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 .
Continued Examination Under 37 CFR 1.114
A request for continued examination under 37 CFR 1.114, including the fee set forth in 37 CFR 1.17(e), was filed in this application after final rejection. Since this application is eligible for continued examination under 37 CFR 1.114, and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114. Applicant's submission filed on 05/27/2025 has been entered.
Response to Amendment
This is a non-final Office action in response to Applicant’s remarks and amendments filed on 05/27/2025. Claims 1 and 13 are amended. Claims 2 and 14 – 17 are canceled. Claim 18 is new. Claims 1, 3 – 13, and 18 are pending review in the current Office action.
In light of the amended title, the specification objection set forth in the previous Office action is withdrawn.
The 35 U.S.C. 103 rejection over An in view of Utsuno is maintained with the rejection of claim 1 rewritten to address the amendment.
Response to Arguments
Applicant's arguments filed 05/27/2025 have been fully considered but they are not persuasive.
Applicant argues, see pg. 8 – 9, that the presence of lithium halide at the interphase is not an inherent feature. Specifically, applicant argues that the wetting agent is utilized to stabilize the solid electrolyte/electrode interface and that Fig. 44A of the specification shows that Li6PS5Cl-LiCl/PC exhibits better cycling performance than that of Li6PS5Cl/PC, which indicates that halide-containing crystalline lithium argyrodite with carboxylic wetting agent along is not sufficient to form a robust and suitable interphase layer and that excess halide in the solid electrolyte results in a more stable interface.
Examiner respectfully disagrees for the following reasons. First, An’s inorganic solvent, corresponds to claimed wetting agent, is also necessarily used to stabilize the solid electrolyte/electrode interface, that is, the solvent is added at the interface of the solid electrolyte and electrode to reduce contact impedance between the electrode and solid electrolyte (An: [0010]). Furthermore, the examiner respectfully notes that the claim recitation “to form a solid electrolyte, halide containing interphase layer between the solid electrolyte composition and an electrode” establishes an intended use/inherent function for the solid electrolyte composition. A recitation of the intended use of the claimed invention must result in a structural difference between the claimed invention and the prior art in order to patentably distinguish the claimed invention from the prior art. If the prior art structure is capable of performing the intended use, then it meets the claim. Therefore, modified An, by rendering obvious the claimed structure of a solid electrolyte comprising a solid, halide-containing crystalline lithium argyrodite {i.e. provides halide-containing crystalline lithium argyrodite overlapping in scope with the claimed formula} and a wetting agent applied at the interface between the solid electrolyte and electrode, one with ordinary skill in the art would reasonably expect the solid electrolyte of modified An to be capable of forming the claimed interphase.
Examiner acknowledges that Fig. 44A shows that a battery using Li6PS5Cl—LiCl/PC exhibits better cycling performance than the example battery using Li6PS5Cl/PC, and further, as established in the specification and the arguments, that Fig. 44A suggests that Li6PS5Cl—LiCl/PC is capable of providing a more stable/robust interphase layer (See Instant specification: [0147];[0168]); however, as established in the rejection below, modified An’s taught halide-containing crystalline lithium argyrodite includes argyrodites having excess amounts of chloride, and Utsuno further provides a reason for increasing the chloride amount (Utsuno: [0026];[0035];[0055 – 0057]). Therefore, modified An, as established below, appears to teach/suggest solid electrolyte compositions including excess chloride amounts, which, as noted by the applicant are capable of providing a more stable interface formation. As such, applicant’s arguments, regarding the presence of the interphase layer in modified An are unpersuasive.
Applicant further argues that An and Utsuno lack reasonable expectation of success, see pg. 9 – 10. Specifically applicant argues that the required standard is lacking under MPEP 2143 and there is no motivation to combine An with Utsuno.
In response to applicant’s argument 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, Utsuno explicitly teaches utilizing their chlorine-containing sulfide with an argyrodite-crystal structure as the solid electrolyte of a lithium ion battery in [0136 – 0137]. Utsuno further teaches that the solid electrolyte is compatible with lithium metal negative electrodes in [0107] and transition metal oxide positive electrodes, including LiFePO4, in [0122], which are both explicitly exemplified to be used in a battery embodiment of An (An: [0047 – 0048]). Furthermore, Utsuno teaches obtaining a solid electrolyte having high ionic conductivity through their chlorine-containing sulfide solid electrolyte with an argyrodite-crystal structure in [0015] and [0026]. As such, because An already suggests using sulfide solid electrolytes and indicates a desire to obtain a solid state battery with improved performance {An: [0021 – 0022];[0105]}, and Utsuno teaches a sulfide solid electrolyte that is highly conductive and compatible with electrode materials exemplified by An, the solid electrolyte taught in Utsuno appears applicable to An and the prior art rejection seems to properly support prima facie obviousness [See MPEP 2123(I)].
Applicant further argues that An additionally requires lithium salt as part of the electrolyte.
Examiner acknowledges that An teaches including lithium salt in the electrolyte; however, the citations of An provided by the applicant are with respect to the polymer electrolyte compositions exemplified to be used in An, not necessarily the inorganic solid electrolyte compositions (An: [0016 – 0020]); therefore, applicant’s argument regarding the inclusion of lithium salt is unpersuasive. Furthermore, the claim is directed to a solid electrolyte composition that “comprises a solid, halide-containing crystalline lithium argyrodite”, as such, the scope of the claim, by using “comprises” does not necessarily exclude unrecited elements, such as lithium salt. Additionally, although the claims are interpreted in light of the specification, limitations from the specification are not read into the claims. See In re Van Geuns, 988 F.2d 1181, 26 USPQ2d 1057 (Fed. Cir. 1993).
Specification
The abstract of the disclosure is objected to because the content of the abstract is directed to methods for wet chemical synthesis of lithium argyrodites, and thus is not descriptive of the claimed invention, which is an electrochemical energy storage device comprising halide-containing lithium argyrodite solid electrolytes. A corrected abstract of the disclosure is required and must be presented on a separate sheet, apart from any other text. See MPEP § 608.01(b).
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, 3 – 13, and 18 are rejected under 35 U.S.C. 103 as being unpatentable over An (CN107394272A – cited in previous Office action mailed 02/25/2025), hereinafter An, in view of Utsuno (WO 2018/092366 A1, US PG Pub. 2019/0319305 A1 used as English translation – cited in previous Office action mailed 02/25/2025).
Regarding Claims 1 and 11 – 12, An discloses an electrochemical energy storage device (solid-state lithium ion battery; [0010]) comprising a solid electrolyte ([0010];[0015]) and a wetting agent (organic solvent; [0010 – 0012]).
The organic solvent disclosed by An reads on the claimed wetting agent, because, like the claimed wetting agent, the organic solvent functions to reduce contact impedance between the electrolyte and electrode in the battery and ultimately allow for improved performance of the solid-state lithium ion battery (An: [0022]; Instant Specification: [0164 – 0165]). Furthermore, materials listed/exemplified to be used as the organic solvent in An, such propylene carbonate, are claimed and disclosed by the applicant to be wetting agents (An: [0022];[0046 – 0050]; Instant Specification: [0164]).
In Example 1 of An, the organic solvent is propylene carbonate and the solid electrolyte is a solid polymer electrolyte composed of polyethylene carbonate, poly(vinylidene fluoride-hexafluoropropylene), and lithium bis (trifluoromethylsulfonyl imide) ([0046]). The negative electrode of the example battery is a lithium metal electrode and the positive electrode is a lithium iron phosphate electrode ([0047 – 0048]).
As an alternative to polymer electrolytes, An also teaches using inorganic solid electrolytes for the solid-state lithium ion battery ([0015]). Inorganic solid electrolytes taught by An include materials such as Li7La3ZrO12, Li10GeP2S12, Li3OCl0.5Br0.5, Li3xLa(2/3)-xTiO3, Li5La3Ta2O12, Li5La3Nb2O12, Li5.5La3Nb1.74In0.25O12, Li3N-LiCl, Li3N-LiBr, Li3N-LiI, Li14Zn(GeO4)4, LiZr2(PO4)3, Li3OCl, LiPON, and Li2S-MaSb wherein 0.04 < x < 0.14, M = Al, Si, or P, and the values of a and b are 1 – 3, respectively.
An does not specifically disclose wherein the solid electrolyte composition comprises a solid, halide-crystalline lithium argyrodite, and further wherein the halide-containing crystalline lithium argyrodite is represented by a formula chosen from the group consisting of LimPSnXo and LimPSn, where m is a number in the range of 4-8, n is a number in the range of 3-6, X represents at least one halide, and o is a number in the range of 0-3 (Claim 11).
Utsuno teaches a sulfide solid electrolyte with an argyrodite-crystal structure represented by LiaPSbClc wherein 5.0 ≤ a ≤ 6.5, 6.1 ≤ a + c ≤ 7.5 {i.e. 0.4 ≤ c ≤ 2.5}, 0.5 ≤ a - b ≤ 1.5 {i.e. 3.5 ≤ b ≤ 6}, b > 0, and c > 1.0 are satisfied ([0035];[0055 – 0057]). Utsuno further teaches that the electrolyte material has improved ion conductivity due to the inclusion of chlorine, and is compatible with negative electrodes including elemental metals like metal lithium and positive electrodes including transition metal oxides like LiFePO4 ([0015];[0026];[0107];[0122]).
Since An already teaches using inorganic sulfide solid electrolytes that include Li, S, and P, it would have been obvious to one with ordinary skill in the art, before the effective filing date of the claimed invention, to modify the battery of Example 1, to include the sulfide solid electrolyte taught by Utsuno, and thus obtain a solid electrolyte composition within the claimed scope, with a reasonable expectation of success in obtaining a solid electrolyte with improved conductivity and suitable for An’s solid-state lithium ion battery.
By including a sulfide solid electrolyte represented by LiaPSbClc wherein 5.0 ≤ a ≤ 6.5, 6.1 ≤ a + c ≤ 7.5 {i.e. 0.4 ≤ c ≤ 2.5}, 0.5 ≤ a - b ≤ 1.5 {i.e. 3.5 ≤ b ≤ 6}, b > 0, and c > 1.0 are satisfied, modified An’s solid electrolyte composition includes halide-containing crystalline lithium argyrodites such as Li6PS5Cl·0.5LiCl and Li6PS5Cl. As such, the solid electrolyte of modified An provides halide-containing crystalline lithium argyrodites with chloride contents that overlap the claimed chloride content range, expressed as Li6PS5Cl·xLiCl where x is 0 – 2 (Claim 12).
Utsuno’s taught ranges for the molar ratios of Li, S, and Cl in LiaPSbClc provide the advantageous effects of stable crystal structure and improved ion conductivity ([0005];[0026];[0047 – 0053]). Furthermore, Utsuno teaches that increasing the Cl content reduces the lattice constant of the argyrodite crystal structure and ultimately allows for improvements in ion conductivity ([0026]).
Therefore, selection of halide-containing crystalline lithium argyrodites with chloride contents within the claimed range, such as Li6PS5Cl·0.5LiCl {x = 0.5} and Li6PS5Cl {x = 0}, would have been obvious to one with ordinary skill in the art to optimize the crystal structure and conductivity of the sulfide solid electrolyte material of modified An, with a reasonable expectation of success and without undue experimentation [MPEP 2144.05(II)].
Modified An, as established above, includes the claimed electrolyte composition characterized by a halide-containing crystalline lithium argyrodite structure represented by xLiX·Li6PS5X.
Modified An does not explicitly disclose the electrolyte composition characterized to form a solid electrolyte, halide containing interphase layer between the solid electrolyte composition and an electrode; however, the recitation “to form a solid electrolyte, halide containing interphase layer between the solid electrolyte composition and an electrode” establishes an intended use/inherent function for the solid electrolyte composition. Regarding product and apparatus claims, when the structure recited in the reference is substantially identical to that of the claims, claimed properties or functions are presumed to be inherent.
Furthermore, in the instant specification, the applicant indicates that a lithium halide-containing interphase at the interface of the electrode and electrolyte can form in a battery when a LiCl-rich argyrodite solid electrolyte is used with trace amounts of carboxylic acid ester ([0163 – 0164]).
As such, since modified An renders obvious the claimed solid electrolyte composition and structure {i.e. propylene carbonate wetting agent and halide-containing crystalline lithium argyrodite solid electrolyte}, including electrode materials {i.e. lithium metal negative electrode and lithium transition metal positive electrode} disclosed in the instant specification: [00169], a skilled artisan would reasonably expect, the battery of modified An to form the claimed solid electrolyte, halide containing interphase layer between the solid electrolyte composition and an electrode.
Regarding Claims 3 – 5, modified An discloses all limitations as set forth above. In the battery embodiment of modified An, the organic solvent, which corresponds to the claimed wetting agent, is disclosed to be propylene carbonate (An: Example 1; [0046 – 0050]), thus, modified An further discloses wherein the wetting agent is a carboxylic acid ester (Claim 3) and wherein the carboxylic acid ester is propylene carbonate (Claim 5), which is a carboxylic acid ester included in the claimed group consisting of ethylene carbonate, dimethyl carbonate, ethyl-methyl carbonate, and propylene carbonate (Claim 4).
Regarding Claims 6 – 7, modified An discloses all limitations as set forth above. In the battery embodiment, modified An further discloses using 10 µL/cm2 of the propylene carbonate (An: Example 1; [0046 – 0050]), which is within the claimed carboxylic acid ester volume range of 5 µL/cm2 to about 30 µL/cm2 (Claim 6), and further, 8 µL/cm2 to about 16 µL/cm2 (Claim 7).
Regarding Claims 8 – 9, modified An discloses all limitations as set forth above. Fig 2 of An shows the charge and discharge curve of the battery of Example 1 at 50°C ([0044][0080]). The specific capacity of the example battery, based on Fig. 2, is shown to be about 160 mAh g-1.
Modified An does not explicitly disclose wherein the device when cycling at a C-rate of 0.2 C is characterized by a specific capacity of at least 170 mAh g-1 after cycle 1 of charge/discharge (Claim 8), and further, wherein the device when cycling at a C-rate of 1 C is characterized by a specific capacity of at least 116 mAh g1 after at least 200 cycles of charge/discharge (Claim 9).
However, since An already exemplifies obtaining capacities as high as 160 mAh g-1 (Refer to Fig. 2 in An), and modified An renders obvious the claimed battery composition and structure {i.e. propylene carbonate wetting agent and halide-containing crystalline lithium argyrodite solid electrolyte}, including electrode materials {i.e. lithium metal negative electrode and lithium transition metal positive electrode} disclosed in the instant specification: [00169], a skilled artisan would reasonably expect, given the same test/operating conditions, the battery of modified An to, provide the claimed cycling characteristics.
Regarding Claim 10, modified An discloses all limitations as set forth above. An teaches, with respect to example 1, that the combination of solid electrolyte and organic solvent at the interface of the electrolyte and electrode in the solid-state battery allows for improved interface impedance and good charge/discharge cycle characteristics ([0023];[0080]).
Modified An does not explicitly disclose wherein the device when under a current density of 0.2 mA cm-2 exhibits a flat polarization voltage marked by a variance in voltage of no greater than 10% over a period of time of at least 1000 hours
However, since modified An renders obvious the claimed battery composition and structure {i.e. propylene carbonate wetting agent and halide-containing crystalline lithium argyrodite solid electrolyte}, including electrode materials {i.e. lithium metal negative electrode and lithium transition metal positive electrode} disclosed in the instant specification: [00169], a skilled artisan would reasonably expect, given the same test/operating conditions, the battery of modified An to, provide the claimed flat polarization voltage.
Regarding Claim 13, An discloses an electrochemical energy storage device (solid-state lithium ion battery; [0010]) comprising a solid electrolyte ([0010];[0015]) and a wetting agent (organic solvent; [0010 – 0012]).
The organic solvent disclosed by An reads on the claimed wetting agent, because, like the claimed wetting agent, the organic solvent functions to reduce contact impedance between the electrolyte and electrode in the battery and ultimately allow for improved performance of the solid-state lithium ion battery (An: [0022]; Instant Specification: [0164 – 0165]). Furthermore, materials listed/exemplified to be used as the organic solvent in An, such propylene carbonate, are claimed and disclosed by the applicant to be wetting agents (An: [0022];[0046 – 0050]; Instant Specification: [0164]).
In Example 1 of An, the organic solvent is propylene carbonate and the solid electrolyte is a solid polymer electrolyte composed of polyethylene carbonate, poly(vinylidene fluoride-hexafluoropropylene), and lithium bis (trifluoromethylsulfonyl imide) ([0046]). The negative electrode of the example battery is a lithium metal electrode and the positive electrode is a lithium iron phosphate electrode ([0047 – 0048]).
As an alternative to polymer electrolytes, An also teaches using inorganic solid electrolytes for the solid-state lithium ion battery ([0015]). Inorganic solid electrolytes taught by An include materials such as Li7La3ZrO12, Li10GeP2S12, Li3OCl0.5Br0.5, Li3xLa(2/3)-xTiO3, Li5La3Ta2O12, Li5La3Nb2O12, Li5.5La3Nb1.74In0.25O12, Li3N-LiCl, Li3N-LiBr, Li3N-LiI, Li14Zn(GeO4)4, LiZr2(PO4)3, Li3OCl, LiPON, and Li2S-MaSb wherein 0.04 < x < 0.14, M = Al, Si, or P, and the values of a and b are 1 – 3, respectively.
An does not specifically disclose wherein the solid electrolyte composition comprises a solid, halide-crystalline lithium argyrodite represented by a formula chosen from the group consisting of LimPSnXo and LimPSn, where m is a number in the range of 4-8, n is a number in the range of 3-6, X represents at least one halide, and o is a number in the range of 0-3.
Utsuno teaches a sulfide solid electrolyte with an argyrodite-crystal structure represented by LiaPSbClc wherein 5.0 ≤ a ≤ 6.5, 6.1 ≤ a + c ≤ 7.5 {i.e. 0.4 ≤ c ≤ 2.5}, 0.5 ≤ a - b ≤ 1.5 {i.e. 3.5 ≤ b ≤ 6}, b > 0, and c > 1.0 are satisfied ([0035];[0055 – 0057]). Utsuno further teaches that the electrolyte material has improved ion conductivity due to the inclusion of chlorine, and is compatible with negative electrodes including elemental metals like metal lithium and positive electrodes including transition metal oxides like LiFePO4 ([0015];[0026];[0107];[0122]).
Since An already teaches using inorganic sulfide solid electrolytes that include Li, S, and P, it would have been obvious to one with ordinary skill in the art, before the effective filing date of the claimed invention, to modify the battery of Example 1, to include the sulfide solid electrolyte taught by Utsuno, and thus obtain a solid electrolyte composition within the claimed scope, with a reasonable expectation of success in obtaining a solid electrolyte with improved conductivity and suitable for An’s solid-state lithium ion battery.
Modified An, as established above, includes the claimed electrolyte composition characterized by a halide-containing crystalline lithium argyrodite structure represented by xLiX·Li6PS5X.
Modified An does not explicitly disclose the electrolyte composition characterized to form a solid electrolyte, halide containing interphase layer between the solid electrolyte composition and an electrode; however, the recitation “to form a solid electrolyte, halide containing interphase layer between the solid electrolyte composition and an electrode” establishes an intended use/inherent function for the solid electrolyte composition. Regarding product and apparatus claims, when the structure recited in the reference is substantially identical to that of the claims, claimed properties or functions are presumed to be inherent.
Furthermore, in the instant specification, the applicant indicates that a lithium halide-containing interphase at the interface of the electrode and electrolyte can form in a battery when a LiCl-rich argyrodite solid electrolyte is used with trace amounts of carboxylic acid ester ([0163 – 0164]).
As such, since modified An renders obvious the claimed battery composition and structure {i.e. propylene carbonate wetting agent and halide-containing crystalline lithium argyrodite solid electrolyte}, including electrode materials {i.e. lithium metal negative electrode and lithium transition metal positive electrode} disclosed in the instant specification: [00169], a skilled artisan would reasonably expect, the battery of modified An to form the claimed solid electrolyte, halide containing interphase layer between the solid electrolyte composition and an electrode.
Regarding Claim 18, An discloses all limitations as set forth above. As established above, the solid electrolyte composition of modified An includes a halide-containing crystalline lithium argyrodite represented by LiaPSbClc wherein 5.0 ≤ a ≤ 6.5, 6.1 ≤ a + c ≤ 7.5 {i.e. 0.4 ≤ c ≤ 2.5}, 0.5 ≤ a - b ≤ 1.5 {i.e. 3.5 ≤ b ≤ 6}, b > 0, and c > 1.0 are satisfied (Utsuno: [0035];[0055 – 0057]); therefore, modified An teaches wherein o {i.e. amount of Cl} is a number in the range 0.4 – 2.5, which significantly overlaps the claimed range of 0.5 – 3 inclusive of end points.
Utsuno’s taught ranges for the molar ratios of Li, S, and Cl in LiaPSbClc provide the advantageous effects of stable crystal structure and improved ion conductivity ([0005];[0026];[0047 – 0053]). Furthermore, Utsuno teaches that increasing the Cl content reduces the lattice constant of the argyrodite crystal structure and ultimately allows for improvements in ion conductivity ([0026]).
Therefore, selection of halide-containing crystalline lithium argyrodites with chloride contents within the claimed range, such as Li6PS5Cl·0.5LiCl {x = 0.5} and Li6PS5Cl {x = 0}, would have been obvious to one with ordinary skill in the art to optimize the crystal structure and conductivity of the sulfide solid electrolyte material of modified An, with a reasonable expectation of success and without undue experimentation [MPEP 2144.05(II)].
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to ARYANA Y ORTIZ whose telephone number is (571)270-5986. The examiner can normally be reached M-F 7:00 AM - 5:00 PM.
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If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Jonathan Leong can be reached at (571) 270-1292. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
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/A.Y.O./Examiner, Art Unit 1751
/JONATHAN G LEONG/Supervisory Patent Examiner, Art Unit 1751 10/29/2025
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