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
Claims 6-12 are withdrawn from further consideration pursuant to 37 CFR 1.142(b) as being drawn to a nonelected Group 2, there being no allowable generic or linking claim. Election was made without traverse in the reply filed on 8/12/25. Claims 1, 3-5, 14-33, & 24-26 were examined.
Claim Objections
Claim 16 is objected to because of the following informalities:
Claim 16 recites “an anode comprising a Na alloy selected NaxSn,…”, which appears to contain a typographical error of missing the word “from” and should have been written “an anode comprising a Na alloy selected from NaxSn,…”.
Appropriate correction is required.
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.
Claims 1, 3-5, & 24-26 is rejected under 35 U.S.C. 103 as being unpatentable over Yushin et al. US 2018/0205111 A1, and further in view of Park et al. “High-Voltage Superionic Halide Solid Electrolytes for All-Solid-State Li-Ion Batteries” and Stenzel et al. “Ternary Halides of the A3MX6 Type II The System Ag3-xNaxYCl6: Synthesis, Structures, Ionic Conductivity”.
Regarding Claim 1, Yushin discloses an electrolyte for a sodium based solid battery [0032], wherein the solid electrolyte is a halide compound (in this case, fluorine) [0033], such as LiPF6 [0032]. Yushin further discloses that the battery can be either a lithium or sodium battery [0027, 0032], describing lithium and sodium as analogues to each other, and as such the electrolyte can comprise lithium or sodium metal salts such as LiPF6 or analogously NaPF6 [0032].
Yushin fails to specifically disclose that the halide compound is based on the parent compound Na3YCl6.
Park discloses an alkali metal chloride electrolyte compound, specifically Li3-xM1-xZrxCl6, wherein M is yttrium [Page 2 Right Column Lines 5-6] and x is 0-0.6 [Page 3 Lines 1-2], and Park discloses that the parent compound is Li3YCl6 [Page 2 Left Column Lines 17-21]. Park discloses that by substituting zirconium for yttrium and sodium (described as “aliovalent substitution”), the ionic conductivity of the compound is improved [Page 2 Right Column Lines 14-20].
Thus, as Yushin discloses that lithium and sodium are analogues to each other, with the specific example of using alternative solid electrolytes LiPF6 and NaPF6 [0032], it would have been obvious to one of ordinary skill in the art to use the sodium analogue with the formula of Park (i.e. Na3-xY1-xZrxCl6), comprising Zr substituted for Y and Na, as the solid electrolyte in the battery of Yushin with improved ionic conductivity. The solid electrolyte of modified Yushin would therefore be the same as the claimed composition and would therefore be expected to have enhanced sodium diffusivity.
As further supported by Stenzel, this class of compounds (substituted sodium yttrium chlorides) has been shown to be useful as an electrolyte as it has good ionic conductivity, and would therefore be recognized by one of ordinary skill in the art as useful in the battery of Yushin. See Annotated Figure 4 of Stenzel showing various substituted sodium yttrium chlorides having higher ionic conductivity than the parent compound Na3YCl6:
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Stenzel Annotated Figure 4
Examiner notes that the preamble of the claim stating “for sodium-based all-solid state batteries” was identified as intended use, and was therefore not given undue weight during examination.
Regarding Claim 3, modified Yushin discloses that the electrolyte has a deficiency of Na compared to the parent compound Na3YCl6, since as modified by Park some of the sodium has been replaced with Zr [Page 2 Right Column Lines 14-20]. In the absence of a more detailed definition provided in the instant specification, the phrase “engineered framework” was given its broadest reason interpretation as meaning “having a designed crystal structure”. As mentioned above with regards to claim 1, Park discloses that the electrolyte (Na3-xY1-xZrxCl6) has a crystal structure [Park Page 3 Lines 2-4], thus modified Yushin discloses that the electrolyte has an engineered framework.
Regarding Claim 4, modified Yushin, as modified by Park, discloses that the electrolyte has the formula Na3-xY1-xZrxCl6 wherein 0<x<1, as mentioned above with regards to Claim 1.
Regarding Claim 5, modified Yushin is relied upon for the reasons given above in addressing Claim 4, however fails to specifically disclose a formula for the electrolyte that meets the limitations in Claim 5. Specifically, modified Yushin does not disclose an electrolyte with the formula Na2.25Y0.25Zr0.75Cl6.
Stenzel discloses a compound with a similar formula to modified Yushin except comprising the substituted metal ion Ag instead of Zr (Ag3-xNaxYCl6) [Abstract]. Stenzel discloses that with decreasing Na content (thus increasing Ag content), the ion conductivity is improved [Abstract].
One of ordinary skill in the art would therefore recognize the amount of substituted metal ion ( Ag+ of Stenzel or Zr+ of Park) as being a result effective variable and would seek to optimize this parameter, and would therefore arrive at the claimed ranged to achieve a compound with improved ion conductivity. See MPEP 2144.05. Therefore, it would have been obvious to one of ordinary skill in the art prior to the effective filing date of the present invention to select a value of x (amount of substituted metal ion, in this case Zr) within the claimed range to provide a compound with improved ion conductivity as suggested by Stenzel.
Thus, modified Yushin discloses a formula that reads on Claim 5.
Regarding Claim 24, as mentioned with regards to Claim 1 above, modified Yushin discloses a composition comprising a sodium-ion conductive material (Na3-xY1-xZrxCl6), which is based on a parent compound Na3YCl6 wherein Na or Y is substituted with Zr. The material taught by modified Yushin is the same as the material claimed in Claim 24, and therefore would be expected to possess the required configuration (suitable as an interface between a high voltage oxide cathode and a sodium-based solid electrolyte) in a sodium all-solid state battery.
Examiner notes that the limitation of the claim stating “configured for use as an interface between a high voltage oxide cathode and a sodium-based solid electrolyte in a sodium all-solid-state battery” was identified as intended use, and was therefore not given undue weight during examination.
Regarding Claim 25, modified Yushin discloses that the material has the formula Na3-xM1-xZrxCl6 where 0<x<1, as modified by Park similarly to Claim 4 above.
Regarding Claim 26, as mentioned with regards to claim 5 above, modified Yushin with the modification of Stenzel discloses a formula that reads on Claim 26.
Claims 14-18 & 20-21 are rejected under 35 U.S.C. 103 as being unpatentable over Zhamu et al. US 2019/0165365 A1, and further in view of Yushin et al. US 2018/0205111 A1, Park et al. “High-Voltage Superionic Halide Solid Electrolytes for All-Solid-State Li-Ion Batteries”, and Stenzel et al. “Ternary Halides of the A3MX6 Type II The System Ag3-xNaxYCl6: Synthesis, Structures, Ionic Conductivity”. Further evidence provided by Zhang et al. “NASICONs-type solid-state electrolytes: The history, physicochemical properties, and challenges”.
Regarding Claim 14, Zhamu discloses a sodium based all solid state battery (alkali metal battery that is sodium ion based) [0017, 0028] and a transition metal oxide cathode [0029], and a solid electrolyte [0116] that can comprise sodium (NASICON-type compound comprising Na)[0125-0126], thus Zhamu discloses a sodium-based solid electrolyte.
Zhamu fails to disclose a halide compound included in the battery.
Yushin discloses an electrolyte for a sodium based solid battery [0032], wherein the solid electrolyte is a halide compound (in this case, fluorine) [0033], such as LiPF6 [0032]. Yushin further discloses that the battery can be either a lithium or sodium battery [0027, 0032], describing lithium and sodium as analogues to each other, and as such the electrolyte can comprise lithium or sodium metal salts such as LiPF6 or analogously NaPF6 [0032].
Yushin fails to specifically disclose that the halide compound is based on the parent compound Na3YCl6.
Park discloses an alkali metal chloride electrolyte compound, specifically Li3-xM1-xZrxCl6, wherein M is yttrium [Page 2 Right Column Lines 5-6] and x is 0-0.6 [Page 3 Lines 1-2], and Park discloses that the parent compound is Li3YCl6 [Page 2 Left Column Lines 17-21]. Park discloses that by substituting zirconium for yttrium and sodium (described as “aliovalent substitution”), the ionic conductivity of the compound is improved [Page 2 Right Column Lines 14-20].
Thus, as Yushin discloses that lithium and sodium are analogues to each other, with the specific example of using alternative solid electrolytes LiPF6 and NaPF6 [0032], it would have been obvious to one of ordinary skill in the art to use the sodium analogue with the formula of Park (i.e. Na3-xY1-xZrxCl6), comprising Zr substituted for Y and Na, as the solid electrolyte in the battery of Yushin with improved ionic conductivity. The solid electrolyte of modified Yushin would therefore be the same as the claimed composition and would therefore be expected to have enhanced sodium diffusivity.
As further supported by Stenzel, this class of compounds (substituted sodium yttrium chlorides) has been shown to be useful as an electrolyte as it has good ionic conductivity, and would therefore be recognized by one of ordinary skill in the art as useful in the battery of Yushin. See Annotated Figure 4 of Stenzel showing various substituted sodium yttrium chlorides having higher ionic conductivity than the parent compound Na3YCl6:
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Stenzel Annotated Figure 4
Thus, modified Yushin discloses a halide compound for use as an electrolyte in a sodium-based solid battery. Modified Yushin discloses that a solid electrolyte has the formula, as modified by Park, of Na3-xY1-xZrxCl6 wherein x = 0-0.6 [Park Page 3 Lines 1-2]. Modified Yushin discloses that the solid electrolyte has improved ionic conductivity [Page 2 Right Column Lines 14-20], and additionally would be beneficial for use in solid state batteries [Page 6 Right Column Lines 1-9].
Therefore, it would have been obvious to one of ordinary skill in the art prior to the effective filing date of the present invention to incorporate the solid electrolyte of modified Yushin in the battery of Zhamu to improved ionic conductivity, thus the solid electrolyte of modified Yushin would define a buffer layer, having the formula Na3-xY1-xZrxCl6 wherein the metallic element Zr is substituted into pristine Na3YCl6.
Regarding Claim 15, modified Zhamu, as modified by Yushin in view of Park as mentioned with regards to Claim 14, discloses that the buffer layer comprises the solid electrolyte of modified Yushin, and as mentioned with regards to Claim 3 above, modified Yushin discloses that the solid electrolyte is an engineered framework (given its broadest reasonable interpretation) with an Na deficiency compared to pristine Na3YCl6. Thus, modified Zhamu discloses that the buffer layer comprises a composite (the solid electrolyte of Yushin) comprising the limitations of Claim 15.
Additionally, Zhamu discloses that the cathode can further comprise a sodium ion conducting electrolyte [0059], however is silent as to the cathode specifically comprising a composite with the limitations of Claim 15.
As mentioned above modified Yushin discloses that the solid electrolyte improved ionic conductivity. Therefore, it would have been obvious to one of ordinary skill in the art prior to the effective filing date of the present invention to use the solid electrolyte of modified Yushin in the cathode of Zhamu as the “sodium ion conductive electrolyte” to provide a cathode with a composite comprising an engineered framework and an Na-deficiency to achieve improved ionic conductivity.
Regarding Claim 16, Zhamu discloses that the anode comprises an alloy of Sodium and Sn or Sb [0017].
Regarding Claim 17, as mentioned with regards to claim 1, Zhamu discloses that the solid electrolyte is a NASICON type [0125-0126], which are known in the art to be considered stable as evidenced by Zhang et al. [Page 2 Left Column Lines 22-26, Page 2 Left Column Lines 51-54].
Regarding Claim 18, Zhamu discloses that the cathode comprises NaCrO2 [0029].
Regarding Claim 20, as mentioned with regards to Claims 4, Yushin in view of Park discloses that the composition has the formula Na3-xY1-xZrxCl6 wherein 0<x<1. As mentioned with regards to claims 14 & 15 above, modified Zhamu with the modification of Yushin in view of Park discloses that the buffer layer and the cathode each comprises the composition of modified Yushin and thus reads on the claimed formula.
Regarding Claim 21, similarly to Claims 5 & 26 addressed above, Yushin in view of Park discloses that the composition has the formula Na3-xY1-xZrxCl6 wherein 0<x<1. However Yushin and Park fail to specifically disclose that the composition has the formula Na2.25Y0.25Zr0.75Cl6.
Stenzel discloses a compound with a similar formula to modified Yushin except comprising the substituted metal ion Al instead of Zr (Ag3-xNaxYCl6) [Abstract]. Stenzel discloses that with decreasing Na content (thus increasing Al content), the ion conductivity is improved [Abstract].
One of ordinary skill in the art would therefore recognize the amount of substituted metal ion ( Al+ of Stenzel or Zr+ of Park) as being a result effective variable and would seek to optimize this parameter, and would therefore arrive at the claimed ranged to achieve a compound with improved ion conductivity. See MPEP 2144.05. Therefore, it would have been obvious to one of ordinary skill in the art prior to the effective filing date of the present invention to select a value of x (amount of substituted metal ion, in this case Zr) within the claimed range to provide a compound with improved ion conductivity as suggested by Stenzel.
Thus, modified Yushin discloses a formula that reads on Claim 21.
As mentioned with regards to claims 14 & 15 above, modified Zhamu with the modification of Yushin in view of Park discloses that the buffer layer and the cathode each comprises the composition of modified Yushin, and would therefore comprise the formula of Claim 21 as modified by Stenzel.
Claim 19 is rejected under 35 U.S.C. 103 as being unpatentable over Zhamu, Yushin, Park, and Stenzel, and further in view of Aryanpour et al. US 2018/0287167 A1.
Regarding Claim 19, as mentioned with regards to Claim 14, Zhamu discloses that the solid electrolyte can comprise sodium (NASICON-type compound comprising Na)[0125-0126], however fails to specifically disclose that the solid electrolyte is Na3PS4.
Aryanpour discloses a sodium-based solid battery [0042] comprising a sodium-based solid electrolyte [0042], similar to Zhamu. Aryanpour discloses that the anode can be a sodium alloy with one or both of Sn and Sb [0013], similar to Zhamu. Aryanpour discloses that the solid electrolyte can be one of either Na3PS4 or a NASICON type (similar to Zhamu) [0042].
Therefore, it would have been obvious to one of ordinary skill in the art prior to the effective filing date to substitute one known sodium-based solid electrolyte, i.e. Na3PS4 of Aryanpour, for another sodium-based solid electrolyte, i.e. a NASICON type of Zhamu, with reasonable expectation of success. The simple substitution of one sodium-based solid electrolyte for another to obtain predictable results is not patentable. See KSR International Co v. Teleflex Inc., 127 S. Ct. 1727,82 USPQ2d 1385 (2007); MPEP 2143 B.
In addition, by teaching the two alternative electrolytes, Aryanpour demonstrates that these are known equivalents in the art, and the selection of either electrolyte would have been obvious to one having ordinary skill in the art. See MPEP 2144.06.
Thus, modified Zhamu discloses that the solid electrolyte is Na3PS4.
Claim 22 is rejected under 35 U.S.C. 103 as being unpatentable over Zhamu, Yushin, Park, and Stenzel as applied to Claim 14 above, and further in view of Dou et al . US 2020/0176817 A1.
Regarding Claim 22, modified Zhamu is silent as to the capacity retention of the battery after 200 cycles.
Dou discloses a sodium battery [0146] that comprises a sodium alloy anode [0151], similar to Zhamu, and a sodium chromium oxide cathode [0150], similar to Zhamu. Dou discloses that the batteries of the examples of the invention all have a capacity retention of 80% or more after 500 cycles (Table 2) [0169].
Dou discloses that a battery with this capacity retention has improved storage performance [0171].
One of ordinary skill in the art would recognize capacity retention as a result effective variable and would seek to optimize the capacity retention of the battery of Zhamu, and would therefore arrive at the claimed range to a battery with improved storage performance. See MPEP 2144.05. Therefore, it would have been obvious to one of ordinary skill in the art prior to the effective filing date of the present invention to select a capacity retention within the claimed range to provide a battery with improved storage performance as suggested by Dou.
Conclusion
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/A.E.G./Examiner, Art Unit 1726
/JEFFREY T BARTON/Supervisory Patent Examiner, Art Unit 1726 29 October 2025