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 .
Status of Claims
The Applicant’s amendment and arguments, filed 05/14/2026, has been entered. Claims 12-13, 21, and 27 are amended; claims 1-4, 14, 16-20, 23-26, and 28-29 stand as originally or previously presented; and claims 5-11, 15, and 22 are canceled. Support for the amendments is found in the original filing, and there is no new matter.
Upon considered said amendments and arguments, the previous 35 U.S.C.112(b), 35 U.S.C.102, and 35 U.S.C.103 rejection set forth in Office Action mailed 11/17/2025 has been withdrawn. The previously allowed subject matter of Claims 1-2 and 4 in Office Action mailed 11/17/2025 has been withdrawn.
Amended and new grounds of rejections under U.S.C.112(b) and 35 U.S.C. 103 citing to newly cited art and the originally cited art are set forth below as necessitated by the claim amendments.
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.
Claim(s) 12, 16-21 and 23-26 is/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.
Claim 12 recites the limitation “wherein the inorganic compound includes, a higher ratio of fluorine to zirconium and a lower ratio of carbon to zirconium, compared to when the process as described in claim 1 is not used.” in lines 13-14. The limitation is indefinite as there may be a variation that is outside of the claimed process of claim 1 (i.e. 5 hours of contact between the solid and the fluorinated atmosphere) that could produce a higher claimed ratio. Claims 16-21 and 23-26 are hereby rejected due to dependency on rejected Claim 12.
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.
Claim(s) 1-4, 12-14, 16-21, 23-26, and 28 is/are rejected under 35 U.S.C. 103 as being unpatentable over Chao et al. (US 20210202983 A1, hereinafter Chao), in view of Breddemann et al. (“Fluorination of Li-Rich Lithium-Ion-Battery Cathode Materials by Fluorine Gas: Chemistry, Characterization, and Electrochemical Performance in Half Cells, hereinafter Breddemann).
Regarding Claim 1, Chao discloses the limitations regarding a fluorination process comprising bringing a fluorine into contact with an inorganic compound M having a garnet-type structure (Chao, providing a solution including a fluoride salt and a solvent and immersing at least one surface of the sintered lithium-stuffed garnet thin film or pellet in the solution at a temperature between, or equal to, 0° C. and 60° C, resulting in a fluorinated surface, [0005, 0179]), which is based on the elements Li, La, Zr, A and O and for which the relative composition of the Li, La, Zr and A cations corresponds to the formula (I): LixLa3ZrzAW (I) wherein:
A denotes at least one element selected from the group consisting of Al, Ga, Nb, Fe, W and Ta;
x, z and w denote real numbers;
1.20 < z ≤ 2.10;
0 < w ≤ 0.80;
4.00 ≤ x ≤ 10.50 (Chao, lithium-stuffed garnet thin film or pellet bulk is characterized by a formula selected from the group consisting of LiALaBM’CM’’DZrEOF, wherein 4<A<8.5, 1.5<B<4, 0≤C<2, 0≤D<2; 0<E<2, 10<F<14, and wherein M′ and M″ are each, independently, selected from the group consisting of Al, Nb, W, and Ta, [0172];
Li = Li, and 4<A<8.5, overlapping the claimed range of 4.00 ≤ x ≤ 10.50;
La = La, and 1.5<B<4;
Zr = Zr, and 0<E<2, meeting the claimed range of 1.20 < z ≤ 2.10;
A = M’ or M’’ = Al, Nb, W, and Ta, and 0≤C<2, meeting the claimed range of 0 < w ≤ 0.80).
Chao discloses providing a solution including a fluoride salt and a solvent and immersing at least one surface of the sintered lithium-stuffed garnet thin film or pellet in the solution at a temperature between, or equal to, 0° C. and 60° C (Chao, [0005]), and a fluorinated surface resists the formation of oxides, carbonates, hydroxides, peroxides, and organics that spontaneously form on LLZO surfaces under ambient conditions (Chao, Abstract).
Chao is silent regarding a fluorination process comprising bringing an atmosphere comprising difluorine gas into contact with an inorganic compound M having a garnet-type structure, the duration of the contact between the solid and the fluorinated atmosphere is between 2 minutes and 4 hours, and the temperature at which the fluorination is carried out is between 20°C and 300°C, as claimed.
Breddemann discloses a fluorination process comprising bringing an atmosphere comprising difluorine gas into contact (Breddemann, Li-rich material were mildly fluorinated with F2, Page 3338, paragraph starting with “Li-rich material…”) with an inorganic compound (Breddemann, Li-rich cathode material of the general formula 0.35Li2MnO3·0.65Li[Mn0.45Ni0.35Co0.20]O2, Page 3338, paragraph starting with “Li-rich material…”),
the duration of the contact between the solid and the fluorinated atmosphere is between 2 minutes and 4 hours (Breddemann, immediately after exposure to the fluorine gas, the pressure began to drop, stabilizing within a few minutes indicating that the reaction was over, Page 3338, paragraph starting with “Li-rich material…”; the Examiner notes that “a few minutes” would at least overlap with the claimed range of between 2 minutes and 4 hours. In addition, a skilled artisan would recognize that contact between the material and fluorine should continue until the reaction was over, as disclosed by Breddemann); and
the temperature at which the fluorination is carried out is between 20°C and 300 °C (Breddemann, pressures between 0.10 to 1.00 bar in a transparent 120mL batch
PFA-reactor at room temperature, Page 3338, paragraph starting with “Li-rich material…”; the Examiner notes that a skilled artisan would recognize that room temperature has a range of 20°C – 25°C, and the disclosed range of 20°C – 25°C falls within the claimed range of 20°C and 300 °C).
Breddemann teaches that the treatment of Li-rich HE-NCM cathode material with low pressures (a few hundred mbar) of elementary fluorine gas at room temperature led to the elimination of surface species (such as LiOH, Li2CO3, Li2O, etc.), and as a consequence, the resulting improved passivation including thin amorphous LiF film led to increased capacity and long-term stability of the battery (Breddemann, Page 3347, paragraph starting with “the treatment of Li-rich…”).
Chao and Breddemann are analogous to the current invention as they are all directed towards surface fluorination of an inorganic material.
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for the lithium-stuffed garnet of modified Chao to be alternatively fluorinated with F2, as taught by Breddemann, because the result of eliminating surface species (such as LiOH, Li2CO3, Li2O, etc.), would have been reasonably predicted, as taught by both Chao and Breddemann, as noted above (see MPEP 2143(I)(A)).
In addition, it would have been obvious to one having ordinary skill in the art before the time of the effective filing date of the current invention to select the overlapping time of the disclosed in order to ensure that the reaction was complete because selection of overlapping portions of ranges has been held to be a prima facie case of obviousness (see MPEP 2144.05 (I)).
Regarding Claim 2, modified Chao discloses all of the claim limitations as set forth above. Modified Chao discloses the limitations regarding a fluorination process (Breddemann, material was mildly fluorinated with F2, Page 3338, paragraph starting with “Li-rich material…”), wherein the inorganic compound M comprises the oxide of formula (II): Lix1La3ZrzAWO12 (II), wherein z and w are as defined in claim 1 and x1 is a positive real number which is such that the electroneutrality of the oxide is ensured (Chao, lithium-stuffed garnet thin film or pellet bulk is characterized by a formula selected from the group consisting of LiALaBM’CM’’DZrEOF, wherein 4<A<8.5, 1.5<B<4, 0≤C<2, 0≤D<2; 0<E<2, 10<F<14, and wherein M′ and M″ are each, independently, selected from the group consisting of Al, Nb, W, and Ta, [0172];
Li = Li, and 4<A<8.5, x1 is a positive real number;
La = La, and 1.5<B<4;
Zr = Zr, and 0<E<2, overlapping the claimed range of 1.20 < z ≤ 2.10;
A = Al, Nb, W, and Ta, and 0≤C<2, overlapping the claimed range of 0 < w ≤ 0.80
O = O, and 10<F<14, overlapping the claimed amount of 12).
It would have been obvious to one having ordinary skill in the art before the time of the effective filing date of the current invention to select the overlapping portions of the disclosed because selection of overlapping portions of ranges has been held to be a prima facie case of obviousness (see MPEP 2144.05 (I)).
Regarding Claim 3, modified Chao discloses all of the claim limitations as set forth above. Modified Chao discloses the limitations regarding a fluorination process (Breddemann, material was mildly fluorinated with F2, Page 3338, paragraph starting with “Li-rich material…”) comprising bringing an atmosphere comprising difluorine gas into contact with an oxide of formula (II): Lix1La3ZrzAWO12 (II),
A denotes at least one element selected from the group consisting of Al, Ga, Nb, Fe, W and Ta;
x1, z and w denote real numbers;
1.20 < z ≤ 2.10;
0 < w ≤ 0.80;
x1 is a positive real number which is such that the electroneutrality of the oxide is ensured (Chao, lithium-stuffed garnet thin film or pellet bulk is characterized by a formula selected from the group consisting of LiALaBM’CM’’DZrEOF, wherein 4<A<8.5, 1.5<B<4, 0≤C<2, 0≤D<2; 0<E<2, 10<F<14, and wherein M′ and M″ are each, independently, selected from the group consisting of Al, Nb, W, and Ta, [0172];
Li = Li, and 4<A<8.5, overlapping the claimed range of 4.00 ≤ x ≤ 10.50;
La = La, and 1.5<B<4;
Zr = Zr, and 0<E<2, overlapping the claimed range of 1.20 < z ≤ 2.10;
A = M’ or M’’ = Al, Nb, W, and Ta, and 0≤C<2, overlapping the claimed range of 0 < w ≤ 0.80
O = O, and 10<F<14, overlapping the claimed amount of 12).
It would have been obvious to one having ordinary skill in the art before the time of the effective filing date of the current invention to select the overlapping portions of the disclosed because selection of overlapping portions of ranges has been held to be a prima facie case of obviousness (see MPEP 2144.05 (I)).
Regarding Claim 4, modified Chao discloses all of the claim limitations as set forth above. Modified Chao discloses the limitations regarding a fluorination process (Breddemann, material was mildly fluorinated with F2, Page 3338, paragraph starting with “Li-rich material…”), wherein the element zirconium is partially replaced by the element hafnium (Chao, M′ and M″ are each, independently, selected from the group consisting of Hf, [0172]).
Regarding Claim 12, modified Chao discloses all of the claim limitations as set forth above. Modified Chao discloses the limitations regarding a garnet-type inorganic compound based on the elements Li, La, Zr, A, O, and optionally Hf, which is obtained by a fluorination process (Breddemann, material was mildly fluorinated with F2, Page 3338, paragraph starting with “Li-rich material…”), wherein the garnet-type inorganic compound in which the relative composition of the Li, La, Zr and A cations corresponds to the formula (I): LixLa3ZrzAW (I) wherein:
A denotes at least one element selected from the group consisting of Al, Ga, Nb, Fe, W and Ta;
x, z and w denote real numbers;
1.20 < z ≤ 2.10;
0 < w ≤ 0.80;
4.00 ≤ x ≤ 10.50 (Chao, lithium-stuffed garnet thin film or pellet bulk is characterized by a formula selected from the group consisting of LiALaBM’CM’’DZrEOF, wherein 4<A<8.5, 1.5<B<4, 0≤C<2, 0≤D<2; 0<E<2, 10<F<14, and wherein M′ and M″ are each, independently, selected from the group consisting of Al, Nb, W, and Ta, [0172];
Li = Li, and 4<A<8.5, overlapping the claimed range of 4.00 ≤ x ≤ 10.50;
La = La, and 1.5<B<4;
Zr = Zr, and 0<E<2, overlapping the claimed range of 1.20 < z ≤ 2.10;
A = M’ or M’’ = Al, Nb, W, Hf and Ta, and 0≤C<2, overlapping the claimed range of 0 < w ≤ 0.80)
wherein the inorganic compound includes a higher ratio of fluorine to zirconium (Chao, a surface of a sintered LLZO thin film has a 2.9 Zr3d% and a 29.03 F1s%, resulting in a ratio of 29.03/2.9 = 10, [0344-0346]) and a lower ratio of carbon to zirconium, compared to when the process is not used (Chao, the result shows that the treated surface is stable for at least 30 hours in dry room environments, i.e., room temperature and −40° C. dew point, whereas the untreated surface forms lithium carbonate during the exposure time, [0335-0339], Figure 2).
It would have been obvious to one having ordinary skill in the art before the time of the effective filing date of the current invention to select the overlapping portions of the disclosed because selection of overlapping portions of ranges has been held to be a prima facie case of obviousness (see MPEP 2144.05 (I)).
Regarding Claim 13, modified Chao discloses all of the claim limitations as set forth above. Modified Chao discloses the limitations regarding an inorganic compound having a garnet-type structure based on the elements O, Li, La, Zr, and A and for which the relative proportions of which are those of the formula (I): LixLa3ZrzAW (I) wherein:
A denotes at least one element selected from the group consisting of Al, Ga, Nb, Fe, W and Ta;
x, z and w denote real numbers;
1.20 < z ≤ 2.10;
0 < w ≤ 0.80;
4.00 ≤ x ≤ 10.50 (Chao, lithium-stuffed garnet thin film or pellet bulk is characterized by a formula selected from the group consisting of LiALaBM’CM’’DZrEOF, wherein 4<A<8.5, 1.5<B<4, 0≤C<2, 0≤D<2; 0<E<2, 10<F<14, and wherein M′ and M″ are each, independently, selected from the group consisting of Al, Nb, W, and Ta, [0172];
Li = Li, and 4<A<8.5, overlapping the claimed range of 4.00 ≤ x ≤ 10.50;
La = La, and 1.5<B<4, overlapping the claimed amount of 3;
Zr = Zr, and 0<E<2, overlapping the claimed range of 1.20 < z ≤ 2.10;
A = M’ or M’’ = Al, Nb, W, and Ta, and 0≤C<2, meeting the claimed range of 0 < w ≤ 0.80),
and wherein the fluorine is concentrated at a surface of the compound (Chao, a surface of a sintered LLZO thin film has 29.03 F1s%, [0344-0346]))
With respect to the limitations the compound having at least one of the following characteristics:
a signal located between -125.0 and -129.0 ppm, on a (19F) solid- state NMR spectrum, the reference at δ=0 ppm being that of the compound CF3COH,
a ratio R less than or equal to 50%, R being the ratio between the intensity of the vibrational band of the C-O bond of the carbonate groups (symmetric stretching v) located around 1090 cm-1 to the intensity of the stretching band of the bonds in the ZrO6 octahedra located around 648 cm-1, these two intensities being determined by Raman spectroscopy;
it is submitted that such limitations are simply measurements of, and thus descriptions of, inherent properties of the recited lithium-stuffed garnet thin film.
Applicant discloses a signal located between -125.0 and -129.0 ppm, on a (19F) solid- state NMR spectrum, the reference at δ=0 ppm being that of the compound CF3COH is generally attributed to a fluorine involved in an Li-F bond (see Instant Specification Page 13, lines 10-15), and it is generally considered that the C-O vibrational band of the carbonate groups is located at 1090±20 cm-1. This band is generally located between 1080 and 1100 cm-1 (see Instant Specification Page 14, lines 6-9). Further, Applicant discloses that it is observed that the fluorination process has the effect of reducing the amount of carbonate groups which are present, in particular at the surface of the solid, or even of making them disappear (see Instant Specification Page 16, lines 22-28).
Accordingly, it is reasonably interpreted that the fluorine involved in an Li-F bond is critical to the recited signal located between -125.0 and -129.0 ppm, and fluorination would minimize the intensity of the C-O vibrational bands, such that it would fulfil the recited measurements and necessarily possess the inherent properties.
Modified Chao discloses the fluorine is incorporated into, or bonded to, the lithium-stuffed garnet. (Chao, [0008]), as carbon of the carbonate peak diminishes, lanthanum (La 4d around 102 eV), Zirconia (3d around 182 eV), and Fluorine (around 691 eV) peaks were observed (Chao, [0334], Figure 1), and the treatment of Li-rich HE-NCM cathode material with low pressures (a few hundred mbar) of elementary fluorine gas at room temperature led to the elimination of surface species (such as LiOH, Li2CO3, Li2O, etc.), and as a consequence, the resulting improved passivation including thin amorphous LiF film led to increased capacity and long-term stability of the battery (Breddemann, Page 3347, paragraph starting with “the treatment of Li-rich…”).
It is submitted that the lithium-stuffed garnet thin film of modified Chao is substantially similar to the instant inorganic compound such that the lithium-stuffed garnet thin film of modified Chao would reasonably possess the same properties and exhibit the same results.
Therefore, based upon such substantial similarities, it appears reasonable that the lithium-stuffed garnet thin film of modified Chao would inherently possess physical properties, e.g. a signal located between -125.0 and -129.0 ppm, on a (19F) solid- state NMR spectrum, the reference at δ=0 ppm being that of the compound CF3COH and the intensity of the C-O vibrational bands are minimized, and such that the lithium-stuffed garnet thin film of modified Chao would necessarily fulfill the recited limitations, i.e.
a signal located between -125.0 and -129.0 ppm, on a (19F) solid- state NMR spectrum, the reference at δ=0 ppm being that of the compound CF3COH,
a ratio R less than or equal to 50%, R being the ratio between the intensity of the vibrational band of the C-O bond of the carbonate groups (symmetric stretching v) located around 1090 cm-1 to the intensity of the stretching band of the bonds in the ZrO6 octahedra located around 648 cm-1, these two intensities being determined by Raman spectroscopy.
Assuming, arguendo, that such properties are not inherent, it is submitted that before the effective filing date of the current invention, one having ordinary skill in the art would find such properties obvious over the claimed inorganic compound. The skilled artisan would reasonably find that the disclosed lithium-stuffed garnet thin film of modified Chao is so similar to the instant inorganic compound that the prior art garnet-type solid electrolyte would also exhibit:
a signal located between -125.0 and -129.0 ppm, on a (19F) solid- state NMR spectrum, the reference at δ=0 ppm being that of the compound CF3COH;
a ratio R less than or equal to 50%, R being the ratio between the intensity of the vibrational band of the C-O bond of the carbonate groups (symmetric stretching v) located around 1090 cm-1 to the intensity of the stretching band of the bonds in the ZrO6 octahedra located around 648 cm-1, these two intensities being determined by Raman spectroscopy.
Regarding Claim 14, modified Chao discloses all of the claim limitations as set forth above. Modified Chao discloses the limitations regarding an inorganic compound (Chao, lithium-stuffed garnet thin film, [0172]), wherein the element zirconium is partially replaced by the element hafnium (Chao, M′ and M″ are each, independently, selected from the group consisting of Hf, [0172]).
Regarding Claims 16-18 and 23-24, modified Chao discloses all of the claim limitations as set forth above. Modified Chao discloses the limitations regarding an inorganic compound (Chao, lithium-stuffed garnet thin film, [0172]).
With respect to the limitations the compound having at least one of the following characteristics:
the crystalline structure of which consists of a skeleton of LaO8 dodecahedra (La of coordination number 8) (24c site) and of ZrO6 octahedra (Zr of coordination number 6) (Claim 16);
the crystalline structure of which consists of a skeleton of LaO8 dodecahedra of coordination number 8 (24c site) and of ZrO6 octahedra (Zr of coordination number 6) (16a site) (Claim 17);
some Li atoms, are present at the 24d tetrahedral sites or 48g and 96h octahedral sites (Claim 18);
having a cubic crystal structure (Claim 23);
the crystal structure belongs to the Ia3d space group or to the I-43d space group (Claim 24).
it is submitted that such limitations are simply measurements of, and thus descriptions of, inherent properties of the recited lithium-stuffed garnet thin film.
Applicant discloses garnet-type oxides have an ideal structure of chemical formula A3B2(XO4)3 and generally crystallize into a body-centered cubic lattice belonging to the Ia3d space group (see Instant Specification Page 1, Lines 10-14), and the fluorination is carried out under "mild" conditions so that the crystalline structure of the starting solid is not adversely affected. In other words, the fluorinated inorganic compound has the same crystalline structure as the starting solid (see Instant Specification Page 15-16).
Accordingly, it is reasonably interpreted a mildly fluorinated garnet would not have its crystal structure adversely affected, such that it would fulfil the recited measurements and necessarily possess the inherent properties.
Modified Chao discloses a method of preparing lithium-stuffed garnet powder (Chao, [0317-0319]) and the material was mildly fluorinated with F2, (Breddemann, Page 3338, paragraph starting with “Li-rich material…”).
It is submitted that the lithium-stuffed garnet thin film that is mildly fluorinated with F2 of modified Chao is substantially similar to the instant inorganic compound such that the lithium-stuffed garnet thin film of modified Chao would reasonably possess the same properties and exhibit the same results.
Therefore, based upon such substantial similarities, it appears reasonable that the lithium-stuffed garnet thin film of modified Chao would inherently possess physical properties, e.g. crystal structure.
Assuming, arguendo, that such properties are not inherent, it is submitted that before the effective filing date of the current invention, one having ordinary skill in the art would find such properties obvious over the claimed inorganic compound. The skilled artisan would reasonably find that the disclosed lithium-stuffed garnet thin film of modified Chao is so similar to the instant inorganic compound that the prior art garnet-type solid electrolyte would also exhibit:
the crystalline structure of which consists of a skeleton of LaO8 dodecahedra (La of coordination number 8) (24c site) and of ZrO6 octahedra (Zr of coordination number 6) (Claim 16);
the crystalline structure of which consists of a skeleton of LaO8 dodecahedra of coordination number 8 (24c site) and of ZrO6 octahedra (Zr of coordination number 6) (16a site) (Claim 17);
some Li atoms, are present at the 24d tetrahedral sites or 48g and 96h octahedral sites (Claim 18);
having a cubic crystal structure (Claim 23);
the crystal structure belongs to the Ia3d space group or to the I-43d space group (Claim 24).
Regarding Claim 19, modified Chao discloses all of the claim limitations as set forth above. Modified Chao discloses the limitations regarding an inorganic compound an inorganic compound (Chao, lithium-stuffed garnet thin film, [0172]), comprising La-F (Chao, the fluorine is bonded to La, [0274]) and/or Zr-F bonds (Chao, the fluorine is bonded to Zr, [0273]).
Regarding Claim 20, modified Chao discloses all of the claim limitations as set forth above. Modified Chao discloses the limitations regarding an inorganic compound (Chao, lithium-stuffed garnet thin film, [0172]).
With respect to the limitations the compound having at least one of the following characteristics:
having, by (19F) solid-state NMR spectroscopy, the reference at δ=0 ppm being that of the compound CF3COOH, a signal between -98.0 and -102.0 ppm, and/or a signal between - 58.0 and -62.0 ppm,
it is submitted that such limitations are simply measurements of, and thus descriptions of, inherent properties of the recited garnet-type solid electrolyte.
Applicant discloses a signal between -98.0 and -102.0 ppm, and/or a signal between - 58.0 and -62.0 ppm, on a (19F) solid-state NMR spectrum, the reference at δ=0 ppm being that of the compound CF3COH is generally attributed to the formation of La-F and Zr-F bonds, respectively (see Instant Specification Page 13, lines 23-29).
Accordingly, it is reasonably interpreted that the presence of La-F and Zr-F bonds are critical to the recited signal located between -98.0 and -102.0 ppm, and/or a signal between - 58.0 and -62.0 ppm such that it would fulfil the recited measurements and necessarily possess the inherent properties.
Modified Chao discloses a lithium-stuffed garnet thin film, wherein the fluorine is bonded to La (Chao, [0274]), and the fluorine is bonded to Zr (Chao, [0273]).
It is submitted that the lithium-stuffed garnet thin film of modified Chao is substantially similar to the instant inorganic compound such that the lithium-stuffed garnet thin film of modified Chao would reasonably possess the same properties and exhibit the same results.
Therefore, based upon such substantial similarities, it appears reasonable that the lithium-stuffed garnet thin film of modified Chao would inherently possess physical properties, e.g. a signal located between -125.0 and -129.0 ppm, on a (19F) solid- state NMR spectrum, the reference at δ=0 ppm being that of the compound CF3COH, such that the lithium-stuffed garnet thin film of modified Chao would necessarily fulfill the recited limitations, i.e. a signal between -98.0 and -102.0 ppm, and/or a signal between -58.0 and -62.0 ppm, on a (19F) solid- state NMR spectrum, the reference at δ=0 ppm being that of the compound CF3COH.
Assuming, arguendo, that such properties are not inherent, it is submitted that before the effective filing date of the current invention, one having ordinary skill in the art would find such properties obvious over the claimed inorganic compound. The skilled artisan would reasonably find that the disclosed lithium-stuffed garnet thin film of modified Chao is so similar to the instant inorganic compound that the lithium-stuffed garnet thin film of modified Chao would also exhibit a signal between -98.0 and -102.0 ppm, and/or a signal between - 58.0 and -62.0 ppm, on a (19F) solid- state NMR spectrum, the reference at δ=0 ppm being that of the compound CF3COH.
Regarding Claim 21, modified Chao discloses all of the claim limitations as set forth above. Modified Chao discloses the limitations regarding an inorganic compound (Chao, lithium-stuffed garnet thin film, [0172]), of which the proportion of fluorine in the compound expressed by weight of the element fluorine relative to the total weight, is less than or equal to 10.0% and is greater than or equal to 0.01% (Breddemann, fluorination of materials by three different concentrations: low (0.432 wt-%F), a middle (1.008wt-%F), and high (1.728 wt-% F), Page 3338, paragraph starting with “We studied the fluorination …”; the disclosed F amounts of 0.432 wt-%F, 1.008 wt-%F, and 1.728 wt-%F falls within the claimed range of 0.01% to 10%), and calculated using 19F-NMR (Breddemann, 19F MAS NMR studies were carried out for the low and high fluorinated materials,Page 3341, paragraph starting with “7Li and 19F MAS NMR studies…”).
Regarding Claims 25-26, modified Chao discloses all of the claim limitations as set forth above. Modified Chao discloses the limitations regarding an inorganic compound (Chao, lithium-stuffed garnet thin film, [0172]).
With respect to the limitations the compound having at least one of the following characteristics:
having a ratio R less than or equal to 50%, R being the ratio between the intensity of the vibrational band of the C-O bond of the carbonate groups (symmetric stretching v) located around 1090 cm-1 to the intensity of the stretching band of the bonds in the ZrO6 octahedra located around 648 cm-1, these two intensities being determined by Raman spectroscopy and R being determined after storing the inorganic compound in an air-filled sealed flask for a period of at least two months, in particular of two months (Claim 25);
characterized in that the intensity of the vibrational mode v3 and/or of the vibrational mode v2 of the carbonate groups, these modes being respectively located between 1350 and 1600 cm-1 and between 890 and 1350 cm-1, is less than or equal to 50%, this intensity being determined by infrared spectroscopy in total attenuated reflectance mode (Claim 26),
it is submitted that such limitations are simply measurements of, and thus descriptions of, inherent properties of the recited garnet-type solid electrolyte.
Applicant discloses that it is generally considered that the C-O vibrational band of the carbonate groups is located at 1090±20 cm-1. This band is generally located between 1080 and 1100 cm-1 (see Instant Specification Page 14, lines 6-9). Further, Applicant discloses that it is observed that the fluorination process has the effect of reducing the amount of carbonate groups which are present, in particular at the surface of the solid, or even of making them disappear (see Instant Specification Page 16, lines 22-28).
Accordingly, it is reasonably interpreted that Applicant is directed towards minimizing the intensity of the C-O vibrational bands, and making the carbonate group disappear is desirable, such that it would fulfil the recited measurements and necessarily possess the inherent properties.
Modified Chao discloses that as carbon of the carbonate peak diminishes, lanthanum (La 4d around 102 eV), Zirconia (3d around 182 eV), and Fluorine (around 691 eV) peaks were observed (Chao, [0334], Figure 1). The Examiner notes that the carbon of the carbonate peak diminishes the garnet of modified Chao, so the claimed ratio R (Claim 25) and the carbonate vibrational band intensity (Claim 26) would be converging towards 0%, which falls within the claimed range of less than or equal to 50%.
It is submitted that the lithium-stuffed garnet thin film of modified Chao is substantially similar to the instant inorganic compound such that the lithium-stuffed garnet thin film of modified Chao would reasonably possess the same properties and exhibit the same results. Therefore, based upon such substantial similarities, it appears reasonable that the lithium-stuffed garnet thin film of modified Chao would inherently possess physical properties, e.g.
having a ratio R less than or equal to 50%, R being the ratio between the intensity of the vibrational band of the C-O bond of the carbonate groups (symmetric stretching v) located around 1090 cm-1 to the intensity of the stretching band of the bonds in the ZrO6 octahedra located around 648 cm-1, these two intensities being determined by Raman spectroscopy and R being determined after storing the inorganic compound in an air-filled sealed flask for a period of at least two months, in particular of two months (Claim 25);
characterized in that the intensity of the vibrational mode v3 and/or of the vibrational mode v2 of the carbonate groups, these modes being respectively located between 1350 and 1600 cm-1 and between 890 and 1350 cm-1, is less than or equal to 50%, this intensity being determined by infrared spectroscopy in total attenuated reflectance mode (Claim 26),
such that the lithium-stuffed garnet thin film of modified Chao would necessarily fulfill the recited limitations, i.e.
having a ratio R less than or equal to 50%, R being the ratio between the intensity of the vibrational band of the C-O bond of the carbonate groups (symmetric stretching v) located around 1090 cm-1 to the intensity of the stretching band of the bonds in the ZrO6 octahedra located around 648 cm-1, these two intensities being determined by Raman spectroscopy and R being determined after storing the inorganic compound in an air-filled sealed flask for a period of at least two months, in particular of two months (Claim 25);
characterized in that the intensity of the vibrational mode v3 and/or of the vibrational mode v2 of the carbonate groups, these modes being respectively located between 1350 and 1600 cm-1 and between 890 and 1350 cm-1, is less than or equal to 50%, this intensity being determined by infrared spectroscopy in total attenuated reflectance mode (Claim 26).
Assuming, arguendo, that such properties are not inherent, it is submitted that before the effective filing date of the current invention, one having ordinary skill in the art would find such properties obvious over the claimed inorganic compound. The skilled artisan would reasonably find that the disclosed lithium-stuffed garnet thin film of modified Chao is so similar to the instant inorganic compound that the lithium-stuffed garnet thin film of modified Chao would also exhibit
having a ratio R less than or equal to 50%, R being the ratio between the intensity of the vibrational band of the C-O bond of the carbonate groups (symmetric stretching v) located around 1090 cm-1 to the intensity of the stretching band of the bonds in the ZrO6 octahedra located around 648 cm-1, these two intensities being determined by Raman spectroscopy and R being determined after storing the inorganic compound in an air-filled sealed flask for a period of at least two months, in particular of two months (Claim 25);
characterized in that the intensity of the vibrational mode v3 and/or of the vibrational mode v2 of the carbonate groups, these modes being respectively located between 1350 and 1600 cm-1 and between 890 and 1350 cm-1, is less than or equal to 50%, this intensity being determined by infrared spectroscopy in total attenuated reflectance mode (Claim 26).
Regarding Claim 28, modified Chao discloses all of the claim limitations as set forth above. Modified Chao discloses the limitations regarding an inorganic compound (Chao, lithium-stuffed garnet thin film, [0172]), a solid electrolyte of a lithium ion battery comprising the inorganic compound (Chao, garnet solid-state electrolyte separator (80 μm thick), [0341]).
Claim(s) 27 and 29 is/are rejected under 35 U.S.C. 103 as being unpatentable over Chao et al. (US 20210202983 A1, hereinafter Chao), in view of Breddemann et al. (“Fluorination of Li-Rich Lithium-Ion-Battery Cathode Materials by Fluorine Gas: Chemistry, Characterization, and Electrochemical Performance in Half Cells, hereinafter Breddemann), as applied to Claim 12 above, and further in view of Engel et al. (US 20150295274 A1, hereinafter Engel).
Regarding Claim 27, modified Chao discloses all of the claim limitations as set forth above. Modified Chao is silent regarding an electrode E comprising:
a metal support;
a layer of a composition (C) in contact with the metal support, said composition (C) comprising:
the inorganic compound
at least one electroactive compound (EAC);
optionally at least one material which conducts the Li ions other than the fluorinated oxide (LiCM);
optionally at least one electrically-conductive material (ECM),
optionally a lithium salt (LIS); and
optionally at least one polymer binder material (P).
Engel discloses an electrode E (Engel, battery cell comprising a cathode, Claim 12) comprising:
a metal support (Engel, cathode current collector is an aluminum film, [0020]);
a layer of a composition (C) in contact with the metal support, said composition (C) comprising:
the inorganic compound (Engel, garnet with cathode active material, the garnet serving as an ion conductor, [0065])
at least one electroactive compound (EAC) (Engel, the cathode active material is selected from a lithiated transition metal oxide, which is selected from Li(NiCoMn)O2, [0026]);
optionally at least one electrically-conductive material (ECM) (Engel, the cathode can furthermore encompass additives to improve conductivity, such as conductive carbon black, [0066]), and
optionally at least one polymer binder material (P) (Engel, the cathode may include a binder such as PVdF (polyvinylidene fluoride, [0024]).
Engel discloses that garnet can improve ion conductivity of a cathode (Engel, [0065]).
Modified Chao and Engel are analogous to the current invention as they are all directed towards usage of a garnet in a battery.
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for the battery of modified Chao to include the cathode of Engel and to use the garnet of modified Chao as the ion conductor of the cathode, in order to improve the ion conductivity of the cathode.
Regarding Claim 29, modified Chao discloses all of the claim limitations as set forth above. Modified Chao discloses the limitations regarding a method of preparing a lithium battery (Chao, full cell architecture, [0341]), the method comprising: preparing an electrode comprising the inorganic compound (Engel, garnet with cathode active material, and the garnet serving as an ion conductor, [0065]).
Response to Arguments
Applicant’s arguments, see Pages 9-19, filed 05/14/2026, with respect to the rejection(s) of claim(s) 3, 12, and 13 under 35 U.S.C. 102 and 35 U.S.C. 103 have been fully considered and are persuasive. Therefore, the rejection has been withdrawn. However, upon further consideration, a new ground(s) of rejection is made in view of Chao et al. (US 20210202983 A1, hereinafter Chao), in view of Breddemann et al. (“Fluorination of Li-Rich Lithium-Ion-Battery Cathode Materials by Fluorine Gas: Chemistry, Characterization, and Electrochemical Performance in Half Cells, hereinafter Breddemann), as noted above.
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to KEVIN NGUYEN whose telephone number is (703)756-1745. The examiner can normally be reached Monday-Thursday 9:50 - 7:50 ET.
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, NICHOLAS A SMITH can be reached at (571) 272-8760. 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.
/K.N./Examiner, Art Unit 1752
/OSEI K AMPONSAH/Primary Examiner, Art Unit 1752
Prosecution Insights