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 statements (IDSs) submitted on 07/13/2023, 01/31/2024, and 11/26/2024 are in compliance with the provisions of 37 CFR 1.97. Accordingly, the information disclosure statements are being considered by the examiner.
Drawings
The drawings received on 07/13/2023 were received and are acceptable.
Specification
The specification filed on 07/13/2023 was received and is acceptable.
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) 1-9 is/are rejected under 35 U.S.C. 103 as being unpatentable over Kim et al. (US 20230009297 A1, hereinafter Kim) in view of Gai et al. (Improving the Li-ion conductivity and air stability of cubic Li7La3Zr2O12 by the co-doping of Nb, Y on the Zr site. Journal of the European Ceramic Society, 38(4), 1673-1678, hereinafter Gai, as filed in IDS dated 7/13/2023), and further in view of Jin et al. (US 20220085405 A1, hereinafter Jin).
Regarding Claim 1, Kim discloses the limitations regarding a solid electrolyte with high-entropy garnet-type structure (Kim, …Li3+xLa3Zr2-yMyO12 (M-doped LLZO, wherein M=Ga, W, Nb, Ta, Al, or a combination thereof, 0≤x≤10, and 0<y<2), [0080]). Although Kim does not specifically disclose high-entropy, it is understood in the art that this is equivalent to multi doping with unique dopants, which Kim does disclose. Kim discloses regarding a high-entropy garnet-type structure oxide represented by following formula (1): LiaLa3ZrbTacM1dM2eM3fO12 (1) wherein in the formula (1) , M1, M2, and M3 are respectively W, Sc, Sn, Nb, Y, Si, Sb, Te, Ti, Mo, Mg, or Nd, b+c+d+e+f=2, 5<a<8, 0.01<b<0.6, 0.01<c<0.6, 0.01<d<0.6, 0.01<e<0.6, and 0≤f<0.6. However, Kim is silent on the specific inclusion of yttrium (Y) as a dopant.
Gai discloses a high-entropy garnet-type structure oxide represented by following formula (1): LiaLa3ZrbTacM1dM2eM3fO12 (1) wherein in the formula (1) , M1, M2, and M3 are respectively W, Sc, Sn, Nb, Y, Si, Sb, Te, Ti, Mo, Mg, or Nd, b+c+d+e+f=2, 5<a<8, 0.01<b<0.6, 0.01<c<0.6, 0.01<d<0.6, 0.01<e<0.6, and 0≤f<0.6. (Gai, …Y2O3 and Nb2O5 were used to achieve the co-doping of Y3+ and Nb5+ on Zr4+ sites in LLZO., Introduction).
Gai teaches that the larger diameter of Y3+ (0.9 Å) compared to Zr4+ (0.72 Å) and Nb5+ (0.69 Å) might be beneficial for the diffusion of Li+ and is expected to enhance the Li+ conductivity (Gai, Introduction).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to dope the solid electrolyte of Kim with up to 3 dopants as it is known in the art that dopants modify the properties of electrolytes and to use the doping strategy of Gai in the already doped electrolyte of Kim, in order to increase the diffusion and conductivity of Li+ and therefore the performance of the electrolyte.
The examiner takes note of the fact that the prior art ranges for the molar ratio and element selection of Li, La, Zr, O and as well as Ta, W, Nb, and Y (M in the case of the prior art), shown in the table below, overlap or encompass the claimed ranged for the same parameters. Absent any additional and more specific information in the prior art, a prima facie case of obviousness exists. In re Peterson, 315 F.3d 1325, 65 USPQ2d 1379 (Fed. Cir. 2003). MPEP 2144.05. Furthermore, adding the Y of Gai to Kim’s solid electrolyte with dopants of Ta, W and Nb would have had an expectation of success as Jin discloses a garnet-type solid electrolyte such as Li7-xLa3(Zr2-x, Mx)O12, with M=In, Si, Ge, Sn, Sb, Sc, Ti, Hf, V, W, Te, Nb, Ta, Al, Ga, Fe, Bi, Y, Mg, Ca, or combinations thereof and 0<x<2, ([0008]).
Claim 1
Modified Kim Formula [0080]
LiaLa3ZrbTacM1dM2eM3fO12
Subscript range
Li3+xLa3Zr2-yMyO12
Subscript range
Li
5 < a < 8
Li
3 ≤ 3+x ≤ 13
La
3
La
3
Zr
0.01 < b < 0.6
Zr
2 < 2-y < 0
Ta
0.01 < c < 0.6
M (Ga, W, Nb, Ta, Al)
0 < y < 2
M1 (W, Sc, Sn, Nb, Y, Si, Sb, Te, Ti, Mo, Mg, Nd)
0.01 < d < 0.6
M (Ga, W, Nb, Ta, Al) or Y
0 < y < 2
M2 (W, Sc, Sn, Nb, Y, Si, Sb, Te, Ti, Mo, Mg, Nd)
0.01 < e < 0.6
M (Ga, W, Nb, Ta, Al) or Y
0 < y < 2
M3 (W, Sc, Sn, Nb, Y, Si, Sb, Te, Ti, Mo, Mg, Nd)
0 ≤ f < 0.6
M (Ga, W, Nb, Ta, Al) or Y
x = 0, 0.125, 0.25, or 0.5
O
12
O
12
Regarding Claim 2, Modified Kim discloses all of the claim limitations set forth above. Modified Kim discloses the limitation of a solid electrolyte with high-entropy garnet-type structure (Kim, …Li3+xLa3Zr2-yMyO12 (M-doped LLZO, wherein M=Ga, W, Nb, Ta, Al, or a combination thereof, 0≤x≤10, and 0<y<2, [0080]), wherein b, c, d, e, and f in the formula (1) have identical values a solid electrolyte with high-entropy garnet-type structure (Kim, …Li3+xLa3Zr2-yMyO12 (M-doped LLZO, wherein M=Ga, W, Nb, Ta, Al, or a combination thereof, 0≤x≤10, and 0<y<2), [0080] in this case, if subscript of all the dopants were chosen to be 0.25, as is within their provided range, they would have identical values, meeting the above limitation).
Regarding Claim 3, Modified Kim discloses all of the claim limitations set forth above. Modified Kim discloses the limitation of a solid electrolyte with high-entropy garnet-type structure (Kim, …Li3+xLa3Zr2-yMyO12 (M-doped LLZO, wherein M=Ga, W, Nb, Ta, Al, or a combination thereof, 0≤x≤10, and 0<y<2, [0080]), wherein M1, M2, and M3 in the formula (1) are W, Nb, (Kim, …Li3+xLa3Zr2-yMyO12 (M-doped LLZO, wherein M=Ga, W, Nb, Ta, Al, or a combination thereof0≤x≤10, and 0<y<2, [0080]), and Y (Gai, …Y2O3 and Nb2O5 were used to achieve the co-doping of Y3+ and Nb5+ on Zr4+ sites in LLZO, Introduction). The examiner takes note of the fact that the prior art ranges for the molar ratio and element selection of Li, La, Zr, O and as well as Ta, W, Nb, and Y (M in the case of the prior art), shown in the table below, overlap or encompass the claimed ranged for the same parameters. Absent any additional and more specific information in the prior art, a prima facie case of obviousness exists. In re Peterson, 315 F.3d 1325, 65 USPQ2d 1379 (Fed. Cir. 2003). MPEP 2144.05.
Claim 1
Modified Kim Formula [0080]
LiaLa3ZrbTacM1dM2eM3fO12
Subscript range
Li3+xLa3Zr2-yMyO12
Subscript range
Li
5 < a < 8
Li
3 ≤ 3+x ≤ 13
La
3
La
3
Zr
0.01 < b < 0.6
Zr
2 < 2-y < 0
Ta
0.01 < c < 0.6
M (Ga, W, Nb, Ta, Al)
0 < y < 2
M1 (W, Sc, Sn, Nb, Y, Si, Sb, Te, Ti, Mo, Mg, Nd)
0.01 < d < 0.6
M (Ga, W, Nb, Ta, Al) or Y
0 < y < 2
M2 (W, Sc, Sn, Nb, Y, Si, Sb, Te, Ti, Mo, Mg, Nd)
0.01 < e < 0.6
M (Ga, W, Nb, Ta, Al) or Y
0 < y < 2
M3 (W, Sc, Sn, Nb, Y, Si, Sb, Te, Ti, Mo, Mg, Nd)
0 ≤ f < 0.6
M (Ga, W, Nb, Ta, Al) or Y
x = 0, 0.125, 0.25, or 0.5
O
12
O
12
Regarding Claim 4, Modified Kim discloses all of the claim limitations as set forth above.
Modified Kim discloses the limitation of a solid electrolyte with high-entropy garnet-type structure (Kim, …Li3+xLa3Zr2-yMyO12 (M-doped LLZO, wherein M=Ga, W, Nb, Ta, Al, or a combination thereof, [0080]).
Modified Kim is silent on the high-entropy garnet-type structure oxide comprises Li5.8La3Zr0.4Ta0.4Nb0.4Y0.4W0.4O12, or Li6.4La3Zr0.4Ta0.4Nb0.4Y0.6W0.2O12.
Jin discloses a solid electrolyte with high-entropy garnet-type structure (Kim, …Li3+xLa3Zr2-yMyO12 (M-doped LLZO, wherein M=Ga, W, Nb, Ta, Al, or a combination thereof, [0080]), wherein the high-entropy garnet-type structure oxide comprises Li5.8La3Zr0.4Ta0.4Nb0.4Y0.4W0.4O12, or Li6.4La3Zr0.4Ta0.4Nb0.4Y0.6W0.2O12 (Jin, Li7-xLa3(Zr2-x, Mx)O12, with M=In, Si, Ge, Sn, Sb, Sc, Ti, Hf, V, W, Te, Nb, Ta, Al, Ga, Fe, Bi, Y, Mg, Ca, or combinations thereof and 0<x<2, [0008])
Jin teaches Li7-xLa3(Zr2-x, Mx)O12, with M=In, Si, Ge, Sn, Sb, Sc, Ti, Hf, V, W, Te, Nb, Ta, Al, Ga, Fe, Bi, Y, Mg, Ca, or combinations thereof and 0<x<2 (Jin, [0008])
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to attempt to broaden the range of the amount of yttrium present in the LLZO of Modified Kim, as taught by Jin, in order to further tweak electrolyte properties including the diffusion and conductivity of Li+ and therefore the performance of the electrolyte.
The examiner takes note of the fact that the prior art ranges for the molar ratio and element selection of Li, La, Zr, O and as well as Ta, W, Nb, and Y (M in the case of the prior art), shown in the table below, overlap or encompass the claimed ranged for the same parameters. Absent any additional and more specific information in the prior art, a prima facie case of obviousness exists. In re Peterson, 315 F.3d 1325, 65 USPQ2d 1379 (Fed. Cir. 2003). MPEP 2144.05.
Claim 4
Kim Formula [0080]
LiaLa3ZrbTacM1dM2eM3fO12
Subscript range
Li3+xLa3Zr2-yMyO12
Subscript range
Li
5.8, 6.4
Li
3 ≤ 3+x ≤ 13
La
3, 3
La
3
Zr
0.4, 0.4
Zr
2 < 2-y < 0
Ta
0.4, 0.4
M (Ga, W, Nb, Ta, Al) or Y
0 < y < 2
Nb
0.4, 0.4
M (Ga, W, Nb, Ta, Al) or Y
0 < y < 2
W
0.4, 0.2
M (Ga, W, Nb, Ta, Al) or Y
0 < y < 2
Y
0.4, 0.6
M (Ga, W, Nb, Ta, Al) or Y
0 < x < 2
O
12
O
12
Regarding Claim 5, Modified Kim discloses all of the claim limitations set forth above. Modified Kim discloses the limitation of a solid electrolyte with high-entropy garnet-type structure (Kim, …Li3+xLa3Zr2-yMyO12 (M-doped LLZO, wherein M=Ga, W, Nb, Ta, Al, or a combination thereof, 0≤x≤10, and 0<y<2, [0080]), wherein f in the formula (1) is 0 (Kim, …Li3+xLa3Zr2-yMyO12 (M-doped LLZO, wherein M=Ga, W, Nb, Ta, Al, or a combination thereof, 0≤x≤10, and 0<y<2, [0080] in this case, if one of Nb, W, or Y was eliminated as allowed by the combination, it’s subscript would be equal to zero, meeting the above limitation).
Regarding Claim 6, Modified Kim discloses all of the claim limitations set forth above. Modified Kim discloses the limitation of a solid electrolyte with high-entropy garnet-type structure (Kim, …Li3+xLa3Zr2-yMyO12 (M-doped LLZO, wherein M=Ga, W, Nb, Ta, Al, or a combination thereof, 0≤x≤10, and 0<y<2, [0080]), wherein b, c, d, and e in the formula (1) have identical values (Kim, …Li3+xLa3Zr2-yMyO12 (M-doped LLZO, wherein M=Ga, W, Nb, Ta, Al, or a combination thereof, 0≤x≤10, and 0<y<2, [0080] in this case, if subscript of all the dopants were chosen to be 0.25, as is within their provided range, they would have identical values, meeting the above limitation).
Regarding Claim 7, Modified Kim discloses all of the claim limitations as set forth above. Modified Kim discloses the limitation of a solid electrolyte with high-entropy garnet-type structure (Kim, …Li3+xLa3Zr2-yMyO12 (M-doped LLZO, wherein M=Ga, W, Nb, Ta, Al, or a combination thereof, [0080]), wherein the high-entropy garnet-type structure oxide comprises Li6.5La3Zr0.5Ta0.5Nb0.5Y0.5O12, (Kim, …Li3+xLa3Zr2-yMyO12 (M-doped LLZO, wherein M=Ga, W, Nb, Ta, Al, or a combination thereof, 0≤x≤10, and 0<y<2, [0080], Gai, …Y2O3 and Nb2O5 were used to achieve the co-doping of Y3+ and Nb5+ on Zr4+ sites in LLZO, Introduction, and Jin Li7-xLa3(Zr2-x, Mx)O12, with M=In, Si, Ge, Sn, Sb, Sc, Ti, Hf, V, W, Te, Nb, Ta, Al, Ga, Fe, Bi, Y, Mg, Ca, or combinations thereof and 0<x<2, [0008]); The examiner takes note of the fact that the prior art ranges for the molar ratio and element selection of Li, La, Zr, O and as well as Ta, W, Nb, and Y (M in the case of the prior art), shown in the table below, overlap or encompass the claimed ranged for the same parameters. Absent any additional and more specific information in the prior art, a prima facie case of obviousness exists. In re Peterson, 315 F.3d 1325, 65 USPQ2d 1379 (Fed. Cir. 2003). MPEP 2144.05.
Claim 7
Kim Formula [0080]
LiaLa3ZrbTacM1dM2eM3fO12
Subscript range
Li3+xLa3Zr2-yMyO12
Subscript range
Li
6.5
Li
3 ≤ 3+x ≤ 13
La
3
La
3
Zr
0.5
Zr
2 < 2-y < 0
Ta
0.5
M (Ga, W, Nb, Ta, Al) or Y
0 < y < 2
Nb
0.5
M (Ga, W, Nb, Ta, Al) or Y
0 < y < 2
Y
0.5
M (Ga, W, Nb, Ta, Al) or Y
0 < x < 2
O
12
O
12
Regarding Claim 8, Modified Kim discloses all of the claim limitations as set forth above.
Modified Kim discloses the limitation of a solid electrolyte with high-entropy garnet-type structure (Kim, …Li3+xLa3Zr2-yMyO12 (M-doped LLZO, wherein M=Ga, W, Nb, Ta, Al, or a combination thereof, [0080]), wherein the high-entropy garnet-type structure oxide is prepared by solid state sintering (Kim, -The oxide solid electrolyte may be prepared using, for example, sintering., [0080]).
MPEP 2113 teaches that "Even though product-by-process claims are limited by and defined by the process, determination of patentability is based on the product itself. The patentability of a product does not depend on its method of production. If the product in the product-by-process claim is the same as or obvious from a product of the prior art, the claim is unpatentable even though the prior product was made by a different process." In re Thorpe, 777 F.2d 695, 698, 227 USPQ 964, 966 (Fed. Cir. 1985)
Regarding Claim 9, Modified Kim discloses all of the claim limitations as set forth above. Modified Kim discloses the limitation of an all solid-state lithium-ion battery (Kim, the all-solid secondary battery, [0099]), comprising:
a positive plate (Kim, …the cathode layer 10 maybe include a current collector 11 and a cathode active material layer 12, [0094]);
a negative plate (Kim, …the anode layer includes an anode current collector and a first anode active material layer on the anode current collector, Abstract);
a solid electrolyte with high-entropy garnet-type structure (Kim, …Li3+xLa3Zr2-yMyO12 (M-doped LLZO, wherein M=Ga, W, Nb, Ta, Al, or a combination thereof, [0080])
disposed between the positive plate and the negative plate (Kim, a solid electrolyte between the cathode layer and the anode layer, Abstract).
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure. Luo specifically discloses the doping of LLZO at the Zr site with 3 distinct dopants at one time. Showing there is precedent in the art for continued doping at Zr site.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to JOSHUA P BISTANY-RIEBMAN whose telephone number is (571)272-9591. The examiner can normally be reached Mon-Fri. 7:30am-5pm.
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If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Nicholas A Smith can be reached at 5712728760. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
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/JOSHUA P BISTANY-RIEBMAN/Examiner, Art Unit 1752
/NICHOLAS A SMITH/Supervisory Primary Examiner, Art Unit 1752