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.
Claim Rejections - 35 USC § 102/103
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 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.
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.
Claim(s) 1 4, and 6 are rejected under 35 U.S.C. 102(a)(1) as anticipated by or, in the alternative, under 35 U.S.C. 103 as obvious over Bohnsack (“Ternary Chlorides of the Rare-Earth Elements with Lithium, Li3MCl6 (M = Tb-Lu, Y, Sc): Synthesis, Crystal Structures, and Ionic Motion, Journal of Inorganic and General Chemistry”, 1997, Vol. 623, pp. 1067 – 1073, cited in 06/25/2024 IDS, NPL provided), hereinafter Bohnsack, as evidenced by Shao (CN107425218A, cited in 06/25/2024, Machine translation provided).
Regarding Claim 1, Bohnsack discloses a solid electrolyte material (a ternary halide material with lithium-conductivity; first paragraph of Introduction section in right column on pg. 1067 and last paragraph in Li+-ion conductivity section in left column on pg. 1072), comprising Li (Refer to Li3YCl6 in Table 1), Y (Refer to Li3YCl6 in Table 1), which an element that is neither Li or a metalloid and thus is within the claimed scope of M; and Cl (Refer to Li3YCl6 in Table 1), which is an element within the group consisting of F, Cl, Br and I and thus is within the claimed scope of X.
In the instant specification, the applicant discloses calculating the average ionic radius of Li and M in the claimed material through the formula:
∑
r
c
∙
R
c
/
∑
R
c
, where rc represents the ionic radius of Li and M element(s) and Rc represents the amount of Li and M element(s) ([0014]). The applicant further discloses using the formula:
∑
r
A
∙
R
A
/
∑
R
A
to calculate the average ionic radius of X contained in the claimed material, where rA represents the ionic radius of the X element(s) and RA represents the amount of X element(s) ([0015]). The applicant further provides that the ionic radii of Li, Y, and Cl are 0.76, 0.90, and 1.81 ([0115]).
Bohnsack teaches preparing the ternary halide material by melting a mixture of binary components LiCl and MCl3 where M = Y in a ratio of 3:1; therefore, based on the applicant’s equation and ionic radii of Li, Y and Cl, the average ionic radius ratio of the ternary halide material, Li3YCl6, is 0.674 which is within the claimed range of an average ionic radius of Li and M by an average ionic radius of X greater than 0.424.
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=
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)
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=
0.795
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=
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≈
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Bohnsack teaches that Li3YCl6 crystallizes into two phases, Li3YbCl6-type and Li3ErCl6-type (Figs. 1 – 2; second paragraph in right column in Crystal structure of the Li3MCl6 chlorides (M=Tb-Lu, Y, Sc) section on pg. 1071). Bohnsack further teaches that the crystal structure includes a hexagonal closest packing of chloride atoms (first and second paragraphs in Crystal structure of the Li3MCl6 chlorides (M=Tb-Lu, Y, Sc) section in right column on pg. 1069; first and second paragraphs in left column in Crystal structure of the Li3MCl6 chlorides (M=Tb-Lu, Y, Sc) section on pg. 1071). In the instant specification, the applicant teaches that “crystal phases assigned to hexagonal crystals” refers to crystal phases that have a crystal structure similar to Li3ErCl6 (Instant Specification: [0017]). Therefore, since Bohnsack teaches that Li3YCl6 possesses a Li3ErCl6-type phase with hexagonal packing of chloride atoms, one with ordinary skill in the art would necessarily expect Bohnsack’s material, Li3YCl6, to necessarily and inherently contain a crystal phase assigned to hexagonal crystals.
Bohnsack does not explicitly disclose the solid electrolyte Li3YCl6 satisfying a mathematical formula (I): FWHM/2θp ≤ 0.015 wherein, FWHM represents a half width of an X-ray diffraction peak in an X-ray diffraction pattern obtained by performing X-ray diffraction measurement on the solid electrolyte material by using Cu-Ka radiation, the X-ray diffraction peak having the highest intensity within a range of diffraction angles 2θ greater than or equal to 25° and less than or equal to 35°, and 2θp represents a diffraction angle at a center of the X-ray diffraction peak.
In the instant application, the applicant discloses preparing a first embodiment of the solid electrolyte material by mixing raw materials, such as different halide components, using a mortar and pestle, ball mill or a mixer to obtain a mixed powder and performing a heat treatment at temperature higher than or equal to 100°C and lower than or equal to 650°C for 1 hour or longer in vacuum or inert atmosphere (Instant Specification: [0033 – 0036]).
Bohnsack teaches preparing the ternary halide material by melting a mixture of binary components LiCl and MCl3 in a ratio of 3:1 at a temperature of 650°C and subsequently cooling at rate of -1°C/h to room temperature in a vacuum atmosphere (Refer to left and right column paragraphs of Experiments section on pg. 1068). Furthermore, Bohnsack teaches Li3YCl6 crystallizes into an Li3ErCl6-type structure under higher temperature modification {i.e. at least 310°C} (second paragraph in right column in Crystal structure of the Li3MCl6 chlorides (M=Tb-Lu, Y, Sc) section on pg. 1071).
While Bohnsack does not disclose a step of mixing the raw materials components using a pestle, ball mill, or mixer to obtain the mixture of binary components prior to heating, one with ordinary skill in the art would reasonably expect Bohnsack’s binary components to be mixed as such because 1) Bohnsack refers to raw materials as a mixture and thus implies a mixing step (Refer to left and right column paragraphs of Experiments section on pg. 1068) and 2) because such mixing methods are understood/known in the art to be used when preparing solid electrolyte materials. For example, Shao teaches ball-milling raw materials, including halide raw materials, to obtain a solid electrolyte precursor prior to heating and obtaining the solid electrolyte material (Shao: [0026 – 0030]).
Therefore, since the halide solid electrolyte material of Bohnsack has a composition within the claimed scope, a method of making significantly similar to the applicant’s taught method (Instant Specification: [0033 – 0036]), and further appears to have a crystal structure {i.e. hexagonal/ similar to Li3ErCl6-type} suggested by the applicant to be required to satisfy the claimed equation (Instant Specification: Table 1; [0111 – 0112]), one with ordinary skill in the art would necessarily expect Bohnsack’s ternary halide material to provide an XRD-pattern significantly similar to applicant’s material and thus provide a FWHM and 2θp satisfying the claimed equation FWHM/2θp ≤ 0.015. Where the claimed and prior art products are identical or substantially identical in structure or composition, or are produced by identical or substantially identical processes, a prima facie case of either anticipation or obviousness has been established. In re Best, 562 F.2d 1252, 1255, 195 USPQ 430, 433 (CCPA 1977). [See MPEP 2112.1]
Assuming, arguendo, applicant is able to provide sufficient evidence showing that the Li3YCl6 halide material would not necessarily and inherently satisfy the claimed equation, the examiner further relies on the following alterative rejection.
Alternatively, since Bohnsack’s material is significantly similar to applicant’s material in regard to composition, preparation method, and crystal structure, it would have been obvious to one with ordinary skill in the art, before the effective filing date of the claimed invention that Bohnsack’s ternary halide material would provide a diffraction pattern that provides a FWHM and 2θp that is significantly close to/at least overlap the claimed FWHM/2θp range and thus establishing a prima facie case of obviousness [See MPEP 2144.05(II)].
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63
157
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Greyscale
One with ordinary skill in the art would appreciate/recognize that applicant’s FWHM/2θp range of ≤ 0.015 suggests a sharp/thin peak at the X-ray diffraction peak having the highest intensity within a range of diffraction angles 2θ greater than 25° or equal to 35°C. One would further appreciate, based on the Scherrer’s equation (included above), where τ corresponds to crystallite size and β corresponds to line broadening of the FWHM, that a shorter FWHM {i.e. narrower peaks} corresponds to larger crystals and thus a material of greater crystallinity.
Bohnsack further appears to show that higher crystallinities provide greater conductivities (Refer to Fig. 4 and first paragraph in Li+-ion conductivity section in right column on pg. 1071).
As such, absent a showing of criticality, it would have been obvious to one with ordinary skill in the art, before the effective filing date of the claimed invention to form the halide material as taught in Bohnsack that satisfies the claimed equation though routine optimization of the material’s crystallinity, and thus the conductivity, with a reasonable expectation of success and without undue experimentation [See MPEP 2144.05(II)].
Regarding Claim 4, Bohnsack discloses all limitations as set forth above. In Bohnsack, the halogen element, X, in the solid electrolyte material Li3YCl6 is chloride, which is within the claimed scope of at least one element selected from the group consisting of Cl and Br.
Regarding Claim 6, Bohnsack discloses all limitations as set forth above. As established above, Bohnsack’s ternary lithium halide material includes chloride as the halogen. In addition, the material also includes lithium and a rare earth metal, yttrium (Refer to Li3YCl6; Table 1). The molar ratio of Li to the halide of the material is 0.5 {i.e. Li/X = 3/6}, which is with the claimed range of greater than or equal to 0.3 and less than or equal to 0.6.
Claim Rejections - 35 USC § 103
The text of those sections of Title 35, U.S. Code not included in this action can be found in the section above in the current Office action.
Claim(s) 2 – 3 and 7 are rejected under 35 U.S.C. 103 as being unpatentable over Bohnsack (“Ternary Chlorides of the Rare-Earth Elements with Lithium, Li3MCl6 (M = Tb-Lu, Y, Sc): Synthesis, Crystal Structures, and Ionic Motion, Journal of Inorganic and General Chemistry, Vol. 623, pp. 1067 – 1073) and Shao (CN107425218A), as applied to claim 1 above, and further in view of Schlaikjer ("Ionic conduction in calcium doped polycrystalline lithium iodide.", 1971, Journal of the Electrochemical Society 118, no. 9, pp. 1447 – 1450, See 06/25/2024 IDS, NPL provided).
Regarding Claims 2 – 3, Bohnsack discloses all limitations as set forth above. Bohnsack’s ternary halide material has application as a solid electrolyte material due to being a lithium ion conductive material.
Bohnsack does not disclose M containing a group 2 element (Claim 2) or further wherein the group 2 element is Ca (Claim 3).
Schlaikjer specifically teaches doping a lithium halide material, lithium iodide, with calcium, in an amount of up to 3% (mol), to increase the ionic conductivity of the lithium iodide material (Refer to Fig. 1; second paragraph of the Introduction section on pg. 1447 and; and the first paragraph of the Results section on pg. 1448). Schlaikjer further teaches that divalent calcium ions induce Schottky defects in the crystal structure of the material which improve the mobility of cation vacancies and ultimately allow for improved ionic conductivity (Refer to third paragraph of the Discussion section on pg. 1450).
Since Bohnsack’s material is also an Li-ion conductive material that includes lithium and a halogen, it would have been obvious to one with ordinary skill in the art, before the effective filing date of the claimed invention to modify Bohnsack’s material by including a group 2 metal, such as Ca, as taught by Schlaikjer, with a reasonable expectation of success in making the lithium metal halide material a more effective solid electrolyte material by further increasing the ionic conductivity of the material.
Claim(s) 5 is rejected under 35 U.S.C. 103 as being unpatentable over Bohnsack (“Ternary Chlorides of the Rare-Earth Elements with Lithium, Li3MCl6 (M = Tb-Lu, Y, Sc): Synthesis, Crystal Structures, and Ionic Motion, Journal of Inorganic and General Chemistry, Vol. 623, pp. 1067 – 1073) and Shao (CN107425218A), as applied to claims 1 and 4 above, and further in view of Tomita ("Substitution effect of ionic conductivity in lithium ion conductor, Li3InBr6− xClx.", 2008, Solid State Ionics 179, no. 21-26, pp. 867-870)
Regarding Claim 5, Bohnsack discloses all limitations as set forth above. As established above, Bohnsack’s ternary lithium halide material includes chloride as the halogen (Refer to Li3YCl6 in Table 1).
Bohnsack does not disclose wherein: X is Cl and Br.
Tomita teaches a lithium ion conductor material comprising lithium, a rare earth metal, indium, and halides, Br and Cl (Refer to second paragraph of Introduction and first paragraph of Experimental section on pg. 867). The molar ratio of Li to halide in Tomita’s material is also 0.5 (Refer formula: Li3InBr6-xClx). Tomita further teaches that the combination of Cl and Br increases the stability of the crystal structure and provides changes in the lattice volume that ultimately increases the ion conductivity of the material (Refer to first and second paragraphs in AC conductivity section pgs. 868 – 869 and the Conclusion section on pg. 870).
Since Bohnsack’s ternary halide material already includes chloride and a rare earth metal, it would have been obvious to one with ordinary skill in the art, before the effective filing date of the claimed invention, to further modify Bohnsack’s ternary halide material by adding bromide as an additional halogen element, as taught by Tomita, with a reasonable expectation of success in making the lithium metal halide material a more effective solid electrolyte material by further increasing the ionic conductivity of the material.
Claim(s) 7 is rejected under 35 U.S.C. 103 as being unpatentable over Bohnsack (“Ternary Chlorides of the Rare-Earth Elements with Lithium, Li3MCl6 (M = Tb-Lu, Y, Sc): Synthesis, Crystal Structures, and Ionic Motion, Journal of Inorganic and General Chemistry, Vol. 623, pp. 1067 – 1073) and Shao (CN107425218A), as applied to claim 1 above, and further in view of Shao (CN107425218A).
Regarding Claim 7, Bohnsack discloses all limitations as set forth above. Bohnsack’s ternary halide material has application as a solid electrolyte material due to being a lithium ion conductive material.
Bohnsack does not explicitly disclose 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 negative electrode, and the electrolyte layer contains the solid electrolyte material according to Claim 1.
Shao teaches a solid electrolyte material comprising Li, divalent metals, and halides ([0012]). Shao further teaching using the solid electrolyte material in the electrolyte material between a positive electrode sheet and negative electrode sheet of a lithium ion battery ([0042]).
Since Bohnsack’s ternary halide material is also a lithium ion conductive material, it would have been obvious to one with ordinary skill in the art, before the effective filing date of the claimed invention, to routinely apply the material in the electrolyte layer of a lithium ion battery, as taught by Shao, with a reasonable expectation of success in achieving a lithium ion battery with a suitable electrolyte.
Conclusion
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/A.Y.O./Examiner, Art Unit 1751
/Haroon S. Sheikh/Primary Examiner, Art Unit 1751
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