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 .
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 a prior Office action.
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.
Response to Arguments
Applicant's arguments filed 06/24/2026 have been fully considered but they are not persuasive.
In response to applicant’s argument regarding claim 1 on page 12 of applicant’s remarks that Yao only teaches a single cation M in addition to the lithium, the examiner disagrees, and notes, as stated in the rejection, that Yao recites “Ion-conducting material A includes at least one of the following: Li+, Na+…” ([0055]), thus including the possibility that ‘A’ is composed of Li and Na together.
In response to applicant’s argument regarding claim 1 on page 12 of applicant’s remarks that the rejection adds the Rajagopal reference to add a small amount of sodium, the examiner disagrees, and notes, as stated in the rejection, that Rajagopal was added to teach specifically a low amount of sodium in the formula is beneficial to ionic conductivity, since too much sodium may be detrimental thereto (page 4, section 3.1).
In response to applicant’s argument regarding claim 1 on pages 12-13 of applicant’s remarks that the motivation cited in the office action of “improved conductivity brought on by inclusion of low amounts of sodium” appears to apply to sulfide-based solid state electrolytes and not to halogen-based solid state electrolytes such as those claimed, the examiner disagrees, and notes the lack of evidence for this assertion, as one skilled in the art would understand that Rajagopal teaches a lower amount of sodium added to the electrolyte compound in particular is what allows for the increase in ionic conductivity, and makes no suggestion that this principle would not also be applicable in solid electrolytes of slightly different composition.
In response to applicant’s argument regarding claim 1 on page 13 of applicant’s remarks that it can be seen from the table of Yao that the substitution of lithium with sodium produces a reduction in ionic conductivity, the examiner disagrees. As stated above, the teaching of Rajagopal is that low amounts of sodium are the key to the gains in ionic conductivity, and that higher amounts result in a decrease instead. Furthermore, the examiner notes that the particular formulae present in the table of Yao were not cited in the rejection. The literature of the art is relevant for all it contains, including nonpreferred embodiments (MPEP 2123 (I)).
In response to applicant’s argument regarding claim 1 on page 13 of applicant’s remarks that compositions T10 and T11 contain nanocrystals in addition to the amorphous regions, the examiner notes, as stated above, these compositions of Yao were not relied upon for the rejection, but further, even if they were, the claim does not require that no crystalline domains be present whatsoever, only that the compound is amorphous. Even if Yao taught that some of the compositions contain crystalline portions, this would not make the composition overall no longer amorphous. At best, the compound would be somewhat amorphous, still meeting the claim limitation.
In response to applicant’s argument regarding claim 1 on page 13 of applicant’s remarks that Yao does not teach that 0< q/s ≤ 0.02, the examiner notes one cannot show nonobviousness by attacking references individually where the rejections are based on combinations of references. See In re Keller, 642 F.2d 413, 208 USPQ 871 (CCPA 1981); In re Merck & Co., 800 F.2d 1091, 231 USPQ 375 (Fed. Cir. 1986). In this case, as stated in the rejection, this limitation was met by modified Yao, which incorporates the teachings of Rajagopal to select a low value for q, such as 0.1, in order to achieve an increased ionic conductivity, resulting in q/s of 0.1/6 = 0.0167 with modified Yao, which is within the claimed range.
In response to applicant’s argument regarding claim 1 on pages 13-14 of applicant’s remarks that the examiner made a mathematical error with regard to Yao, and that the coefficient for the element lithium in the solid state electrolyte must be greater than or equal to 1, the examiner disagrees. As stated above and in the rejection, the ‘A’ of the formula of Yao may include both Li and Na, and thus the ‘a’ represents the sum of the portions of each of Li and Na, as is the case with the claimed variable p.
In response to applicant's argument regarding claim 1 on page 14 of applicant’s remarks that the examiner's conclusion of obviousness is based upon improper hindsight reasoning, it must be recognized that any judgment on obviousness is in a sense necessarily a reconstruction based upon hindsight reasoning. But so long as it takes into account only knowledge which was within the level of ordinary skill at the time the claimed invention was made, and does not include knowledge gleaned only from the applicant's disclosure, such a reconstruction is proper. See In re McLaughlin, 443 F.2d 1392, 170 USPQ 209 (CCPA 1971). In this case, the values selected were not arbitrary, but were selected from those ranges given by Yao as modified by Rajagopal, as stated in the rejection.
In response to applicant’s argument regarding claim 1 on page 14 of applicant’s remarks that there is no teaching, suggestion, or motivation to combine the references, the examiner recognizes that obviousness may be established by combining or modifying the teachings of the prior art to produce the claimed invention where there is some teaching, suggestion, or motivation to do so found either in the references themselves or in the knowledge generally available to one of ordinary skill in the art. See In re Fine, 837 F.2d 1071, 5 USPQ2d 1596 (Fed. Cir. 1988), In re Jones, 958 F.2d 347, 21 USPQ2d 1941 (Fed. Cir. 1992), and KSR International Co. v. Teleflex, Inc., 550 U.S. 398, 82 USPQ2d 1385 (2007). In this case, as stated in the rejection, the motivation to modify Yao to use very low amounts of sodium is given by Rajagopal, which suggests doing so may result in an increased ionic conductivity.
In response to applicant’s argument regarding claim 1 on page 14 of applicant’s remarks that Yao teaches away from the modification where a portion of Li is substituted with Na in the solid electrolyte, the examiner disagrees, and notes, as stated in the rejection, that this limitation is taught by Yao, when Yao states that A is at least one of Li+ and Na+ ([0055]).
In response to applicant’s argument regarding claim 1 on page 16 of applicant’s remarks that one of ordinary skill in the art would not have a reasonable expectation of success for the teaching from Rajagopal of improved ionic conductivity through Na doping in the electrolyte, because the data in Yao demonstrates that Na doping causes a decrease in ionic conductivity of the amorphous halide-based compounds of Yao, the examiner disagrees. As stated above and in the rejection, Rajagopal discloses as Yao does that high amounts of sodium may be problematic, but Rajagopal teaches further that low amounts of sodium in the electrolyte may improve the conductivity, and as such, one skilled in the art would have reasonably expected to see an improvement in ionic conductivity as a result of specifically low amounts of Na being included in the solid state electrolyte of Yao.
Conclusion
THIS ACTION IS MADE FINAL. Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
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/T.G.H./Examiner, Art Unit 1754
/SUSAN D LEONG/Supervisory Patent Examiner, Art Unit 1754
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