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/Restriction
Applicant’s election without traverse of Group I in the reply filed on May 7th, 2026 is acknowledged. Claims 26-31 are withdrawn from further consideration pursuant to 37 CFR 1.142(b) as being drawn to a nonelected method of preparing the all-solid-state secondary battery, there being no allowable generic or linking claim.
Specification
The disclosure is objected to because of an informality in the description of the reference characters. Specifically, reference numeral 11 is denoted as the cathode current collector 11 throughout the document, but in [0084], it is labeled as the first anode active material layer 11. Appropriate correction is required.
Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
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.
Claims 1, 3, 9, 13, 16, 19, and 21-23 are rejected under 35 U.S.C. 103 as being unpatentable over Oh (US20210202936A1) and further in view of Zhamu (US20200028205A1).
Regarding claim 1, Oh teaches a solid-state secondary battery (claim 1; [0003]), comprising:
a cathode (claim 1) comprising a cathode active material ([0028] lines 6-12);
an anode (claim 1) comprising an anode current collector (anode current collector 150; [0020]; Figs. 1-3), a first anode active material layer (first anode layer comprises a non-silicon metal or metalloid capable of alloying with lithium, claim 1; tin layer 180, [0023]), and a second anode active material layer (second anode layer includes silicon or silicon oxide, claim 1; silicon layer 160, [0023]);
and a solid electrolyte arranged between the cathode and the anode (solid electrolyte layer 130, Fig. 1-3),
the second anode active material layer (silicon layer 160, [0023]) is arranged between the anode current collector and the first anode active material layer (see Fig. 1C below),
the second anode active material layer (i.e. the silicon layer) comprises a second anode active material, and the second anode active material comprises: a carbon-containing anode active material, or a carbon-containing anode active material, and at least one of a metallic anode active material and a metalloid anode active material (silicon layer 160 may be replaced with a silicon-based composite layer 210, and layer 210 may further include conductive additives such as carbon black, carbon fibers, or carbon nanotubes and/or a second anode active material such as graphite or hard carbon [0024]),
PNG
media_image1.png
536
1052
media_image1.png
Greyscale
and wherein the first anode active material layer (tin layer 180, [0023]) is arranged adjacent to the solid electrolyte (see Fig. 1C below).
Fig. 1C from Oh
Oh additionally teaches that the first active material layer (tin layer 180, [0023]) comprises tin, which is capable of alloying with lithium ([0015]) and may be replaced with tin-based composite layers (Fig. 2B; the tin composite layer may include silicon particles ([0016], [0024]) and conductive additives such as graphite or hard carbon, [0024] lines 23-27). Further, Oh teaches that other soft metals and metalloids capable of alloying with lithium can also be used in place of tin, or in addition to tin [0027].
Oh does not expressly teach a battery wherein the first anode active material layer comprises an M1-M2Ox composite, a Li-M1-M2Ox composite, or a combination thereof, wherein M1 is a first metal and M2 is a second metal, the first metal and second metal are each independently at least one element that reacts with lithium to form a lithium alloy or a lithium compound, and x is a number greater than 0.
Zhamu discloses a lithium secondary battery containing an anode that comprises particles of an anode active material (claim 1). Zhamu further discloses that the anode active material may be selected from, among other materials, lithiated and un-lithiated oxides of elements such as tin (Sn) (i.e. Zhamu discloses Sn in metal form in addition to the oxide form, SnO2, as anode active materials; claim 13), and further explicitly teaches SnO₂ as a main anode active material ([0015] and [0043]). Zhamu additionally teaches that the disclosed anode active material configuration may provide rapid recharge capability, high specific energy, long cycle life, and suppression of lithium dendrite-induced internal short circuits and thermal runaway ([0009]-[0010]).
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to modify the first anode active material layer (i.e. the tin/tin composite layer) of Oh (hereby referred to as “modified Oh”) to include the tin oxide composite (SnO₂) anode active material as taught by Zhamu, because Oh expressly teaches that the first anode active material layer may be provided as a tin composite layer, and Zhamu teaches that tin oxide (SnO₂) particles are a known anode active material suitable for rechargeable lithium secondary batteries. Such modification would have involved including a known lithium-reactive anode active material into the composite first anode active material layer of Oh while preserving the layered anode architecture taught by Oh. One of ordinary skill in the art would have had reasonable expectation of success because Zhamu teaches that the disclosed anode active material configuration may improve cycle life and safety ([0009]-[0010]).
Accordingly, the first anode active material of modified Oh comprises an M1-M2Ox composite wherein M1 is a first metal and M2 is a second metal (M1=Sn, M2=Sn), the first metal and second metal are each independently at least one element that reacts with lithium to form a lithium alloy or a lithium compound, and x is a number greater than 0 (x=2), as claimed. Therefore, all limitations of claim 1 are either met or rendered obvious by modified Oh.
Regarding claim 3, modified Oh teaches all limitations of claim 1 as described above, and further discloses with the modification of Zhamu that the first anode active material comprises an anode active material comprising a M1-M2Ox composite that includes SnO₂, where M1=Sn, M2=Sn, and x=2 (Zhamu, claim 13; [0015], [0043], [0134]; Fig. 1).
Regarding claim 9, modified Oh teaches all limitations of claim 1 as described above. However, Oh does not expressly teach the all-solid-state secondary battery wherein the first anode active material layer comprises a plurality of pores.
Zhamu teaches that the anode active material layer contains an electrically conductive porous layer having pores to accommodate the anode active material particles (claim 1). Zhamu further teaches that the electrically conductive porous layer serves as the backbone or framework of the anode active material layer ([0013] lines 9-19).
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to further modify the first anode active material layer to include the porous structure taught by Zhamu, because Zhamu teaches that the porous framework accommodates the anode active material and facilitates the disclosed electrode configuration. Such modification would represent the application of a known electrode structural feature to a similar battery system for its known purpose, yielding the predictable result of a first anode active material layer comprising a plurality of pores while preserving the layered architecture of Oh. Accordingly, Oh as modified by Zhamu (hereby referenced to as “modified Oh”) teaches or renders obvious the limitations of claim 9.
Regarding claim 13, modified Oh teaches all limitations of claim 1 as described above and further teaches the all-solid-state secondary battery comprises a metal thin film (anode current collector 150 may be formed from stainless steel, nickel, or nickel-plated copper. The anode current collector can be any thin (<30 microns) electronically conductive material that has a stable interface in contact with tin, [0022]) disposed between the second anode active material layer and the anode current collector (Fig. 1A-1C).
Regarding claim 16, modified Oh teaches all limitations of claim 1 as described above. Oh further teaches that the anode current collector can be formed from stainless steel, nickel, or nickel-plated copper, or any thin (<30 microns) electronically conductive material that has a stable interface in contact with tin (anode current collector 150, [0022]).
Oh does not expressly teach the all-solid-state secondary battery further comprising a lithium film or a lithium alloy film that is located between the second anode active material layer and the anode current collector.
Zhamu teaches that for a lithium metal battery, one may use a thin Li foil attached to a Cu foil as the current collector configuration ([0110] lines 10-12). Accordingly, the term "thin Li foil" corresponds to the "lithium film" limitation in the claim, and the copper (Cu) foil functions as the anode current collector.
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to modify the anode of Oh to include a lithium film or lithium alloy film located between the second anode active material layer and the anode current collector as taught by Zhamu, because Zhamu teaches that applying a thin Li foil (lithium film) attached to a current collector is a standard and well-known practice for forming high-performance lithium metal battery anodes ([0026]). Such modification would represent the predictable use of known prior art elements according to their established functions. Specifically, the predictable result of attaching a thin lithium film (or foil) to a current collector is to provide a reliable source of lithium ions and ensure uniform plating/stripping at the current collector interface, thereby optimizing battery efficiency and capacity. Furthermore, a person of ordinary skill in the art would have known that the lithium film can be applied to current collectors like nickel or stainless steel, as taught by Oh, or attached directly to copper, as taught by Zhamu, with a reasonable expectation that both approaches would predictably yield a functional anode electrode.
Regarding claim 19, modified Oh teaches all limitations of claim 1 as described above, and further teaches wherein the silicon layer may be replaced with a silicon-based composite layer, which may further include conductive additives such as carbon black, carbon fibers, or carbon nanotubes, which are forms of amorphous carbon ([0024]). Thus, Oh discloses that the second anode active material layer comprises a carbon-containing anode active material comprising amorphous carbon, and the metallic anode active material or the metalloid anode active material comprises silicon.
Regarding claim 21, modified Oh teaches all limitations of claim 1 as described above, and further discloses an additional tin layer (tin layers 330 and 350; Fig. 3A) arranged between the anode current collector and the second anode active material layer (i.e. the silicon-based composite layer; Fig. 3A). Oh further teaches that the first active material layer (i.e. the tin layer) comprises tin, which is capable of alloying with lithium ([0015]). Oh also teaches that other soft metals and metalloids capable of alloying with lithium can also be used in place of tin, or in addition to tin [0027]. Thus, Oh discloses a third anode active material layer arranged between the anode current collector and the second anode active material layer wherein the third anode active material layer is a metal layer comprising lithium or a lithium alloy.
PNG
media_image2.png
486
736
media_image2.png
Greyscale
Fig. 3A from Oh
Regarding claim 22, modified Oh teaches all limitations of claim 1 as described above, and further teaches:
the first anode active material comprises tin ([0023]),
the anode current collector may be formed from stainless steel, nickel, or nickel-plated copper ([0022]),
and the second anode active material comprises silicon and may further include a binder, conductive additives, and an electrolyte [(0024)].
Thus, Oh discloses that the anode current collector, the first anode active material layer, and the second anode active material layer, including all regions therebetween, are Li-free regions that do not comprise lithium in an initial state, as they are not disclosed to be comprised of lithium materials.
Regarding claim 23, modified Oh teaches all limitations of claim 1 as described above, and further teaches the solid electrolyte is an oxide-containing solid electrolyte, a sulfide-containing solid electrolyte, or a combination thereof. In particular, Oh expressly discloses that possible solid electrolytes include but are not limited to inorganic oxide, sulfide, or phosphate electrolytes, solid polymer electrolytes, and gel polymer electrolytes (pg. 2, column 2, [0024], lines 12-16).
Claim 2 is rejected under 35 U.S.C. 103 as being unpatentable over Oh (US20210202936A1) in view of Zhamu (US20200028205A1) as applied to claim 1 above, and further evidenced by Pourbaix (Marcel Pourbaix, Atlas of Electrochemical Equilibria in - Aqueous Solutions, National Association of Corrosion Engineers, 1974.) and Xie (Xie et. al. Li-ion diffusion behavior in Sn, SnO and SnO2 thin films studied by galvanostatic intermittent titration technique, Solid State Ionics, Volume 181, Issues 35–36, 2010).
Regarding claim 2, modified Oh teaches all limitations of claim 1 as described above, and further teaches the first anode active material layer wherein, in the M1-M2Ox composite and the Li-M1-M2Ox composite, the first metal and the second metal are the same or different from each other (consistent with the modification in the rejection of claim 1, the first active material tin (Sn) layer of Oh may be modified to include an M1-M2Ox composite such as SnO₂, where M1=Sn, M2=Sn, and x=2, or a related binary metal oxide).
Modified Oh does not expressly describe the thermodynamic phase stability or electrochemical behavior of its Sn-SnO₂ composite at pH 7 or less.
Pourbaix evidences the definitive thermodynamic equilibrium and phase behavior of the tin-water system. Specifically, as shown in Figure 1 of Pourbaix (pg. 478, Chapter IV, Section 17.4, Figure 1: Potential-pH Equilibrium Diagram for the System Tin-Water at 25 °C), both elemental tin (Sn) and its oxides (SnO and SnO₂) reside entirely within thermodynamically stable solid phase boundaries Sn(s), SnO(s), and SnO2(s), under standard operational electrochemical potential windows at a pH of 7 or less. Soluble tin ions only form under extreme oxidizing/acidic or highly alkaline boundaries. Thus, modified Oh discloses, with Sn as the identity of the first and second metal, that the first and second metal maintain a solid state in a solution with a pH of 7 or less, as evidenced by Pourbaix.
Regarding the limitation of lithium-ion diffusivity, modified Oh does not expressly quantify the lithium-ion diffusivity of the metallic tin or tin oxide film. However, this missing parameter is rendered obvious by modified Oh in view of Xie.
Xie discloses that the apparent lithium-ion chemical diffusion coefficient for a metallic Sn film, as determined by galvanostatic intermittent titration technique (GITT), ranges from 10− 16 to 10− 14 cm2 s− 1 for metallic Sn films and 10− 15 to 10− 13 cm2 s− 1 for tin oxide films (abstract; pg. 1614, right column, lines 26-31) at room temperature (the Sn based films were deposited at room temperature, pg. 1612, left column, section “3. Results and discussion”, lines 1-2; all electrochemical measurements were performed at 20°C, pg. 1612, left column, lines 19-20). Xie further discloses the optimization of metallic Sn films for the exact same electrochemical utility (battery anode active materials; pg. 1611, left column, para. 1). Thus, since the claimed threshold of 1×10-14 square centimeters per second falls within and overlaps with the upper boundary of the range disclosed by Xie’s, a prima facie case of obviousness is established. Further, it is well-established that discovering the optimum value or range of a result-effective variable (such as optimizing the morphology of a Sn film for optimal lithium-ion diffusivity and battery performance) is routine for a person of ordinary skill in the art. Therefore, further modifying the metallic Sn anode active material of Oh to exhibit the upper-end diffusivity of 1×10-14 square centimeters per second as evidenced by Xie would have been an obvious variation.
Accordingly, the limitation of the first and second metal (which are both tin (Sn) in this case) having a lithium-ion diffusivity of 1×10-14 square centimeters per second at 25°C, as claimed, is rendered obvious by the combined teachings of modified Oh as further evidenced by Pourbaix and Xie.
Claims 4 and 15 are rejected under 35 U.S.C. 103 as being unpatentable over Oh (US20210202936A1) in view of Zhamu (US20200028205A1) as applied to claim 1 above, and further in view of Fan (Fan et. al., Tellurium nanoparticles enhanced electrochemical performances of TeO2-V2O5-Al2O3 glass anode for Lithium-ion batteries. Journal of Non-Crystalline Solids. 521 (2019)).
Regarding claim 4, modified Oh teaches all limitations of claim 1 as described above, and further discloses a first anode active material wherein the first metal and the second metal are identical to or different from each other. Specifically, Oh discloses with the modification of Zhamu that the first anode active material comprises an anode active material comprising a M1-M2Ox composite that includes SnO₂, where M1=Sn, M2=Sn, and x=2 (Zhamu, SnO₂; claim 13; [0015], [0043], [0134]; Fig. 1). Zhamu additionally discloses that the anode active material particles may be selected from the group consisting of lithiated and un-lithiated oxides and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, Mn, V, or Cd, and their mixtures, composites, or lithium-containing composites (Zhamu, [0035]).
However, neither Oh nor Zhamu expressly teach the anode active material layer specifically comprises a Te-TeOx composite, wherein 0<x≤2.
Fan discloses a TeO2-based glass anode for a lithium-ion battery that comprises Te-nanocrystals (i.e. Te metal) randomly distributed in the TeO2-based glass matrix. Fan further discloses that after formation of the Te nanocrystals during discharging/charging cycles, the Te nanocrystals enhanced the electron transfer kinetics while the TeO2-based matrix maintained the anode materials mechanically stable, with both features synergistically contributing to superior rate capability and excellent cycling stability (Fan, pg. 6, “4. Conclusions” section, lines 16-21).
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to substitute the Sn-SnO2 composite of modified Oh in the first anode active material layer with the Te-TeO2 composite of Fan, because Fan explicitly teaches that the combination of Te nanocrystals (i.e. Te metal) and the remaining glass matrix (TeO2) works synergistically to enhance the electron transfer kinetics and mechanical stability. Modifying the metal oxide composite of the first anode active material layer to include a Te-TeO2 composite would be a predictable variation, yielding the predictable results of improved rate capability and mechanical stability as taught by Fan.
Regarding claim 15, modified Oh teaches all limitations of claim 1 as described above. Specifically, Oh discloses with the modification of Zhamu that the first anode active material comprises an anode active material comprising an M1-M2Ox composite that includes SnO₂, where M1=Sn, M2=Sn, and x=2 (Zhamu, SnO₂; claim 13; [0015], [0043], [0134]; Fig. 1). Zhamu additionally discloses that the anode active material particles may be selected from the group consisting of lithiated and un-lithiated oxides and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, Mn, V, or Cd, and their mixtures, composites, or lithium-containing composites (Zhamu, [0035]).
Regarding the M1-M2Ox composite limitation of claim 2, neither Oh nor Zhamu expressly teach the anode active material layer wherein the first anode active material layer comprises an M1-M2Ox composite, wherein the M1-M2Ox composite is Tex-TeyOz, and 0 < x ≤ 3, 0 < y ≤ 2, 0 < z ≤ 2.
Fan discloses a TeO2-based glass anode for a lithium-ion battery that comprises Te-nanocrystals (i.e. Te metal) randomly distributed in the TeO2-based glass matrix. Fan further discloses that the formation of the Te nanocrystals occurred during discharging/charging cycles, and that these formed Te nanocrystals enhanced the electron transfer kinetics while the TeO2-based matrix maintained the anode materials mechanically stable, with both features synergistically contributing to superior rate capability and excellent cycling stability (Fan, pg. 6, “4. Conclusions” section, lines 16-21).
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to modify the M1-M2Ox composite of modified Oh in the first anode active material layer to comprise the Te-TeO2 composite of Fan, because Fan explicitly teaches that the combination of Te nanocrystals (Te) and the glass matrix (TeO2) works synergistically to enhance the electron transfer kinetics and mechanical stability. Modifying the metal oxide composite of the first anode active material layer to include the Te-TeO2 composite of Fan would be a predictable variation, yielding the predictable results of improved rate capability and mechanical stability as taught by Fan.
Regarding the limitation wherein the Li-M1-M2Ox composite in the first anode active material layer is Lia-Tex-TeyOz, wherein 0 < a ≤ 5, 0 < x ≤ 3, 0 < y ≤ 2 and 0 < z ≤ 2, claim 1 gives distinct options for the anode active material: it can comprise an M1-M2Ox composite OR a Li-M1-M2Ox composite. Since the rejection of claim 1 applies to the M1-M2Ox composite, the lithiated alternative Li-M1-M2Ox is not a required limitation of the active material for the purpose of instant claim 1. However, with respect to the limitation that the Li-M1-M2Ox composite comprises Lia-Tex-TeyOz, it is well known in the art that during the discharging/charging cycles of a lithium-ion battery (as applied by Fan), the Te and TeO2 active materials become lithiated. Further, Zhamu explicitly discloses that the anode active material particles may be selected from the group consisting of both lithiated and un-lithiated oxides, tellurides, and combinations thereof (Zhamu, [0035]). Thus, modifying the Te-TeO2 composite to include lithium during battery operation would be an obvious step for a person of ordinary skill in the art to take, and would inherently yield an anode active material layer comprising the claimed Lia-Tex-TeyOz composition.
Claim 5 is rejected under 35 U.S.C. 103 as being unpatentable over Oh (US20210202936A1) in view of Zhamu (US20200028205A1) as applied to claim 1 above, and further in view of Spada (Spada et. al., Self-Supported Fibrous Sn/SnO2@C Nanocomposite as Superior Anode Material for Lithium-Ion Batteries. Materials, 15, 919, (2022).).
Regarding claim 5, modified Oh (as modified by Zhamu) teaches all limitations of claim 1 as described above, including the all-solid-state secondary battery wherein the first anode active material layer comprises an M1-M2Ox composite such as Sn-SnO₂, where M1=Sn, M2=Sn, and x=2.
Oh does not expressly teach a first anode active material layer wherein, in the M1-M2Ox composite, an amount of M2Ox is about 0.05 parts by weight to about 50 parts by weight, based on 100 parts by weight of a total weight of the M1-M2Ox composite.
Spada discloses an anode material for a lithium-ion battery comprising Sn/SnOx@C composites, where tin and tin oxides were homogeneously dispersed in a carbonaceous matrix of carbon nanofibers (abstract). Spada further discloses a specific embodiment of a tin/carbon composite, Sn/SnO2@C–P, with a value of 25.43 wt.% based on a total weight of the Sn/SnO2 composite (pg. 6, Table 1, Sn/SnO2@C–P), which falls within the claimed range. The limitation "parts by weight based on 100 parts by weight of the total weight" is mathematically identical to weight percent (wt.%).
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to further modify the first anode active material layer of Oh by utilizing the specific ratio/weight percentage of the oxide phase within the tin/carbon composite as taught by Spada. One of ordinary skill in the art would have been motivated to make this modification because Spada demonstrates that maintaining the tin oxide phase within this specific quantitative range ensures structural stability and optimized electrochemical phase distribution when dispersed within a carbonaceous matrix. Furthermore, optimizing the relative amounts or ratios of known active material components to achieve a desired balance of electrical resistance (pg. 12, para. 4) and cyclability (pg. 13, para. 1) would be a matter of routine optimization yielding predictable results.
Claim 6 is rejected under 35 U.S.C. 103 as being unpatentable over Oh (US20210202936A1) in view of Zhamu (US20200028205A1) as applied to claim 1 above, and further in view of Spada (Spada et. al., Self-Supported Fibrous Sn/SnO2@C Nanocomposite as Superior Anode Material for Lithium-Ion Batteries. Materials, 15, 919, (2022)) and Zhamu/Jang (US20190260028A1).
Regarding claim 6, modified Oh (as modified by Zhamu) teaches all limitations of claim 1 as described above, including that the first anode active material layer comprises the M1-M2Ox composite Sn-SnO₂, where M1=Sn, M2=Sn, and x=2. However, Oh does not expressly teach a first anode active material layer wherein, in the Li-M1-M2Ox composite:
an amount of Li is about 0.01 parts by weight to about 80 parts by weight, based on 100 parts by weight of a total weight of the Li-M1-M2Ox composite,
an amount of M1 is about 10 parts by weight to about 70 parts by weight, based on 100 parts by weight of the total weight of the Li-M1-M2Ox composite,
and an amount of M2Ox is about 0.05 parts by weight to about 50 parts by weight, based on 100 parts by weight of the total weight of the Li-M1-M2Ox composite.
Regarding the general limitation wherein the first anode active material comprises a Li-M1-M2Ox composite for instant claim 6, claim 1 in which it depends upon gives distinct options for the anode active material: it can comprise an M1-M2Ox composite OR a Li-M1-M2Ox composite. Since the rejection of claim 1 for the instant application applies to the M1-M2Ox composite, the lithiated alternative Li-M1-M2Ox is not a required limitation of the active material for the purpose of instant claim 1.
However, regarding the amounts of tin (Sn) and tin oxide (SnO2) components of the claimed Li-M1-M2Ox composite, Spada discloses an anode material for a lithium-ion battery comprising Sn/SnOx@C composites, where tin and tin oxides were homogeneously dispersed in a carbonaceous matrix of carbon nanofibers (abstract). Spada further discloses a specific embodiment of a tin/carbon composite, Sn/SnO2@C–P, with:
an amount of M1, which is Sn in this case, present in an amount of 62.28 wt.% based on a total weight of the Sn/SnO2 composite (pg. 6, see Table 1, Sn/SnO2@C–P), which falls within the claimed range of about 10 parts by weight to about 70 parts by weight,
and an amount of M2Ox, which is SnO2 in this case, present at a value of 24.43 wt.% based on 100 parts by weight of the total weight of the composite (pg. 6, see Table 1, Sn/SnO2@C–P), which falls within the claimed range of about 0.05 parts by weight to about 50 parts by weight.
PNG
media_image3.png
263
1595
media_image3.png
Greyscale
Table 1 from Spada
The limitation "parts by weight based on 100 parts by weight of the total weight" is mathematically identical to weight percent (wt.%). Spada further discloses that an intermediate LixSnOy phase by insertion of Li+ in SnO2 is formed during cycling (Spada, pg. 9, para. 1, lines 1-3), demonstrating that a Li-Sn-SnOx anode active material composite is a structurally predictable result when cycling tin and tin oxides in a lithium battery environment.
Regarding the amount of Li in the composite, Zhamu/Jang teaches an anode active material layer for a lithium battery that may contain high-capacity anode active materials such as oxides and composites of Sn (in (c) of claim 3), explicitly teaching Sn and SnO2 ([0015]). Zhamu/Jang further discloses that such materials can be pre-intercalated or pre-doped with lithium ions to form a prelithiated active material having an amount of lithium from 0.1% to 54.7% by weight (claim 12), which overlaps with the claimed Li content range of 0.01 parts by weight to about 80 parts by weight.
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to further modify the tin oxide composite within the first anode active material layer of Oh to incorporate the specific amounts of Li, M1 (M1=Sn), and M2Ox (M2Ox =SnO2) taught by Spada and Zhamu/Jang. A prima facie case of obviousness is established when the claimed ranges of components overlap with ranges disclosed in the prior art (see MPEP § 2144.05). Furthermore, selecting optimized weight percent components for a known anode active material composite is a matter of routine optimization for one of ordinary skill in the art.
Claim 7 is rejected under 35 U.S.C. 103 as being unpatentable over Oh (US20210202936A1) and Zhamu (US20200028205A1) as applied to claim 1 above, and further in view of Kim (Kim, et. al., Threshold Switching Characteristics of Te-doped Insulator Thin Films for the Application of Next-generation Non-volatile Memory. PhD thesis, Seoul National University, 2018.)
Regarding claim 7, modified Oh teaches all limitations of claim 1 as described above. Modified Oh does not expressly teach the all-solid-state secondary battery wherein, in the M1-M2Ox composite and the Li-M1-M2Ox composite, the metals M1 and M2 are different from each other, and the M1-M2Ox composite and the Li-M1-M2Ox composite are each independently a Te-SiOx composite wherein 0<x≤2, or a Li-Te-SiOx composite wherein 0<x≤2, as claimed.
Kim teaches a Te-SiO2 thin film comprising a specific microstructure in which Te nanoclusters are distributed within a SiO2 matrix. Kim further teaches that this material has high thermal stability and forms conductive Te filaments during electro-forming (pg. ii, para. 1; pg. 95, “4.2.3 Crystallographic Characteristics of the Te-SiO2 Thin Films” paragraph).
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to further modify the first anode active material of Oh (as previously modified by Zhamu in the rejection of claim 1 above) by incorporating the specific microstructural arrangement of Te and SiO2 taught by Kim, because Kim specifically teaches that a Te-SiO2 thin film having Te nanoclusters distributed in a SiO2 matrix possesses highly advantageous structural, thermal, and conductive properties. A person of ordinary skill in the art would be motivated to utilize this specific composite material as an anode active material to improve the electrical conductivity and thermal stability of the battery's anode structure.
Accordingly, modified Oh (as modified by Zhamu in claim 1 and now further modified by Kim) renders the claim obvious, and therefore teaches the all-solid-state secondary battery wherein, in the M1-M2Ox composite and the Li-M1-M2Ox composite, the metals M1 and M2 are different from each other (in this case, M1=Te, M2=Si, x=2), and the M1-M2Ox is formed of a Te-SiOx composite wherein 0<x≤2 (in this case, Te-SiO2), as claimed.
Claim 8 is rejected under 35 U.S.C. 103 as being unpatentable over Oh (US20210202936A1) and Zhamu (US20200028205A1) as applied to claim 1 above, and further in view of Zhamu/Jang (US20190260028A1).
Regarding claim 8, modified Oh teaches all limitations of claim 1 as described above. However, modified Oh does not expressly teach the all-solid-state secondary battery wherein a thickness of the first anode active material layer is about 10 nanometers to about 500 nanometers, as claimed.
Zhamu/Jang teaches an anode layer configuration comprising high-capacity anode active materials (e.g. Si, Sn, or SnO2; [0015]), a conductive additive, and a binder ([0035]; Fig. 1(B)), such that the anode layer is a thin coating of an anode active material ([0034]; Fig 1(A)). Zhamu/Jang further discloses that this anode active material may be present in the form of a nanoparticle (spherical, ellipsoidal, and irregular shape), nanowire, nanofiber, nanotube, nanosheet, nanobelt, nanoribbon, nanodisc, nanoplatelet, or nanohorn having a thickness or diameter less than 100 nm ([0021]), which overlaps with the claimed range of 10 nm to 500 nm.
It is well-established that a prima facie case of obviousness is established when the claimed range and a prior art range overlap (see MPEP 2144.05). When the difference between the claimed invention and the prior art is merely the selection of a specific numerical range within a broader prior art range, one of ordinary skill in the art would find it obvious to determine the optimal or workable range through routine experimentation. Accordingly, a person of ordinary skill in the art before the effective filing date of the claimed invention would have found it obvious to select a first anode active material thickness to be within the claimed range in order to optimize battery performance and maintain conductivity.
Claims 10-12 are rejected under 35 U.S.C. 103 as being unpatentable over Oh (US20210202936A1) and Zhamu (US20200028205A1) as applied to claim 1 above, and further in view of Yu (Yu et. al., Porous carbon networks containing Si and SnO2 as high performance anode materials for lithium-ion batteries. Materials Letters. 184, pgs 169–172. 2016.)
Regarding claim 10, modified Oh teaches all limitations of claim 9 as described above, including a first anode active material layer comprising a tin oxide composite (SnO₂) as modified by Zhamu in the rejection of claim 1, and a first anode active material layer that comprises a plurality of pores as discussed in the rejection of claim 9 above. Modified Oh further teaches the second anode active material comprises silicon and carbon, as discussed in the rejection of claim 1.
Oh does not expressly teach wherein in the first anode active material layer, at least one of the plurality of pores comprises the second anode active material disposed therein.
Yu discloses an anode composite material for a battery comprising a porous carbon network containing Si and SnO₂. Specifically, Yu discloses a Si-SnO₂-C composite constructed of interconnected amorphous carbon branches containing nano-pores, and Si and SnO₂ nanoparticles disposed within the carbon branches (abstract; pg. 171, right column, lines 3-18). Thus, Yu discloses a composite anode material composition comprising Si (i.e. the second anode active material) disposed within the pores of the carbon or SnO₂ matrix (i.e. the first anode active material). Yu further discloses that an anode comprising the Si-SnO2-C composite exhibits excellent battery performance by providing a large specific surface area, shortened lithium-ion diffusion distance, and an anode that maintains structural stability during charging/discharging processes (pg. 171, right column, lines 14-18).
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to utilize the known composite anode material configuration of Yu in the first anode active material layer of Oh (as previously modified by Zhamu) in order to achieve an anode capable of accommodating volume changes during cycling (pg. 169, “Introduction” section, paragraph 1) and maintaining structural stability during charging/discharging processes.
Regarding claim 11, modified Oh teaches all limitations of claim 1 as described above. However, Oh does not expressly teach the all-solid-state secondary battery wherein the first anode active material layer comprises a plurality of pores.
Zhamu teaches that the anode active material layer contains an electrically conductive porous layer having pores to accommodate the anode active material particles (claim 1). Zhamu further teaches that the electrically conductive porous layer serves as the backbone or framework of the anode active material layer ([0013] lines 9-19).
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to further modify the first anode active material layer of Oh (hereby referred to as “modified Oh”) to include the porous structure taught by Zhamu, because Zhamu teaches that the porous framework accommodates the anode active material and facilitates the disclosed electrode configuration. Such modification would represent the application of a known electrode structural feature to a similar battery system for its known purpose, yielding the predictable result of a first anode active material layer comprising a plurality of pores while preserving the layered architecture of Oh.
However, modified Oh does not expressly teach the first anode active material layer wherein (1) at least one of the plurality of pores comprises the second anode active material disposed therein, and (2) a porosity of the first anode active material layer is less than the porosity of the first anode active material layer that does not comprise the second anode active material disposed therein, or the first anode active material layer is non-porous by incorporation of the second anode active material.
Regarding limitation (1), Yu discloses an anode composite material for a battery comprising a porous carbon network containing Si and SnO₂. Specifically, Yu discloses a Si-SnO₂-C composite constructed of interconnected amorphous carbon branches containing nano-pores, and Si and SnO₂ nanoparticles disposed within the carbon branches (abstract; pg. 171, right column, lines 3-18). Therefore, Yu discloses an anode composite material comprising a material with pores (carbon) and wherein at least one of the plurality of pores comprises a second anode active material (Si and SnO₂ nanoparticles) disposed therein.
Regarding limitation (2), the claim requires a porosity of the first anode active material layer to be less than the porosity of the first anode active material layer that does not comprise the second anode active material. This is inherent in the structure of the composite; by physically disposing the second anode active material (nanoparticles) inside the pores of the first anode active material, the second active material occupies the available pore volume. Consequently, the remaining open pore volume is reduced, mathematically resulting in a lower overall porosity.
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to further modify the first anode active material layer of Oh to incorporate a second anode active material (such as Si and SnO2) within the pores of the first anode active material (porous carbon), as taught by Yu. One of ordinary skill in the art would be motivated to do so because Yu teaches that filling the pores of a porous conductive matrix with active nanoparticles buffers the large volume changes during lithiation/delithiation, improves electrical conductivity, and enhances overall capacity (pg. 169, left column, para. 1 and right column lines 1-3) with the predictable results of a functional anode electrode wherein the porosity of the first anode active material layer to be less than the porosity of the first anode active material layer that does not comprise the second anode active material.
Regarding claim 12, modified Oh teaches all limitations of claim 9 as described above, including a first anode active material layer comprising a tin oxide composite (SnO₂) as modified by Zhamu in the rejection of claim 1, and a first anode active material layer that comprises a plurality of pores as discussed in the rejection of claim 9 above.
However, modified Oh does not expressly teach wherein a size of the plurality of pores in the first anode active material layer is about 3 nanometers to about 50 nanometers, as claimed.
Yu discloses an anode composite material for a battery comprising a porous carbon network containing Si and SnO₂. Specifically, Yu discloses a Si-SnO₂-C composite constructed of interconnected amorphous carbon branches containing nano-pores, and Si and SnO₂ nanoparticles disposed within the carbon branches (abstract; pg. 171, right column, lines 3-18). Yu explicitly discloses a nano-pore size of the interconnected amorphous carbon branches is 1–5 nm (abstract), which overlaps with the claimed range of about 3 nanometers to about 50 nanometers. The claimed range of about 3 to about 50 nm encompasses and extends continuously from the upper boundary of the 1–5 nm range taught by Yu. When the difference between the claimed invention and the prior art is merely a matter of size or range, a prima facie case of obviousness is established when the skilled artisan would have been motivated to optimize the variable (i.e. the pore size) (see MPEP 2144.05). Furthermore, the pore size of the anode active material is recognized in the art as a result-effective variable that may dictate battery performance in terms of volumetric expansion (Yu, pg. 169, “Introduction” section, paragraph 1) and specific capacity (Yu, pg. 169, right column, lines 5-9). In addition, it is well-established that discovering an optimum value within a range that is already known or taught by the prior art is routine experimentation and prima facie obvious to one of ordinary skill in the art (see MPEP 2144.05).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to optimize and select a pore size of the first anode active material layer within the claimed range of about 3 nanometers to about 50 nanometers, based on the teachings of Yu.
Claim 18 is rejected under 35 U.S.C. 103 as being unpatentable over Oh (US20210202936A1) in view of Zhamu (US20200028205A1) as applied to claim 1 above, and further evidenced by Malarkey (Malarkey et. al., Carbon Nanotubes in Neuroscience. Acta Neurochir Suppl. 106: 337-341, 2010).
Regarding claim 18, modified Oh teaches all limitations of claim 1 as described above, and further teaches the all-solid-state secondary battery wherein the carbon-containing anode active material has a particle form (silicon-based composite layer 210 may comprise particles and may further comprise conductive additives such as carbon nanotubes, [0024]).
As evidenced by Malarkey et. al., the size of a single-walled carbon nanotube (SWNT) typically ranges from 0.4 to 2 nm in diameter for SWNTs and 2 to 100 nm for multi-walled carbon nanotubes (MWNTs). Thus, Malarkey evidences that the average particle diameter of the particles in the carbon-containing anode active material is in a range of 0.4 – 100 nm (pg. 1, para. 2, lines 5-7), which falls within the claimed range.
Therefore, modified Oh, as evidenced by Malarkey, discloses that the carbon-containing anode active material has an average particle diameter of less than or equal to about 4 micrometers.
Claim 20 is rejected under 35 U.S.C. 103 as being unpatentable over Oh (US20210202936A1) and Zhamu (US20200028205A1) as applied to claim 1 above, and further in view of Suzuki (US20190157723A1).
Regarding claim 20, modified Oh teaches all limitations of claim 1 as described above, and further teaches the second anode active material in the second anode active material layer comprises a composite consisting of a first particle and a second particle, wherein the first particle consists of amorphous carbon, and the second particle consists of a metal or a metalloid. Specifically, modified Oh teaches the silicon layer may be replaced with a silicon-based composite layer containing silicon particles, which may further include conductive additives such as carbon black, carbon fibers, or carbon nanotubes, which are forms of amorphous carbon ([0024]). Thus, Oh discloses that the second anode active material layer comprises a composite consisting of a first particle and a second particle wherein the first particle consists of amorphous carbon, and the second particle consists of a metal or a metalloid (i.e. silicon).
However, Oh does not expressly teach the amount of the second particle is about 1 weight percent to about 60 weight percent, based on a total weight of the composite.
Suzuki discloses an all-solid-state secondary battery comprising an anode active material layer comprising an anode active material which is a metal alloyable with lithium or forms a compound with lithium (claim 1 and claim 9) and amorphous carbon (claim 19). Further, Suzuki discloses the anode active material may further include a mixture of a first particle comprising an amorphous carbon and a second particle comprising a metal such as Au, Pt, Pd, Si, Ag, Al, Bi, Sn, Zn, or a combination thereof, and further discloses the amount of the second particles may range from about 8 wt % to about 60 wt % with respect to a total weight of the mixture ([0100]). Suzuki further discloses an all-solid-state secondary battery anode comprising this configuration enhances battery characteristics such as long-term reliability in a charged state and improved cycle characteristics ([0076], [0143]).
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to further modify the second anode active material layer of Oh containing carbon particles and silicon particles by utilizing the amount of the second particles (silicon particles) in the range of about 8 wt % to about 60 wt % as disclosed by Suzuki in order to achieve a battery with enhanced cycle characteristics.
Claims 14, 17 and 24-25 are rejected under 35 U.S.C. 103 as being unpatentable over Oh (US20210202936A1) and Zhamu (US20200028205A1) as applied to claim 1 above, further in view of Ono (US20210104778A1), and further evidenced by Huggins (Robert A. Huggins, Lithium alloy negative electrodes, Journal of Power Sources, 1999, Pages 13-19.) and Li (Li et. al., Recent advances in the interfacial stability, design and in situ characterization of garnet-type Li7La3Zr2O12 solid-state electrolytes based lithium metal batteries, Ceramics International, 2021, Pages 13280-13290).
Regarding claim 14, modified Oh teaches all limitations of claim 13 as described above, including a metal thin film (anode current collector 150 may be formed from stainless steel, nickel, or nickel-plated copper, [0022]) disposed between the second anode active material and the anode current collector (Fig. 1A-1C). Oh further teaches the anode current collector can be any thin (<30 microns) electronically conductive material that has a stable interface in contact with tin ([0022]). Thus, although Oh explicitly discloses stainless steel, nickel, or nickel-plated copper, Oh broadly teaches the desirability of any electronically conductive material providing a stable interface in contact with tin.
Oh does not expressly teach the all-solid-state secondary battery wherein the metal thin film comprises one or more of indium, silicon, gallium, tin, aluminum, titanium, zirconium, niobium, germanium, antimony, bismuth, gold, platinum, palladium, magnesium, palladium, silver, or zinc, as claimed.
Ono discloses a negative electrode collector comprising a plurality of layers ([0059]-[0060]), wherein the layer(s) are made up of a metallic material such as Cu, Ni, Fe, Ti, Co, Zn and alloys, for example, such as stainless steel, which have good conductivity ([0059]).
Both Oh and Ono utilize the thin metal film for the same function of providing a highly conductive, stable interface layer for battery electrodes. Since Oh broadly teaches the use of any electronically conductive material for this stable interface, a person of ordinary skill in the art looking to optimize the electrical properties of the battery would have been motivated to look to other known, highly conductive metals such as those disclosed in Ono. Furthermore, because both references collectively teach that metals such as Cu, Ni, Ti, Zn, and alloys such as stainless steel provide stable and highly conductive interfaces for battery electrodes, a person of ordinary skill in the art would have recognized these materials as functionally interchangeable in this context.
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to utilize the metallic materials taught by Ono for the metal thin film of Oh. Utilizing the metal thin film of Oh with the art-recognized equivalent metals taught by Ono would yield predictable results, such as suitable maintenance of conductivity and interfacial stability.
Regarding claim 17, modified Oh teaches all limitations of claim 1 as described above, and further teaches the all-solid-state secondary battery wherein the first anode active material layer comprises tin and/or tin oxide or other disclosed tin composite. Oh further teaches the solid electrolyte may be an oxide-containing solid electrolyte, a sulfide-containing solid electrolyte, or a combination thereof in addition to other examples ([0024], lines 12-16).
However, Oh is silent to the identity of the solid electrolyte composition. Further, Oh is silent to the reduction potential values of both the first anode active material layer and the solid electrolyte. Therefore, Oh does not expressly teach that the first anode active material layer has a greater reduction potential of lithium ions than an ion reduction potential of the solid electrolyte, as claimed.
Regarding the reduction potential for the lithium-tin (Li-Sn) of the first anode active material of modified Oh, Huggins evidences that (Li-Sn) intermetallic alloys exhibit plateau potentials between approximately 0.38 V and 0.66 V vs. Li/Li⁺ (Huggins, pg. 15, right column, Table 1, LiySn values); in this context, the plateau potential is considered equivalent to the reduction potential of the claim.
Regarding the solid electrolyte and the solid electrolyte reduction potential, Ono teaches a solid electrolyte for an all-solid-state battery including sulfide solid electrolyte materials and oxide solid electrolyte materials (Ono, [0047]). Specifically, Ono discloses that the oxide-containing solid electrolyte may include a lithium-lanthanum-zirconium-containing composite oxide (LLZO) (Ono, [0047]), which has a reduction potential of 0.05 V as evidenced by Li et. al. (Li, pg. 13281, col. 2, lines 13-15). Ono further discloses that an all-solid-state battery with this configuration has superior current collection properties (Ono, [0013]).
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to further modify the battery of Oh to utilize the solid electrolyte materials of Ono in order to achieve a battery with improved current collection properties.
As a result, modified Oh discloses a first anode active material layer (first anode active material layer comprises tin; 0.38 V and 0.66 V vs. Li/Li⁺) has a greater reduction potential of lithium ions than an ion reduction potential of the solid electrolyte (LLZO; 0.05 V), with the modification of Ono.
Regarding claim 24, modified Oh teaches all limitations of claim 23 and claim 1 as described above, including an oxide-containing solid electrolyte. However, Oh is silent to the identity of the oxide-containing solid electrolyte composition.
Ono teaches a solid electrolyte for an all-solid-state battery including sulfide solid electrolyte materials and oxide solid electrolyte materials ([0047]). In particular, Ono discloses that the oxide-containing solid electrolyte includes lithium-lanthanum-zirconium-containing composite oxides (LLZO) which reads on the Li3+xLa3M2O12 (where M is Te, Nb, or Zr and x is an integer from 1 to 10) limitation of the claim, and lithium-lanthanum-titanium-containing composite oxides (LLTO) which reads on the LixLayTiO3 (wherein 0<x<2 and 0<y<3) limitation of the claim ([0047]). Ono further discloses that an all-solid-state battery with this configuration has superior current collection properties ([0013]).
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to further modify the battery of Oh to utilize the oxide-containing solid electrolyte materials of Ono in order to achieve a battery with improved current collection properties.
Regarding claim 25, modified Oh teaches all limitations of claim 24 and claim 1 as described above, including a sulfide-containing solid electrolyte. However, Oh is silent to the identity of the sulfide-containing solid electrolyte composition.
Ono teaches a solid electrolyte for an all-solid-state battery including sulfide solid electrolyte materials ([0047]). Ono further discloses that the sulfide-containing solid electrolyte includes one or more of Li2S-P2S5, Li2S-SiS2, Li2S-B2S3, Li2S-GeS2, Li2S-SiS2-LiI, Li3PO4-P2S5 -based materials, and the like ([0047]). Ono further discloses that an all-solid-state battery with this configuration has superior current collection properties ([0013]).
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to further modify the battery of Oh to utilize the sulfide-containing solid electrolyte materials of Ono in order to achieve a battery with improved current collection properties.
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to ALEXIS R OSTWALT whose telephone number is (571)272-8650. The examiner can normally be reached Mon-Fri 7:30am-5pm.
Examiner interviews are available via telephone, in-person, and video conferencing using a USPTO supplied web-based collaboration tool. To schedule an interview, applicant is encouraged to use the USPTO Automated Interview Request (AIR) at http://www.uspto.gov/interviewpractice.
If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Marla McConnell can be reached at 5712707692. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
Information regarding the status of published or unpublished applications may be obtained from Patent Center. Unpublished application information in Patent Center is available to registered users. To file and manage patent submissions in Patent Center, visit: https://patentcenter.uspto.gov. Visit https://www.uspto.gov/patents/apply/patent-center for more information about Patent Center and https://www.uspto.gov/patents/docx for information about filing in DOCX format. For additional questions, contact the Electronic Business Center (EBC) at 866-217-9197 (toll-free). If you would like assistance from a USPTO Customer Service Representative, call 800-786-9199 (IN USA OR CANADA) or 571-272-1000.
/A.R.O./Examiner, Art Unit 1789
/MARLA D MCCONNELL/Supervisory Patent Examiner, Art Unit 1789
Prosecution Insights