphene planes, [0056]; typically <10 nm in thickness, [0056, 0061]; single-layer graphene and multi-layer graphene sheets are collectively called “nano graphene platelets”: NGPs, [0056]) with said pores within said planar layer (sheet of NGP paper is an example of the porous graphene structure layer, [0061], and
wherein said planar layer is not absorbing (no absorption mentioned in reference) and said planar layer is not a three-dimensional skeleton (two-dimensional planes cited above, see also (D) in Fig. 1(A); monolithic body per [0074]).
Zhamu1 fails to explicitly teach the at least one layer of porous graphene with pores having an average characteristic width in the range of 1 - 1000 nm. Zhamu1 does teach in fabricating a conductive layer of porous graphene, it is desired to have a monolithic body having desired interconnected pores that are accessible to liquid electrolyte, and the compressive stress and/or the gap between rollers can be readily adjusted to obtain a desired layer of porous graphene structure that has pores accessible to liquid electrolyte ([0074-0075]). Zhamu1 further teaches an integrated structure that has substantially interconnected pores to accommodate electrolyte, wherein some of the pores in the structure are greater than 100 nm and some smaller than 100 nm ([0095-0096]), but does not explicitly teach this pore size applied to the graphene layer(s).
Zhamu2 is analogous in the art of batteries using graphene sheets in contact with electrolyte and teaches NGPs capable of forming a meso-porous structure having a desired pore size range (e.g. slightly >2 nm) when they were stacked together, and that this size range appears to be conducive to being accessible by the commonly used lithium-containing electrolytes ([0121]).
It would have been obvious, at the time of filing, for a person having ordinary skill in the art to modify the NGP porous graphene layer of Zhamu1 to have the desired pore size range taught by Zhamu2 with the motivation of achieving graphene pores conducive to being accessible by the commonly used lithium-containing electrolytes taught toward by Zhamu2 which was also an inventive goal of Zhamu1 to obtain a desired layer of porous graphene structure that has pores accessible to liquid electrolyte as cited above. The desired pore size range of e.g. slightly >2 nm falls within an obviates the claimed range “pores having an average characteristic width in the range of 1 - 1000 nm”.
Thus, the instant claim 1 is rendered obvious.
Regarding claim 2, modified Zhamu1 teaches the limitations of claim 1 above and the artificial solid-electrolyte interphase layer has a thickness in the range of 1-15 nm (typically <10 nm in thickness, [0056, 0061]). See MPEP 2144.05 I regarding obviousness of ranges that overlap / lie within. Also, see Claim Interpretation note above that “and/or” statements are satisfied when one condition is met by prior art.
Regarding claim 3 and claim 4, modified Zhamu1 teaches the limitations of claim 1 above and teaches the artificial solid-electrolyte interphase layer comprises or consists of said at least one porous graphene layer (as cited above) and at least one additional selective graphene layer, wherein the selective graphene layer is a defective graphene layer (the graphene planes have a controlled amount of point defects which are fast paths for migration of lithium or sodium ions, Zhamu1 [0044, 0070]).
Regarding claim 5, modified Zhamu1 teaches the limitations of claim 1 above and teaches wherein the anode is an elemental metal layer (anode comprising an alkali metal layer, Zhamu1 [0015]).
Regarding claim 7, modified Zhamu1 teaches the limitations of claim 1 above and teaches said at least one layer of porous graphene is at least partially N-doped (NGPs or graphene materials include … doped graphene (e.g. doped by … N), [0063]; nitrogen-doped graphene as interconnected graphene sheets example in [0044]).
Regarding claim 16, modified Zhamu1 teaches the limitations of claim 1 above and teaches the artificial solid-electrolyte interphase layer in the form of a porous graphene layer (dendrite-stopping layer is made from an integral layer of porous graphene structure, [0041]), has a thickness in the range of 1-15 nm, or in the range of 5-10 nm (typically <10 nm in thickness, [0056, 0061]). See MPEP 2144.05 I regarding obviousness of ranges that overlap / lie within. Also, see Claim Interpretation note above that “and/or” statements are satisfied when one condition is met by prior art.
Regarding claim 17, modified Zhamu1 teaches the limitations of claim 1 above and teaches the artificial solid-electrolyte interphase layer comprises or consists of said at least one porous graphene layer and at least one additional selective graphene layer (the graphene planes have a controlled amount of point defects which are fast paths for migration of lithium or sodium ions, Zhamu1 [0044, 0070]), but fails to explicitly teach said at least one porous graphene layer is facing said anode and the at least one additional selective graphene layer is facing said electrolyte.
However, Zhamu1 does teach the graphene planes with the defects (i.e., the selective/defective layer) have fast paths for migration of lithium or sodium ions ([0044]), and thus are selective toward the alkali ions of the electrolyte (electrolyte containing a solvent and a lithium salt or sodium salt dissolved in the solvent, per [0020, 0052]). Zhamu1 also teaches it is known in the art that dendrites commonly grow out of the metal anode, such as lithium, so the dendrite-stopping layer need be placed against the anode ([0003-0004, 0013-0015]). Further, Zhamu2 teaches that the pores in the stacked NGPs of the electrolyte are conducive to being accessible by the commonly used lithium-containing electrolytes ([0121]).
Therefore, it would have been obvious, at the time of filing, for a person having ordinary skill in the art to ensure that the at least one additional selective graphene layer was facing said electrolyte in order to selectively allow for ion migration from the electrolyte, and to ensure the at least one porous graphene layer was facing said anode in order to block dendrite formation from said anode as well as to be accessible to the electrolyte reaching the anode during cycling of the battery, as taught by toward by Zhamu1 and Zhamu2 per the above citations. Rearrangement of parts is also within the ambit of a person having ordinary skill in the art per MPEP 2144.04 VI C and would yield the expected results explained above.
Thus, the instant claim 17 is rendered obvious.
Regarding claim 18, modified Zhamu1 teaches the limitations of claim 3 above and teaches the selective graphene layer is a defective graphene layer, having atomic defects (the graphene planes have a controlled amount of point defects which are fast paths for migration of lithium or sodium ions, Zhamu1 [0044, 0070] – point defect e.g. missing C atom which reads on “atomic defect”), and … wherein said selective graphene layer has a thickness in the range of 0.34-5 nm, or in the range of 0.34-1 nm (0.34 nm for one graphene layer as shown in Zhamu1 Fig. 1(A); single-layer graphene can be as thin as 0.34 nm, Zhamu1 [0061]). Examiner notes that only one “or” condition need be met to satisfy the claim.
Regarding claim 19, modified Zhamu1 teaches the limitations of claim 1 above and teaches the anode is an elemental metal layer, wherein the metal is selected from the group consisting of lithium (rechargeable lithium metal batteries using lithium metal as the anode active material, anode active material layer e.g. a Li foil; Zhamu1 [0040-0041]) … or an alloy or layered composite thereof (lithium metal alloy as the anode active material, [0040]; alkali metal layer in the anode may contain an anode active material selected from lithium metal, … a lithium metal alloy, [0031]).
Claim(s) 6 and 20 is/are rejected under 35 U.S.C. 103 as being unpatentable over Zhamu1 et al. (US 2016/0301075 A1, as cited in the 07/20/2023 IDS) in view of Zhamu2 (US 2013/0059174 A1) as applied to claim 1 above, and further in view of Verbrugge et al. (US 2009/0325071 A1).
Regarding claim 6, modified Zhamu1 teaches the limitations of claim 1 above and teaches the at least one layer of porous graphene is a layer grown (graphene prepared by CVD growth, Zhamu1 [0066]), but fails to explicitly teach such grown directly on an elemental metal layer forming the anode.
Verbrugge is analogous in the art of electrodes for lithium-ion batteries (abstract) and teaches a current collector formed, for example, of a metal such as copper (Cu), nickel (Ni), or stainless steel (SS) that provides suitable electron conductivity for the electrode ([0022]) and that the catalyst-coated current collector may then be placed inside a chemical vapor deposition chamber and graphene layers or planes are grown over the current collector ([0026]) to form a completed current collector-graphene electrode body ([0030]). Verbrugge teaches the resulting electrode is dense, of increased volumetric efficiency relative to the conventional particulate-based electrode, and more efficient because electronically insulating polymeric binders are not required; this latter attribute also leads to a cost reduction through reduced material utilization ([0010]). Zhamu1 teaches in [0148] and example of a copper current collector for the anode.
It would have been obvious, at the time of filing, for a person having ordinary skill in the art to modify the anode of Zhamu1 to be made of an exemplary copper current collector as taught in Zhamu1 (see above citation) and in Verbrugge and to have the graphene layers directly grown thereon through chemical vapor deposition (CVD) as also taught by Verbrugge to form the complete current collector-graphene electrode body which achieves increased volumetric efficiency and cost reduction (as cited above).
Thus, the instant claim 6 is rendered obvious.
Regarding claim 20, modified Zhamu1 teaches the limitations of claim 1 above and teaches and teaches the at least one layer of porous graphene is a layer grown (graphene prepared by CVD growth, Zhamu1 [0066]), but fails to teach such grown directly on an elemental metal layer forming the anode, wherein the metal of said anode is selected from copper or copper nickel alloy or layered structure or an alloy or layered structure based on copper and/or nickel and at least one further metal selected from the group consisting of gold, silver and/or aluminium.
Verbrugge is analogous in the art of electrodes for lithium-ion batteries (abstract) and teaches a current collector formed, for example, of a metal such as copper (Cu), nickel (Ni), or stainless steel (SS) that provides suitable electron conductivity for the electrode ([0022]) and that the catalyst-coated current collector may then be placed inside a chemical vapor deposition chamber and graphene layers or planes are grown over the current collector ([0026]) to form a completed current collector-graphene electrode body ([0030]). Verbrugge teaches the resulting electrode is dense, of increased volumetric efficiency relative to the conventional particulate-based electrode, and more efficient because electronically insulating polymeric binders are not required; this latter attribute also leads to a cost reduction through reduced material utilization ([0010]). Zhamu1 teaches in [0148] and example of a copper current collector for the anode.
It would have been obvious, at the time of filing, for a person having ordinary skill in the art to modify the anode of Zhamu1 to be made of an exemplary copper current collector as taught in Zhamu1 (see above citation) and in Verbrugge and to have the graphene layers directly grown thereon through chemical vapor deposition (CVD) as also taught by Verbrugge to form the complete current collector-graphene electrode body which achieves increased volumetric efficiency and cost reduction (as cited above). The result reads on the “graphene layer grown directly on an elemental copper metal layer forming the anode”.
Thus, the instant claim 20 is rendered obvious.
Claim(s) 21 is/are rejected under 35 U.S.C. 103 as being unpatentable over Zhamu1 et al. (US 2016/0301075 A1, as cited in the 07/20/2023 IDS) in view of Zhamu2 (US 2013/0059174 A1) as applied to claim 1 above, and further in view of Granzier-Nakajima et al. (“Controlling Nitrogen Doping in Graphene with Atomic Precision: Synthesis and Characterization”. Nanomaterials. 2019; 9(3):425. https://doi.org/10.3390/nano9030425).
Regarding claim 21, modified Zhamu1 teaches the limitations of claim 1 above and teaches said at least one layer of porous graphene is at least partially N-doped (NGPs or graphene materials include … doped graphene (e.g. doped by … N), [0063]; nitrogen-doped graphene as interconnected graphene sheets example in [0044]), but fails to explicitly teach wherein the N-doping is in the form of at least one surficial N-doping and/or in the form of an N-doping of the pore boundaries.
Granzier-Nakajima is pertinent to the problem of n-doping of graphene with nitrogen (abstract) and teaches that different configurations of nitrogen within the carbon lattice have different electronic and chemical properties, and the ability to control different types of nitrogen doping configurations allows for the fine tuning of nitrogen doped graphene’s (NG’s) properties (abstract). Granzier-Nakajima at Fig. 1 and section 2 on page 3 teaches common nitrogen dopant configurations in graphene, including pyridinic-N, where a nitrogen atom is accompanied by a vacancy and bonds to two carbon atoms as part of a six-membered ring; and pyrrolic-N, where nitrogen bonds to two carbon atoms as part of a five-membered ring; nitrilic-N is also shown in Fig. 1 where a nitrogen dopant is bonded with one carbon and two hydrogen atoms (see also page 9). These show, in Fig. 1, the doping is in the form of an N-doping of the pore boundaries (or, vacancies – see pg. 2 and pg. 7 under section 3.1 and pg. 9 under section 3.2 explaining vacancy configurations). Each dopant bonding configuration can have different catalytic activities and affect the electronic structure in different ways; therefore, the ability to engineer NG to have the desired dopant configuration will allow control over device sensitivity and improve reproducibility (Granzier-Nakajima pg. 3).
It would have been obvious, at the time of filing, for a person having ordinary skill in the art to tailor the n-doping of graphene with nitrogen in modified Zhamu1 as taught by Granzier-Nakajima to engineer NG to have the desired dopant configuration and affect the electronic structure and chemical properties as desired, expectedly resulting in n-doping of the pore/vacancy boundaries as taught to be common by Granzier-Nakajima.
Thus, the instant claim 21 is rendered obvious.
Relevant Prior Art
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure.
Choi et al. (US 2015/0191358 A1) is pertinent to the problem of growing single and multi-layer graphene sheets and teaches that a high-quality single layer graphene may be grown by using a Cu/Ni multi-layer catalyst by a CVD method ([0010]), further teaching a multi-layer graphene electrode grown on the nickel lower-layered thin film and a single layer graphene channel grown on the copper upper-layered pattern ([0015]), in which the multi-layer graphene grown on the nickel lower-layered thin film may be used as an electrode ([0041]). Zhamu1 teaches in [0148] and example of a copper current collector for the anode.
Zhang et al. (“Nitrogen doping of graphene and its effect on quantum capacitance, and a new insight on the enhanced capacitance of N-doped carbon”. Energy Environ. Sci., 2012,5, 9618-9625, https://doi.org/10.1039/C2EE23442D) teaches that the area-normalized capacitance of lightly N-doped activated graphene with similar porous structure increased (abstract). The increase in bulk capacitance with increasing N concentration, and the increase of the quantum capacitance in the N-doped monolayer graphene versus pristine monolayer graphene suggests that the increase in the EDL type of capacitance of many, if not all, N-doped carbon electrodes studied to date, is primarily due to the modification of the electronic structure of the graphene by the N dopant (Abstract). A large electrochemically accessible surface area, appropriate pore size and distribution, good interconnectivity of pores, continuous pathways for rapid ion transport, large electrical conductivity, and good wettability are all important factors for the electrode material of an electrical double layer (EDL) capacitor (pg. 9618 col. 2 para. 1).
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to Jessie Walls-Murray whose telephone number is (571)272-1664. The examiner can normally be reached M-F, typically 10-4.
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, Matthew Martin can be reached at (571) 270-7871. 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.
/JESSIE WALLS-MURRAY/Primary Examiner, Art Unit 1728
Prosecution Insights