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 03/18/2024 is in compliance with the provisions of 37 CFR 1.97. Accordingly, the information disclosure statement is being considered by the examiner.
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 6-8 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.
Regarding claim 6, claim 6 depends from claim 1, which recites an ion conductor comprising a layered framework structure including Al, Si, and O. However, claim 6 recites compositional formulas (1) and (2) in which the variables b1, d1, b2, and d2 each have lower limits of zero. Consequently, the claimed ranges encompass embodiments in which b1 = 0 and d1 = 0 (or b2 = 0 and d2 = 0) simultaneously, thereby defining compositions that omit both Al and Si from the claimed framework structure. Because claim 6 encompasses embodiments that are inconsistent with the limitations of claim 1 from which it depends, claim 6 is indefinite.
Claims 7-8 are similarly rejected for depending upon claim 6.
Claim Rejections - 35 USC § 102
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 the appropriate paragraphs of 35 U.S.C. 102 that form the basis for the rejections under this section made in this Office action:
A person shall be entitled to a patent unless –
(a)(1) the claimed invention was patented, described in a printed publication, or in public use, on sale, or otherwise available to the public before the effective filing date of the claimed invention.
(a)(2) the claimed invention was described in a patent issued under section 151, or in an application for patent published or deemed published under section 122(b), in which the patent or application, as the case may be, names another inventor and was effectively filed before the effective filing date of the claimed invention.
Claims 1-2, 9-12, and 14-15 are rejected under 35 U.S.C. 102(a)(2) as being anticipated by Reuven (US 20220140384 A1).
Regarding claim 1, Reuven teaches an ion conductor comprising: a Li ion as a Li ion conductive species; and a layered framework structure comprising Al, Si, and O, the Li ion being located between layers in the layered framework structure ([0005, 0011, 0028]; Fig. 1).
Specifically, Reuven discloses a nano-clay (layered mineral aluminosilicate) comprising layered Al–Si–O sheets with Li ions intercalated between the aluminosilicate layers, thereby forming a Li-ion conducting nano-clay solid electrolyte (NCSE) ([0005, 0011, 0028]; Fig. 1).
Reuven further teaches that the layered framework structure may comprise layered mineral aluminosilicates including kaolinite, bentonite, montmorillonite, vermiculite, and saponite ([0005]). Reuven further discloses that the nano-clay comprises layered sheets with Li ions intercalated between the aluminosilicate layers, thereby forming a Li-ion conducting nano-clay solid electrolyte ([0011], [0028], Fig. 1).
Similarly, the instant application discloses that the layered framework structure comprises Al, Si, and O is formed from layered clay minerals including kaolinite, bentonite, montmorillonite, vermiculite, and saponite ([0014]). The instant application further identifies bentonite (Example 1B), montmorillonite (Example 1C), and saponite (Example 1D) as starting materials ([0117]) and teaches that Li ions are introduced into the layered aluminosilicate by cation exchange between the layers ([0030]). Accordingly, Reuven teaches the same type of layered Al–Si–O aluminosilicate framework and Li-ion intercalation between the layers as recited in claim 1, and therefore teaches the claimed layered framework structure comprising Al, Si, and O with Li ions located between the layers.
Regarding claim 9, Reuven teaches all limitations of claim 1 as stated above. Reuven further teaches a limitation wherein the ion conductor is a pressure-formed body ([0020-0021, 0030]).
Specifically Reuven teaches preparing the nano-clay solid electrolyte (NCSE) by compacting or pressing the NCSE powder into a shaped body prior to further processing or sintering ([0020-0021, 0030]).
Regarding claim 10, Reuven teaches all limitations of claim 9 as stated above. Reuven further teaches a limitation wherein the pressure-formed body is a solid electrolyte ([0020-0021, 0030]).
Specifically Reuven teaches that the pressed body is the nano-clay solid electrolyte (NCSE), which functions as the solid electrolyte of the battery ([0020-0021, 0030]).
Regarding claim 11, Reuven teaches all limitations of claim 1 as stated above. Reuven further teaches a limitation wherein the ion conductor is a sintered body ([0020, 0029]).
Specifically Reuven teaches sintering the pressed nano-clay solid electrolyte (NCSE) to produce the final electrolyte body and describes the effect of sintering on the NCSE structure ([0020, 0029]).
Regarding claim 12, Reuven teaches all limitations of claim 11 as stated above. Reuven further teaches a limitation wherein the sintered body is a solid electrolyte ([0020, 0029]).
Specifically Reuven teaches a sintered nano-clay solid electrolyte (NCSE) used as the solid electrolyte of the all-solid-state battery ([0020, 0029]).
Regarding claim 14, Reuven teaches all limitations of claim 1 as stated above. Reuven further teaches a limitation wherein the ion conductor is particles, and the average particle size of the ion conductor is less than or equal to 5 µm ([0005, 0016, 0019, 0020, 0028]).
Specifically, Reuven teaches a nano-clay solid electrolyte (NCSE) comprising nano-clay intercalated with nano Li ions ([0005]). Reuven further teaches that the NCSE is composed of a dense particle network ([0016]) and includes porous particles forming the NCSE structure ([0019]). Reuven additionally teaches that the starting materials are milled to obtain the prerequisite particle size distribution before fabrication ([0020]). Reuven also teaches that the nano-clay comprises approximately 1 nm thick aluminosilicate layers arranged in multilayer stacks; as the multilayer stacks are composed of such layers, the particles forming the stacks necessarily have a thickness smaller than 5 μm ([0028]). Accordingly, Reuven discloses nano-clay ion conductor is composed of nanoscale particles, the average particle size of which would necessarily be less than the claimed upper limit of 5 μm, and falls within the claimed range. Therefore, Reuven teaches the claimed limitation, and claim 14 is anticipated by Reuven.
Regarding claim 15, Reuven teaches all limitations of claim 1 as stated above. Reuven further teaches a battery comprising: a positive electrode; a negative electrode; and an electrolyte layer disposed between the positive electrode and the negative electrode, wherein at least one selected from the group consisting of the positive electrode, the electrolyte layer, and the negative electrode comprises the ion conductor described in claim 1 ([0004-0005, 0028-0029]).
Specifically, Reuven teaches an all-solid-state battery including an anode array (AA), a nano-clay solid electrolyte (NCSE), and a nano-clay cathode (NCC) ([0004-0005]). Reuven further teaches that the NCSE is a Li-ion conducting nano-clay solid electrolyte comprising the claimed layered aluminosilicate ion conductor ([0028-0029]). Thus, Reuven teaches a battery having a positive electrode (NCC), a negative electrode (AA), and an electrolyte layer (NCSE) disposed therebetween, wherein the electrolyte layer comprises the ion conductor of claim 1.
Claims 2 is rejected under 35 U.S.C. 102(a)(2) as being anticipated by Reuven (US 20220140384 A1). Shepelev et al. (Olga Shepelev, Sam Kenig, Hanna Dodiuk, 16 - Nanotechnology Based Thermosets, Editor(s): Hanna Dodiuk, Sidney H. Goodman, Handbook of Thermoset Plastics (Third Edition), William Andrew Publishing, 2014, Pages 623-695) is relied upon as an evidentiary reference in support of the rejection.
Regarding claim 2, , Reuven teaches all limitations of claim 1 as stated above. Reuven further teaches a limitation wherein the layered framework structure comprises at least one selected from the group consisting of Al oxides having an octahedral structure and Si oxides having a tetrahedral structure ([0005]).
Specifically, Reuven teaches that the layered framework structure may comprise layered mineral aluminosilicates including kaolinite, bentonite, montmorillonite, vermiculite, and saponite ([0005]). Furthermore, as evidenced by the Nanotechnology Based Thermosets handbook, montmorillonite, as one of these naturally occurring layered clay minerals possess aluminosilicate framework structures comprising SiO₄ tetrahedral sheets and AlO₆ octahedral sheets (page 623, Fig. 16.1)
Claim Rejections - 35 USC § 103
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 3 is rejected under 35 U.S.C. 103 as being unpatentable over Reuven, as applied to claim 1 above, and further in view of Bae et al. (Bae, Hyun Jeong, et al. "Atomically thin, large area aluminosilicate nanosheets fabricated from layered clay minerals." (2019), Materials Chemistry and Physics 221, 168-177.)
Regarding claim 3, Reuven teaches all limitations of claim 1 as stated above. Reuven does not teach a limitation wherein an X-ray diffraction pattern obtained by X-ray diffractometry of the ion conductor using Cu-Kα radiation has a peak in a range of diffraction angles 2θ greater than or equal to 2° and less than or equal to 10°.
Reuven teaches that the layered framework structure may comprise layered mineral aluminosilicates ([0005]. While Reuven identifies suitable layered aluminosilicates, Reuven does not disclose the claimed X-ray diffraction characteristics. Bae provides this structural teaching.
Specifically, Bae teaches Li-ion exchanged layered aluminosilicate (mica/muscovite) samples characterized by X-ray diffraction (XRD) using a Rigaku Ultima IV XRD system with Cu-Kα radiation (λ = 0.15405 nm) over a 2θ range of 3° to 60° (Bae, p. 169, section 2.2, Measurements). Bae further discloses the resulting X-ray diffraction patterns for the Li-ion exchanged muscovite samples (Fig. 2(a)), wherein the diffraction pattern includes a basal diffraction peak at approximately 5-9° 2θ, which falls within the claimed range of greater than or equal to 2° and less than or equal to 10°.
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filling date of the claimed invention to utilize the X-ray diffraction characteristics taught by Bae in the layered aluminosilicate electrolyte of Reuven because both references are directed to lithium-ion intercalation in layered aluminosilicate materials. Bae merely provides the well-known X-ray diffraction characteristics of a layered framework structure comprising Al, Si, and O, wherein the Li ion being located between layers in the layered framework structure.
Claims 4-6, and 8 are rejected under 35 U.S.C. 103 as being unpatentable over Reuven, as applied to claim 1 above, and further in view of Mineral Data Publishing reference (Dana, E.S., (1892), Dana's system of mineralogy, (6th edition), 690-691, 695-697)
Regarding claim 4, Reuven teaches all limitations of claim 1 as stated above. Reuven does not teach a limitation wherein the layered framework structure further comprises M, and M is at least one element selected from the group consisting of divalent metal elements and trivalent metal elements.
Reuven teaches that the nano-clay may comprise montmorillonite ([0005]). The instant specification acknowledges that montmorillonite is a layered aluminosilicate clay (see EX. 1C of instant application). Although Reuven identifies montmorillonite as a suitable layered mineral aluminosilicate, Reuven does not disclose that the layered framework structure comprises divalent metal elements and trivalent metal elements
However, as evidenced by the Mineral Data Publishing reference, Dana teaches that montmorillonite layered framework has Mg and Fe as structural cations in the crystal composition. Accordingly, the layered framework comprises divalent metal elements (Mg2+) and trivalent metal elements (Fe3+).
Accordingly, Dana teaches that montmorillonite is a layered aluminosilicate having a layered framework containing divalent and trivalent metal elements, while Reuven teaches incorporating Li ions into the interlayer structure of the layered aluminosilicate framework.
Therefore, it would have been obvious before the effective filing date of the claimed invention to one of ordinary skill in the art to utilize the well-known compositional formula of montmorillonite disclosed by Dana in the layered aluminosilicate electrolyte of Reuven because both references are directed to the layered aluminosilicate materials. Reuven expressly identifies montmorillonite as a suitable layered mineral aluminosilicate and teaches Li-ion intercalation into the aluminosilicate layers. Dana merely provides the recognized crystal composition of the same montmorillonite mineral employed by Reuven, thereby suggesting the claimed layered framework structure comprising divalent metal elements and trivalent metal elements.
Regarding claim 5, Reuven, as modified by Dana, teaches all limitations of claim 4 as stated above. Modified Reuven further teaches a limitation wherein M is at least one selected from the group consisting of Mg, Fe, Mn, and Zn.
As discussed with respect to claim 4, Reuven teaches that the nano-clay may comprise montmorillonite ([0005]). Furthermore, as evidenced by the Mineral Data Publishing reference, Dana teaches that montmorillonite layered framework has Mg and Fe as structural cations in the crystal composition. Accordingly, the layered framework comprises metal elements Mg and Fe.
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to utilize the well-known structural composition of the montmorillonite employed by Reuven, as evidenced by Dana, thereby arriving at a layered framework structure in which M is at least one selected from the group consisting of Mg, and Fe. Therefore, claim 5 would have been obvious over Reuven in view of Dana.
Regarding claim 6, Reuven teaches all limitations of claim 1 as stated above. Reuven does not teach a limitation wherein the ion conductor is represented by:
compositional formula (1): M1a1 (Alb1 M2c1) (Sid1 Ale1) O10(OH-Li+x1)2 or
compositional formula (2): M1a2 (M2b2 Alc2) (Sid2 Ale2)O10(OH-Li+x2)2,
wherein M1 is at least one element selected from trivalent metal elements,
M2 is at least one element selected from divalent metal elements,
the compositional formula (1) satisfies 0 ≤ a1 < 0.5, 0 ≤ b1 ≤ 2, 0 ≤ c1 ≤ 2, 0 ≤ d1 ≤ 4, 0 ≤ e1 ≤ 0.5, and 0 < x1 ≤ 1, and
the compositional formula (2) satisfies 0 ≤ a2 < 0.5, 0 ≤ b2 ≤ 3, 0 ≤ c2 ≤ 2, 0 ≤ d2 ≤ 4, 0 ≤ e2 ≤ 0.5, and 0 < x2 ≤ 1.
Specifically, Reuven teaches that the layered framework structure may comprise layered mineral aluminosilicates including kaolinite, bentonite, montmorillonite, vermiculite, and saponite ([0005]). Reuven further teaches that Li and/or Na atoms are intercalated into the interlayer surfaces of the aluminosilicate layers, and that the aluminosilicate layers permit Li and/or Na ion intercalation/deintercalation ([0028]). While Reuven identifies suitable layered aluminosilicates, Reuven does not describe their underlying crystal structure.
However, Dana provides this structural teaching. Dana discloses the chemical composition of montmorillonite, one of the layered aluminosilicate minerals identified by Reuven, as:
(Ca0.14 Na0.02)Σ=0.16 (Al1.68 Mg0.36 Fe0.04)Σ=2.08 (Si3.90 Al0.10)Σ=4.00 O10 (OH)2· 1.02H2O.
Dana therefore teaches a layered aluminosilicate framework comprising Fe, a trivalent metal element (M1), Mg and Ca, divalent metal elements (M2), together with Al, Si, O, and hydroxyl groups.
Accordingly, Dana teaches a layered aluminosilicate composition corresponding to the claimed framework containing trivalent and divalent metal elements, while Reuven teaches incorporation of Li into the interlayer structure of the aluminosilicate framework.
Therefore, it would have been obvious before the effective filing date of the claimed invention to one of ordinary skill in the art to utilize the well-known compositional formula of montmorillonite disclosed by Dana in the layered aluminosilicate electrolyte of Reuven because both references are directed to the layered aluminosilicate materials. Reuven identifies montmorillonite as a suitable layered mineral aluminosilicate and teaches Li intercalation into the aluminosilicate layers. Dana merely provides the recognized chemical composition of one of the layered aluminosilicate minerals employed by Reuven, thereby suggesting the claimed ion conductor represented by the recited compositional formula.
Regarding claim 8, Reuven, as modified by Dana, teaches all limitations of claim 6 as stated above. Dana further teaches a limitation wherein the ion conductor is represented by the compositional formula (2) in which M1 is Fe and M2 is Mg.
As discussed with respect to claim 6, Dana discloses the chemical composition of montmorillonite, one of the layered aluminosilicate minerals identified by Reuven, as:
(Ca0.14 Na0.02)Σ=0.16 (Al1.68 Mg0.36 Fe0.04)Σ=2.08 (Si3.90 Al0.10)Σ=4.00 O10 (OH)2· 1.02H2O.
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to utilize the well-known compositional formula of montmorillonite disclosed by Dana in the layered aluminosilicate electrolyte of Reuven because Reuven expressly identifies montmorillonite as a suitable layered mineral aluminosilicate and teaches Li intercalation into the aluminosilicate layers. Dana merely provides the recognized chemical composition of one of the layered aluminosilicate minerals employed by Reuven, thereby suggesting the claimed ion conductor represented by the compositional formula (2) in which M1 is Fe and M2 is Mg.
Claim 7 is rejected under 35 U.S.C. 103 as being unpatentable over Reuven, as modified by Dana, as applied to claim 6 above, and further in view of Shepelev et al. (Olga Shepelev, Sam Kenig, Hanna Dodiuk, 16 - Nanotechnology Based Thermosets, Editor(s): Hanna Dodiuk, Sidney H. Goodman, Handbook of Thermoset Plastics (Third Edition), William Andrew Publishing, 2014, Pages 623-695).
Regarding claim 7, Reuven, as modified by Dana, teaches all limitations of claim 6 as stated above. Modified Reuven does not teach a limitation wherein the ion conductor is represented by the compositional formula (1) in which M1 is Fe, M2 is Mg, and e1 = 0.
As discussed with respect to claim 6, Dana discloses the chemical composition of montmorillonite, one of the layered aluminosilicate minerals identified by Reuven, as:
(Ca0.14 Na0.02)Σ=0.16 (Al1.68 Mg0.36 Fe0.04)Σ=2.08 (Si3.90 Al0.10)Σ=4.00 O10 (OH)2· 1.02H2O.
As discussed with respect to claim 6, Dana teaches a montmorillonite composition comprising Fe as a trivalent metal element and Mg as a divalent metal element. Dana further discloses a representative montmorillonite composition in which the tetrahedral sheet contains only a minor amount of Al substitution, (Si₃.₉₀Al₀.₁₀)O₁₀, indicating that the tetrahedral substitution level is minimal but not zero. As evidenced by the Nanotechnology Based Thermosets handbook (page 623, Nanoclays section), Shepelev teaches that sodium montmorillonite possesses a Si₄O₁₀ tetrahedral sheet fused to an octahedral Al/Mg sheet, corresponding to a tetrahedral sheet without Al substitution (e₁ = 0). Accordingly, the combined teachings of Dana and Shepelev disclose the well-known idealized montmorillonite framework represented by a Si₄O₁₀ tetrahedral sheet together with the Fe/Mg structural composition taught by Dana in the layered aluminosilicate electrolyte of Reuven.
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to utilize the well-known structural composition of montmorillonite taught by Dana, as further evidenced by the idealized Si₄O₁₀ tetrahedral framework disclosed by Shepelev in the layered aluminosilicate electrolyte of Reuven because all references are directed to the layered aluminosilicate materials. Reuven expressly identifies montmorillonite as a suitable layered mineral aluminosilicate and teaches Li-ion intercalation into the aluminosilicate layers. Dana and Shepelev merely provide the recognized structural composition of the same montmorillonite mineral employed by Reuven, thereby suggesting the claimed ion conductor represented by compositional formula (2), wherein M1 is Fe, M2 is Mg, and e₁ = 0.
Claim 13 is rejected under 35 U.S.C. 103 as being unpatentable over Reuven (US 20220140384 A1). Keneda et al. (US 20170256800 A1) is relied upon as an evidentiary reference in support of the rejection.
Regarding claim 13, Reuven teaches all limitations of claim 1 as stated above. Reuven does not teach a limitation wherein the bulk density of the ion conductor is greater than or equal to 60% of the true density of the ion conductor.
Specifically, Reuven teaches a porous NCSE structure having a porosity of 10–90%, including an embodiment having a porosity of 40–80%. Keneda is relied upon solely as evidentiary support to demonstrate that it was well known in the art that porosity, bulk density, and true density are mathematically related according to:
Porosity (%) = (1 − (Bulk Density / True Density)) × 100 ([0239]).
Accordingly, the bulk density greater than or equal to 60% of the true density corresponds to a porosity of 40% or less. Reuven discloses a porosity range of 10-90%, which encompasses porosity values of 40% or less. Therefore, the claimed density limitation represents an overlapping portion of the porosity range disclosed by Reuven when expressed in terms of the well-known mathematical relationship between porosity, bulk density, and true density. It is noted that where the claimed ranges overlap or lie within the ranges disclosed by the prior art, a prima facie case of obviousness exists. See MPEP 2144.05(I).
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to Lili Rassouli whose telephone number is (571)272-9760. The examiner can normally be reached Monday-Thursday 8:00 AM-4:00 PM.
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/LILI RASSOULI/ Examiner, Art Unit 1728
/MATTHEW T MARTIN/ Supervisory Patent Examiner, Art Unit 1728
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