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 .
Election/Restrictions
Claim 20 is withdrawn from further consideration pursuant to 37 CFR 1.142(b) as being drawn to a nonelected invention, there being no allowable generic or linking claim. Election was made without traverse in the reply filed on 12/03/2025.
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.
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.
Claim(s) 1-8, 10-17, and 19 is/are rejected under 35 U.S.C. 103 as being unpatentable over Foreign Publication CN114792839A (supplied by applicant, used attached machine translation), hereafter Yao, in view of Rajagopal, Rajesh, and Ryu, Kwang-Sun. “A Novel Na Substituted Li3-xNaxPS4 Mixed Ions Solid Electrolyte for All Solid-State Lithium Batteries.” Applied surface science 527 (2020): n. pag. Web, hereafter Rajagopal.
Regarding claim 1, Yao discloses an amorphous solid-state electrolyte ([0004] amorphous solid electrolyte), comprising a compound represented by the following formula: AaMXb, where a ≥ 1, b ≥ 4, A is at least one of Li+, Na+, K+, Cu+, or Ag+; M is Ga, Fe, Nb, Ta, or P; and X is F, Cl, Br, I, O2-, OH, or O22- ([0055]), wherein A is Li and Na, M is Nb or Ta, X is Cl or Br.
Yao is silent on wherein 0 < q ≤ 0.24.
In the analogous art of solid state electrolytes for Li ion batteries, Rajagopal discloses doping a solid state electrolyte with a low level of sodium is associated with an increase in ionic conductivity (page 4, section 3.1).
It would have been obvious to one of ordinary skill in the art, before the effective filing date of the present invention, to modify the invention of Yao with doping of the solid electrolyte with small amounts of sodium, such as q = 0.1, in order to improve the ionic conductivity of the electrolyte, as suggested by Rajagopal.
Thus, where for example p = 1, q = 0.1, r = 0, t = 0, and s = 6, modified Yao discloses Li0.9Na0.1TaCl6, which meets the claimed Formula 1
Lip-q-(α-5)xr=(ß-1)xtM1qM21-rM3αrX1s-tX2ßt
wherein in Formula 1, 0 < p ≤ 7, 0 < q ≤ 0.24, 0 ≤ r ≤ 0.5, 1 < s ≤ 12, 0 ≤ t ≤ 1, 0 < p-q-(α-5)xr=(ß-1)xt, and 0 < q/s ≤ 0.02,
M1 is a monovalent cation and is an element of Group 1 or Group 11 of the Periodic Table, or a combination thereof,
M2 is a pentavalent cation and is at least one element of Group 5 of the Periodic Table,
M3 is a cation element having a valency of α,
X1 is a monovalent anion and is at least one element of Group 17 of the Periodic Table, and
X2 is an anion having a valency of β, and
wherein the compound is amorphous.
Regarding claim 2, modified Yao further discloses wherein a structure of the compound represented by Formula 1 comprises a Li site, an M2 site, and an X1 site, which are three-dimensionally arranged (Yao [0049-0050] glassy network structure), wherein the Li site comprises M1 disposed therein (Li partially substituted with Na by modification of Yao with Rajagopal).
Regarding claim 3, modified Yao discloses wherein M1 comprises Na, K, Ag, Cu, or a combination thereof (Yao [0055]).
Regarding claim 4, Yao discloses wherein M2 comprises Ta, Nb, or a combination thereof ([0055]).
Regarding claim 5, Yao discloses wherein a structure of the compound represented by Formula 1 comprises a Li site, an M2 site, and an X1 site, which are three-dimensionally arranged ([0049-0050] glassy network structure), wherein the M2 site comprises M3 disposed therein ([0055] “at least one cation selected from the chemical elements Ga, Fe, Nb, Ta”, thus there may be multiple cations such as both Ga and Ta).
Regarding claim 6, Yao discloses wherein M3 is a divalent cation element, and M3 comprises Fe (“at least one cation selected from the chemical elements Ga, Fe, Nb, Ta”, thus there may be multiple cations such as both Fe and Ta);
M3 is a trivalent cation element, and M3 comprises Ga ([0055] “at least one cation selected from the chemical elements Ga, Fe, Nb, Ta”, thus there may be multiple cations such as both Ga and Ta); or
M3 is a pentavalent cation element, and M3 comprises Fe ([0055] “at least one cation selected from the chemical elements Ga, Fe, Nb, Ta”, thus there may be multiple cations such as both Fe and Ta).
Regarding claim 7, Yao discloses wherein X1 comprises Cl, Br, F, I, or a combination thereof ([0055] “at least one anion selected from F-, Cl-, Br-, I-”).
Regarding claim 8, Yao discloses wherein a structure of the compound represented by Formula 1 comprises a Li site, an M2 site, and an X1 site, which are three-dimensionally arranged ([0049-0050] glassy network structure), wherein the X1 site comprises X2 disposed therein ([0055] “at least one anion selected from F-, Cl-, Br-, I-”, thus there may be multiple anions such as both Cl- and Br-).
Regarding claim 10, modified Yao discloses the compound represented by Formula 2, as stated above for claim 1:
where for example p = 1, q = 0.1, r = 0, t = 0, and s = 6, modified Yao discloses Li0.9Na0.1TaCl6, which meets the claimed Formula 2
Lip-q-(α-5)xr=(ß-1)xtM1qM21-rM3αrCls-tX2ßt
wherein in Formula 1, 0 < p ≤ 7, 0 < q ≤ 0.24, 0 ≤ r ≤ 0.5, 1 < s ≤ 12, 0 ≤ t ≤ 1, 0 < p-q-(α-5)xr=(ß-1)xt, and 0 < q/s ≤ 0.02,
M1 is Na, K, Ag, Cu, or a combination thereof ([0055]), and
M2 is Ta, Nb, or a combination thereof ([0055]).
Regarding claim 11, modified Yao discloses the compound represented by Formula 3, as stated above for claim 1:
where for example p = 1, q = 0.1, r = 0, t = 0, and s = 6, modified Yao discloses Li0.9Na0.1TaCl6, which meets the claimed Formula 2
Lip-q-(α-5)xr=(ß-1)xtM1qTa1-rM3αrCls-tX2ßt
wherein in Formula 1, 0 < p ≤ 7, 0 < q ≤ 0.24, 0 ≤ r ≤ 0.5, 1 < s ≤ 12, 0 ≤ t ≤ 1, 0 < p-q-(α-5)xr=(ß-1)xt, and 0 < q/s ≤ 0.02,
M1 is Na, K, Ag, Cu, or a combination thereof ([0055]).
Regarding claim 12, modified Yao discloses wherein an ionic radius of M1 in Formula 1 is greater than an ionic radius of Li (implicit, since Na has a much larger ionic radius than Li), and
in Formula 1, ionic radii of X1 and X2 are each independently about 125 picometers or greater (Cl ionic radius is 181pm; Br ionic radius is 196pm).
Regarding claim 13, modified Yao discloses wherein the solid state electrolyte has a first peak at a diffraction angle of 41.5±1.0°2θ and a second peak at a diffraction angle of 29.8±1.0°2θ, when analyzed by an X-ray diffraction using CuKα radiation, and wherein a ratio of an intensity of the second peak to an intensity of the first peak is about 3 or less (these are properties of the compound and are thus inherently met by meeting the compound of formula 1. A chemical composition and its properties are inseparable. Therefore, if the prior art teaches the identical chemical structure, the properties applicant discloses and/or claims are necessarily present (MPEP 2112.01 (II))).
Regarding claim 14, modified Yao discloses wherein a first full width at half maximum of a third peak of the solid-state electrolyte at a diffraction angle of 30.1±1.0°2θ in an X-ray diffraction spectrum of the solid-state electrolyte is greater than a second full width at half maximum of a third peak of a crystalline LiTaCl6 at a diffraction angle of 30.1±1.0°2θ in an X-ray diffraction spectrum of the crystalline LiTaCl6, when measured under a same condition as the solid-state electrolyte and using CuKα radiation, and a ratio of the first full width at half maximum to the second full width at half maximum is about 5 or greater (these are properties of the compound and are thus inherently met by meeting the compound of formula 1. A chemical composition and its properties are inseparable. Therefore, if the prior art teaches the identical chemical structure, the properties applicant discloses and/or claims are necessarily present (MPEP 2112.01 (II))).
Regarding claim 15, modified Yao discloses wherein the compound represented by Formula 1 has an ion conductivity of about 1×10-3 Siemens per centimeter or greater at 25 °C, and the solid-state electrolyte has a lithium diffusion barrier of about 400 millielectronvolts or less (these are properties of the compound and are thus inherently met by meeting the compound of formula 1. A chemical composition and its properties are inseparable. Therefore, if the prior art teaches the identical chemical structure, the properties applicant discloses and/or claims are necessarily present (MPEP 2112.01 (II))).
Regarding claim 16, modified Yao discloses wherein the solid-state electrolyte is electrochemically stable with respect to lithium metal, in a potential window of 0.6 volt to 4.2 volts (these are properties of the compound and are thus inherently met by meeting the compound of formula 1. A chemical composition and its properties are inseparable. Therefore, if the prior art teaches the identical chemical structure, the properties applicant discloses and/or claims are necessarily present (MPEP 2112.01 (II))).
Regarding claim 17, modified Yao discloses a lithium battery ([0078] all solid state lithium metal full battery) comprising:
a cathode layer ([0078] positive electrode layer);
an anode layer ([0078] negative electrode layer); and
an electrolyte layer between the cathode layer and the anode layer ([0083] insulating layer contains solid electrolyte),
wherein the cathode layer, the electrolyte layer, or a combination thereof, comprises the solid-state electrolyte according to claim 1 (see above rejection of claim 1).
Regarding claim 19, modified Yao discloses wherein the lithium battery is a solid-state battery ([0078]).
Claim(s) 9 is/are rejected under 35 U.S.C. 103 as being unpatentable over Foreign Publication CN114792839A (supplied by applicant, used attached machine translation), hereafter Yao, in view of Rajagopal, Rajesh, and Ryu, Kwang-Sun. “A Novel Na Substituted Li3-xNaxPS4 Mixed Ions Solid Electrolyte for All Solid-State Lithium Batteries.” Applied surface science 527 (2020): n. pag. Web, hereafter Rajagopal, as stated above for claim 1, and further in view of Wang, Heng et al. “Borohydride Substitution Effects of Li6PS5Cl Solid Electrolyte.” ACS applied energy materials 4.11 (2021): 12079–12083. Web, hereafter Wang.
Regarding claim 9, Yao discloses wherein X2 is a monovalent anion ([0055] “at least one anion selected from F-, Cl-, Br-, I-”).
Yao is silent on wherein X2 comprises BH4, NO2, NO3, CN, ClO3, or a combination thereof; X2is a divalent anion, and X2 comprises SO4, SO3, CO3, or a combination thereof; or X2 is a trivalent anion, and X2 comprises PO4, BO3, AsO4, P, N, or a combination thereof.
In the analogous art of solid state battery electrolytes, Wang discloses wherein X2 comprises BH4 (page 12080 first paragraph, borohydride substituted solid electrolyte demonstrated increased ionic conductivity).
It would have been obvious to one of ordinary skill in the art, before the effective filing date of the present invention, to further modify the invention of Yao with the BH4 substitution in the solid electrolyte formula in order to further increase ionic conductivity, as suggested by Wang.
Claim(s) 18 is/are rejected under 35 U.S.C. 103 as being unpatentable over Foreign Publication CN114792839A (supplied by applicant, used attached machine translation), hereafter Yao, in view of Rajagopal, Rajesh, and Ryu, Kwang-Sun. “A Novel Na Substituted Li3-xNaxPS4 Mixed Ions Solid Electrolyte for All Solid-State Lithium Batteries.” Applied surface science 527 (2020): n. pag. Web, hereafter Rajagopal, as stated above for claim 17, and further in view of Published Application US20210242490A1, hereafter Ku.
Regarding claim 18, Yao is silent on wherein the electrolyte layer comprises a first electrolyte layer adjacent to the cathode layer, and a second electrolyte layer between the first electrolyte layer and the anode layer, and the first electrolyte layer comprises the solid-state electrolyte.
In the analogous art of solid state batteries, Ku discloses wherein the electrolyte layer comprises a first electrolyte layer adjacent to the cathode layer, and a second electrolyte layer between the first electrolyte layer and the anode layer, and the first electrolyte layer comprises the solid-state electrolyte ([0063-0064] using a first and second electrolyte layer, where the electrolyte closer to the anode has a higher ion conductivity, resulting in improved lithium ion mobility, thereby improving high rate charge/discharge characteristics).
It would have been obvious to one of ordinary skill in the art, before the effective filing date of the present invention, to further modify the invention of Yao with the addition of a second solid electrolyte layer adjacent to the anode with a higher ionic conductivity than the first electrolyte layer, in order to improve the lithium ion mobility, thereby improving high rate charge/discharge characteristics of the battery, as suggested by Ku.
Conclusion
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/T.G.H./Examiner, Art Unit 1754
/SUSAN D LEONG/Supervisory Patent Examiner, Art Unit 1754