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 .
Status of the Claims
Claims 1-7, 9-15, and 22-24 are pending and rejected. Claims 16, 21, and 25 are withdrawn. Claims 8 and 17-20 are cancelled. Claims 1, 3, 4, 7, 11, and 14 are amended.
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.
Claims 2, 3, 10, and 11 are rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
Regarding claim 2, the claim states that the oxide is deposited and gives options for the oxide, however, claim 1 has been amended to require that depositing the oxide comprises niobium oxide. Therefore, it is unclear whether claim 2 is intended to require depositing oxides in addition to niobium oxide or that the metalloid nitride is deposited and the listed oxides are also deposited. For the purposes of examination, either interpretation is considered to meet the claimed requirements. Appropriate action is required without adding new matter.
Regarding claim 3, the claim lists materials from which the oxide is selected, however, claim 1 has been amended to require that depositing the oxide comprises niobium oxide. Therefore, it is unclear whether claim 3 is intended to require depositing the listed oxides in addition to niobium oxide or that the metalloid nitride is deposited and the listed oxides are also deposited. For the purposes of examination, either interpretation is considered to meet the claimed requirements. Appropriate action is required without adding new matter.
Regarding claim 10, the claim states that aluminum oxide is deposited, however, claim 1 has been amended to require that depositing the oxide comprises niobium oxide. Therefore, it is unclear whether claim 10 is intended to require depositing aluminum oxide in addition to niobium oxide or that the metalloid nitride is deposited in combination with aluminum oxide. For the purposes of examination, either interpretation is considered to meet the claimed requirements. Since claim 11 does not remedy the clarity of claim 10, it is also rendered indefinite. Appropriate action is required without adding new matter.
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.
This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention(s) absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and effective filing dates of each claim that was not commonly owned as of the effective filing date of the later invention in order for the examiner to consider the applicability of 35 U.S.C. 102(b)(2)(C) for any potential 35 U.S.C. 102(a)(2) prior art against the later invention.
Claims 1-3, 5-7, 9-13, 15, 23, and 24 are rejected under 35 U.S.C. 103 as being unpatentable over Watanabe, US 2017/0207455 A1 in view of Park, US 2017/0018767 A1, Xiao, US 2015/0180023 A1, and Chen, US 2019/0379056 A1.
Regarding claims 1, 5-7, and 9, Watanabe teaches lithium nickelate-based positive electrode active substance particles having a high energy density which are excellent in charge/discharge cycle characteristics when highly charged, and hardly suffer from generation of gases upon storage under high-temperature conditions, and a process for producing the positive electrode active substance particles, as well as a non-aqueous electrolyte secondary battery (abstract). They teach that the core particle comprises a lithium nickelate composite oxide having a layer structure which is represented by Li1+aNi1-b-cCobMcO2, wherein M is at least one element selected from the group of Mn, Al, B, Mg, Ti, Sn, Zn, and Zr; a is a number of -0.1 to 0.2; b is a number of 0.05 to 0.5; and c is a number of 0.01 to 0.4 (abstract). They teach the active material includes a coating compound Y comprising at least one element selected from the group consisting of Al, Mg, Zr, Ti, and Si; and a coating compound Z comprising an Li element (abstract). They teach that a content of LiOH in the positive electrode active substance particles is not more than 0.40% by weight, a content of lithium carbonate in the positive electrode active substance particles is not more than 0.65% by weight, and a weight ratio of the content of lithium carbonate to the content of lithium hydroxide is not less than 1 (abstract). They teach that lithium nickelate composite oxide particles comprise a more than necessary amount of lithium carbonate or lithium hydroxide as an impurity phase (0006). They teach that the unreacted lithium compounds are main factors causing increase in a powder pH value, and tend to induce not only gelation of an electrode slurry upon production of the slurry, but also generation of gases from the batteries upon storage under high-temperature conditions when the resulting battery is subjected to charging and discharging cycles (0006). They teach forming the coating compound Y on a surface of the core particle X by a vapor phase epitaxy method and then subjecting the resulting particle to humidification treatment and heat treatment in atmospheric air to form the coating compound Z on the particle or vice versa (0025-0029). They teach that by forming the coating, direct contact between an electrolyte solution and the lithium nickelate-based positive electrode active substance particles can be inhibited, and occurrence of side reactions therebetween can be suppressed (0031). They teach that the lithium hydroxide or the lithium carbonate may be a part of the aforementioned coating compound Z comprising an Li element (0043). They teach that the coating compound Y comprises a compound such as Al in the form of an oxide (0044). They teach that the compound Y and the coating compound Z may be present in the form of either an island-shaped coating covering a part of the surface of the core or an overcoat covering a whole part of the surface of the core particle (0045). They teach exposing the lithium nickelate composite oxide particles to atmospheric air to transform LiOH included in the particles into LiOH.H2O and then to lithium carbonate to form the coating compound Z (0077). They teach forming the coating compound Y on the lithium nickelate composite oxide produced with coating compound Z by ALD using TMA and water (0078). They teach that the coating Y was constituted of Al2O3 and the coating compound Z was constituted of LiOH and Li2CO3 (0097 and Table 1). Therefore, Watanabe provides a method of controlling an amount of soluble base content (LiOH or Li2CO3) in a material by adding a coating to provide LiOH and Li2CO3 in the material at a desired weight percentage, where the material comprises LiOH, Li2CO-3, and a lithiated metal oxide, i.e., lithium nickelate composite oxide particles. They provide the material comprising a surface with the lithium carbonate and lithium hydroxide, i.e., coating compound Z, and deposit, using ALD, an oxide on the material. Therefore, they provide an oxide coating on the surface.
They do not teach depositing two or more of an oxide, a nitride, or a fluoride.
Park teaches a composite cathode active material for a lithium battery including a lithium composite oxide, and a coating layer including a metal oxide and a lithium fluoride, wherein the coating layer is disposed on at least a portion of a surface of the lithium composite oxide (abstract). They teach that during charging/discharging of the lithium battery, a side reaction between and electrolyte and a cathode active material may occur resulting in changing the structure of the cathode active material causing the capacity and cycling characteristics of the battery to deteriorate (0037). They teach that a coating layer including the metal oxide and lithium fluoride on a surface of the composite oxide minimizes direct contact between and electrolyte and the cathode active material suppressing the side reaction and change in the structure of the cathode active material so that high-rate characteristics and cycle characteristics are improved (0037). They teach that the metal oxide is at least one selected from Al2O3, B2O3, ZrO2, MgO, SiO2, SnO2, TiO2, etc. (0042). They teach that the lithium composite oxide is selected from materials including LiaNixCoyMnzMcO2-eAe, where 1.0<a≤1.4, 0<x<1, 0≤y<1, 0<z<1, 0≤c<1, 0<x+y+z+c<1, and 0≤e<1, M is at least one selected from Mg, Zn, Ti, Al, B, etc., and A is at least one anion element selected from F, S, Cl, and Br (0044-0045). Therefore, the lithium composite oxide includes a formula overlapping the range of those of Watanabe. They teach that the total thickness of the coating layer may be in the range of about 1 nm to about 1 micrometer (0073). They teach that the coating layer containing lithium fluoride and a coating layer containing aluminum oxide are stacked on a surface of an overlithiated layered oxide (0076).
Xiao teaches an electroactive material for use in an electrochemical cell, like a lithium-ion battery (abstract). They teach that the electroactive material comprises a multifunctional hybrid protective coating system formed over an electroactive material (abstract). They teach that the coating system includes a first oxide-based coating disposed on one or more surfaces of the electroactive material, followed by a second coating deposited by a non-aqueous process (abstract). They teach that the second coating may be a fluoride-based, nitride-based, or carbide-based coating (abstract). They teach that the first and second coatings may be applied by ALD to form conformal ultrathin layers over the electroactive materials (abstract). They teach that the multifunctional hybrid protective coating system can suppress formation of gases within the electrochemical cell and also minimize formation of solid electrolyte interface layers on the electrode to improve battery performance (abstract). They teach that the applied surface coatings are ultra-thin having a thickness of less than or equal to about 100 nm, less than or equal to about 50 nm, less than or equal to 10 nm, or less than or equal to about 5 nm (0044). They teach that the thickness of the oxide coating is less than or equal to about 15 nm, less than or equal to about 5 nm, less than or equal to about 0.5 nm (0046). They teach that the surface coating system is applied to any region of a surface of the electrode material that may be exposed to electrolyte or solvent within the electrochemical cell to minimize deposition, adsorption, or reaction of chemical species (0053). They teach that the oxide-based coating comprises TiO2, Al2O3, tin, ZrO2, and ZnO, in addition to oxides of tin (0054). They teach that the oxide coating provides mechanical protection form the volume change that can occur during lithium-ion battery cycling due to a higher elastic modulus and fracture strength where the second coating disposed over the oxide surface coating provides chemical protection from the chemical side reactions within the electrolyte or other components within the electrochemical cell (0056). They teach that the fluoride coating is an aluminum fluoride coating, a lithium fluoride coating, or a combination thereof (0059 and 0071). They teach that the nitride-based coating may be aluminum nitride, titanium nitride, silicon nitride, vanadium nitride, etc. (0079). Therefore, Xiao teaches forming ultra-thin protective layers on electroactive materials by ALD, where a first oxide coating provides mechanical protection and a second nitride or fluoride-based coating provides chemical protection.
From the teachings of Park and Xiao, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have modified the process of Watanabe to have formed compound Z and then to have deposited the first oxide coating Y and then a second ALD coating of a nitride and/or fluoride because Watanabe teaches forming the coating to inhibit direct contact between an electrolyte solution and the lithium nickelate-based positive electrode particles so as to suppress the occurrence of side reactions therebetween, Park teaches applying oxide and fluoride coatings to positive active materials having compositions similar to those of Watanabe for suppressing side reactions by minimizing contact, and Xiao teaches that ALD provides ultra-thin protective coatings on electroactive materials, where a first oxide coating provides mechanical protection and a second fluoride or nitride-based coating provides chemical protection such that that it will be expected to provide a protective coating layer for the positive electroactive materials of Watanabe so as to provide both mechanical and structural protection as well as chemical protection from potential side reactions. Specifically, Park indicates that the combination of an oxide and fluoride provide protection, where Xiao indicates that the fluoride or nitride-based coating can provide chemical protection such that a nitride or fluoride coating is also expected to provide chemical protection to the particles of Watanabe. Therefore, the particles will be provided with an ALD coating of an oxide layer and a nitride or fluoride layer.
They do not teach that the oxide is niobium oxide. Watanabe teaches depositing an Al2O3 coatings (0097). They teach that the coating compound Y is selected from an oxide of Al, Mg, Zr, Ti, and Si (0016), suggesting that coatings include MgO, SiO2, TiO2, ZrO2 in addition to Al2O3 so as to provide oxides of the listed metals.
Park also teaches that the metal oxide is at least one selected from Al2O3, B2O3, ZrO2, MgO, SiO2, SnO2, TiO2, etc. (0042).
Xiao teaches that the oxide-based coating comprises TiO2, Al2O3, tin, ZrO2, and ZnO, in addition to oxides of tin (0054).
Chen teaches methods for providing a protective coating to components of lithium batteries (abstract). They teach that the cathode comprises a metal layer and a surface that is a lithium-based material (0018). They teach that the cathode also comprises an inert material on the surface of the metal layer deposited by ALD (0018). They teach that the inert material comprises a metal, a metal oxide, a metal halide, a metal oxyfluoride, a metal nitride, metal carbonate, a metal sulfide a metal sulfate, a non-metal oxide, a non-metal carbide, a non-metal, or a mixture of any two or more thereof (0066). They teach that the inert material is selected from the group consisting of Al2O3, TiO2, ZnO, NbO2, ZrO2, MgO, SiO2, AlF3, TiN, etc., or mixtures of any two or more thereof (0066). They teach that the cathodes comprise a metal layer with any cathode material (0067). They teach that the metal layer comprises a cathode material such as a lithium-based cathode material, where the cathode material includes compounds similar to Watanabe (0067-0068). They teach that the inert material has a thickness of 0.1 nm to 10 microns (0071). They teach that the cathode material can comprise two or more layers of the inert material (0072). They teach that the terms “protective” and “inert” mean the same (0038). Therefore, Chen teaches depositing an inert or protective coating on cathode materials, such as those taught by Watanabe, by ALD, where the material of the coating is selected from the group consisting of Al2O3, TiO2, ZnO, NbO2, ZrO2, MgO, SiO2, etc., or mixtures of any two or more thereof and can include nitrides and fluorides.
From the teachings of Chen, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have selected niobium oxide as an oxide of the protective oxide coating because Chen teaches that such a material is a desirable protective coating for cathode materials, including those similar to Watanabe, as an alternative to the oxides taught by Watanabe, Park, and Xiao, where it can be deposited by ALD, such that it will be expected to be a simple substitution of one known protective material for another while still providing the desired result of protecting the cathode material.
As to the number of cycles, Watanabe teaches repeating the ALD steps 1 to 100 times, preferably 2 to 50 times, and more preferably 2 to 10 times (0059), where they provide an example of using 2, 3.5, 4, and 7 (0078, 0099, 0107, 0108, 0110). They teach that a surface coating having a thickness of 17 nm is excessive to merely suppress the occurrence of side reactions at an interface between a positive electrode active substance and an electrolyte solution (0015). They teach that the coating Y is provided to have a very thin film having a thickness of several nm (0061).
As noted above, Park teaches a thickness in the range of 1 nm to 1 micron, about 5 nm to about 500 nm, or about 10 nm to about 100 nm (0073). Xiao teaches a total thickness of less than or equal to 100 nm and down to a total thickness of less than or equal to about 5 nm, where the oxide thickness can be less than or equal to about 15 nm and down to less than or equal to about 0.5 nm (0044 and 0046). Xiao teaches that the ALD process is repeated to grow a film layer by layer on the surface (0067), indicating that as the cycles are repeated, the thickness is increased. Chen teaches that the inert material can have a thickness of 0.1 nm to 10 microns (0071), where the thickness can also be in the range of at least 0.24 nm and at most 500 nm (0040).
From this, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have optimized the number of ALD cycles to be the ranges of claims 1 and 5-6 when using ALD to deposit the oxide and fluoride or nitride-based coatings because Watanabe teaches that the film thickness should be several nm, where it is desirably very thin, and 17 nm is indicated as being excessively thick, and they teach using 2 to 10 ALD cycles, Park teaches that a suitable film thickness can be 1 nm to 1 micron, Xiao also indicates that the films can be very thin, i.e., less than or equal to 5 nm, where the thickness increases as the number of cycles increases, and Chen teaches using a thickness of 0.01 nm to 10 microns, such that by optimizing the number of cycles in the process to have a thin film as desired by Watanabe or a thickness in the range of less than 5 nm as suggested by Xiao, it will be expected to provide a coating having desirable protection while minimizing changes in electrochemical properties. According to MPEP 2144.05 II A, “[W]here the general conditions of a claim are disclosed in the prior art, it is not inventive to discover the optimum or workable ranges by routine experimentation.” In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955).
As to providing the material within a reaction chamber, Xiao teaches that ALD is typically conducted in an apparatus having a vacuum deposition chamber with a holder for the substrate (0062). They teach that the ALD process for deposition of a surface coating onto regions of the electrode material involves reaction of the surface in a deposition chamber with vapor of precursor materials (0062). Therefore, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have provided the material within a reaction chamber because Xiao teaches that ALD is performed in a reaction chamber such that it will be expected to provide the precursor vapor and deposition as desired.
Further, they do not teach that the coating is selectively deposited on LiOH (the other material as required by claim 9) compared to lithium carbonate, however, since they suggest the claimed method, including using the claimed materials, i.e., depositing niobium oxide, the film is also expected to selectively deposit on LiOH compared to lithium carbonate. According to MPEP 2112.01 I, “Where the claimed and prior art products are identical or substantially identical in structure or composition, or are produced by identical or substantially identical processes, a prima facie case of either anticipation or obviousness has been established. In re Best, 562 F.2d 1252, 1255, 195 USPQ 430, 433 (CCPA 1977)”.
Alternatively, as discussed above, Watanabe teaches depositing an oxide comprising at least one of Al, Mg, Zr, Ti, and Si (0055). Park teaches that the metal oxide is at least one selected from Al2O3, B2O3, ZrO2, MgO, SiO2, SnO2, TiO2, etc. (0042). Chen teaches that the inert material is selected from the group consisting of Al2O3, TiO2, ZnO, NbO2, ZrO2, MgO, SiO2, AlF3, TiN, etc., or mixtures of any two or more thereof (0066). From this, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have selected a mixture of oxides such as niobium oxide and alumina because Watanabe, Park, and Chen teach that more than one oxide can be included, where such materials are indicated as being desirable.
Watanabe teaches depositing the oxide layer using trimethyl aluminum and water (0078 and 0099).
Xiao teaches using LiOtBu and TiF4 as precursors for forming a LiF coating by ALD (0087). They teach using TiF4 and TMA (Al(CH3)3) for forming an AlF3 coating by ALD (0088). They teach that suitable precursors for the nitride coating include ammonia and TMA (0071). From this, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have formed the fluoride coating using lithium tert-butoxide, TiF4, and TMA as precursors and the nitride coating using TMA and ammonia because Xiao teaches that such precursors are suitable for forming nitride and fluoride coatings.
The instant specification at page 8, lines 15-21 indicates using TMA and water as a precursor, lithium tert-butoxide and TiF4 as precursors, and where ammonia is also a suitable precursor. Therefore, the material is also expected to deposit on the LiOH (the other material as required by claim 9) selectively compared to lithium carbonate because they teach using the same precursors (LiOtBu and TiF4, TMA and water, ammonia and TMA), as well as depositing niobium oxide, such that the reaction between the precursors and the LiOH and lithium carbonate are expected to show the same selective deposition. According to MPEP 2112.01 I, “Where the claimed and prior art products are identical or substantially identical in structure or composition, or are produced by identical or substantially identical processes, a prima facie case of either anticipation or obviousness has been established. In re Best, 562 F.2d 1252, 1255, 195 USPQ 430, 433 (CCPA 1977)”.
As to determining an amount of the lithium carbonate in the material and basing the number of ALD cycles performed on the amount of lithium carbonate in the material, Watanabe teaches analyzing the surface composition of samples using XPS (0087). They teach that the XPS data indicates that the outermost surface is enriched in compound Y and the surface below that is enriched in compound Z for the sample that was humidified prior to ALD (0097). They teach controlling the amount of lithium carbonate and lithium hydroxide to be within a desired weight percentage of the particles (abstract). They provide data of the weight percentage of lithium carbonate in the samples present as the covering compound, understood to be part of the surface composition (Table 1). Therefore, since they teach determining the surface composition using XPS, where the data provides concentration of lithium carbonate at the surface as indicated in Table 1 and Fig. 6, they provide a step of determining the amount of lithium carbonate by XPS.
Park also teaches performing XPS characterizations to analyze chemical compositions the composite active materials (0194-0197).
From this, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have determined the amount of lithium carbonate by XPS and to have determined the number of cycles based on the amount of lithium carbonate because Watanabe indicates that the surface composition is analyzed by XPS, where the data provides concentration of the elements and Watanabe teaches controlling the amount of lithium carbonate to be within a desired range such that by increasing or decreasing the amount of the ALD coating it will be expected to control the amount of lithium carbonate to be within a desired weight percentage range for the particles, i.e., by increasing the weight of the ALD coating, it will decrease the weight of the lithium carbonate in the particle.
Regarding claims 2 and 3, Watanabe in view of Park, Xiao, and Chen suggest the process of claim 1. As discussed above, it is suggested to deposit niobium oxide, understood to be NbO2 or NbO3.
Alternatively, as discussed above for claim 1, Watanabe in view of Park, Xiao, and Chen also suggest using a combination of oxides, providing the suggestion to use alumina, where since titania, silica, MgO, zirconia, ZnO, B2O3, and SnO2 are also suggested as suitable oxides, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have used these oxides in combination with niobium oxide because they are indicated as being suitable protective materials.
Regarding claims 10 and 11, Watanabe in view of Park, Xiao, and Chen suggest the process of claim 1, where Watanabe teaches that the oxide is aluminum oxide (0097). As noted above, for claims 1, 2, and 3, it is suggested that alumina can be used in combination with niobium. Further, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have selected depositing aluminum oxide first because Watanabe exemplifies it as a coating material and because it will be expected to provide the oxide coating as desired.
Watanabe teaches that the coating compound Z includes LiOH and Li2CO3 (0097). Therefore, when performing the step of forming the coating Z and then applying the aluminum oxide/niobium oxide coating Y, the surface of the material will comprise LiOH and Li2CO3 at a first ratio prior to ALD. Since they teach performing ALD to provide the alumina coating, where it is suggested to provide an alumina/niobium oxide coating, where they teach using TMA and water, i.e., the same precursors taught in the specification (note the discussion above in claim 1 regarding selectivity), the resulting process is also expected to change the ratio of LiOH and lithium carbonate to a second ratio, where the first ratio is larger than the second ratio. Further, the resulting surface is also expected to comprise lithium carbonate and Li-Al-oxide because they suggest providing the claimed process using the claimed precursors. According to MPEP 2112.01 I, “Where the claimed and prior art products are identical or substantially identical in structure or composition, or are produced by identical or substantially identical processes, a prima facie case of either anticipation or obviousness has been established. In re Best, 562 F.2d 1252, 1255, 195 USPQ 430, 433 (CCPA 1977)”.
Regarding claims 12 and 13, Watanabe in view of Park, Xiao, and Chen suggest the process of claim 1. Watanabe further teaches that the material is represented by Li1+aNi1-b-cCobMcO2, wherein M is at least one element selected from the group of Mn, Al, B, Mg, Ti, Sn, Zn, and Zr; a is a number of -0.1 to 0.2; b is a number of 0.05 to 0.5; and c is a number of 0.01 to 0.4 (abstract), such that it includes a range that covers a nickel-rich lithium manganese cobalt oxide such as NCM 811, NCM 523, and NCM 111 and a range in which the nickel content is greater than 20.2 wt. % (note the instant specification at pg. 3, lines 30-32). According to MPEP 2144.05, “in the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists.” In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976).
Regarding claim 23, Watanabe in view of Park, Xiao, and Chen suggest the process of claim 1. Watanabe teaches that the material comprises an NMC cathode material (abstract) and note the discussion above for claims 12 and 13. Park also teaches using lithium nickel cobalt manganese oxide as a cathode active material (0044-0045).
Watanabe teaches using a lithium nickelate composite oxide particle formed from Li1.02Ni0.81Co0.15Al0.04O2 (0076), converting LiOH to Li2CO3 for forming compound Z, and then exposing it to 4 cycles to form an alumina coating (0078 and 0097) for example 1 (0076). For example 2, they teach depositing alumina using 4 cycles and then converting the LiOH to lithium carbonate (0099). They teach that in comparative example 1, the Li1.02Ni0.81Co0.15Al0.04O2 compound is used without any surface treatment (0101). They teach that comparative example 3 is done as in example 1, however, no ALD coating is applied (0104). The carbonate concentration for comparative example 1 (without any surface treatment) is 0.42 wt. %, for comparative example 3 (with humidification and no ALD) is 0.61 wt. %, and the sample of example 1 (with humidification and ALD) the carbonate is 0.55 wt. % (Table 1). Therefore, the carbonate percentage decreases by less than 50% after ALD compared to both the sample having surface treatment with no ALD and the sample having no surface treatment. From this, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention that the process of Watanabe in view of Park, Xiao, and Chen will result in decreasing the carbonate concentration by less than 50% because Watanabe teaches that when coating by ALD the change in carbonate concentration is within such a range. Further, since Watanabe in view of Park, Xiao, and Chen provide the process of claim 1, the resulting carbonate change is also expected to be within the claimed range. According to MPEP 2112.01 I, “Where the claimed and prior art products are identical or substantially identical in structure or composition, or are produced by identical or substantially identical processes, a prima facie case of either anticipation or obviousness has been established. In re Best, 562 F.2d 1252, 1255, 195 USPQ 430, 433 (CCPA 1977)”.
Regarding claims 15 and 24, Watanabe in view of Park, Xiao, and Chen suggest the process of claims 1 and 23. Watanabe further teaches providing a non-aqueous electrolyte secondary battery with a high-energy density produced by using the positive electrode active substance particles (0016 and 0067). They teach producing a positive electrode sheet using the positive electrode active substance particles according to the invention, where a conducting agent, a binder, and the positive electrode active particles are mixed (0068). They teach forming the mixture into a positive electrode slurry and applying it onto a current collector followed by drying and calendaring to produce a positive electrode sheet (0068). They teach assembling the positive electrode sheet, negative electrode, and a separator into a battery (0090-0092).
Park teaches forming a battery including a cathode having the composite cathode active material (0099). They teach forming the cathode by mixing cathode active material, a binder, and a solvent (0101-0105). They teach that the cathode active material may be the composite cathode active material (0105). They teach that a conducting agent may be further added to the cathode active material composition (0103). They teach that the cathode active material composition may be directly coated on a current collector and then dried to prepare a cathode (0104). They teach that a separator is disposed between the cathode and an anode (0124). Therefore, they teach forming cathode material and a battery comprising the cathode material.
Therefore, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have formed a cathode using the material of Watanabe in view of Park and Xiao using typical slurry-making methods as described by Watanabe and then to have form a battery using the material because it will result in forming a battery with a desirable cathode material.
Claims 1-7, 9-13, 15, 23, and 24 are rejected under 35 U.S.C. 103 as being unpatentable over Watanabe, US 2017/0207455 A1 in view of Park, US 2017/0018767 A1, Xiao, US 2015/0180023 A1, and Kim, US 2019/0198865 A1 and alternatively further in view of Tang, US 2014/0043216 A1.
Regarding claims 1, 5-7, and 9, Watanabe teaches lithium nickelate-based positive electrode active substance particles having a high energy density which are excellent in charge/discharge cycle characteristics when highly charged, and hardly suffer from generation of gases upon storage under high-temperature conditions, and a process for producing the positive electrode active substance particles, as well as a non-aqueous electrolyte secondary battery (abstract). They teach that the core particle comprises a lithium nickelate composite oxide having a layer structure which is represented by Li1+aNi1-b-cCobMcO2, wherein M is at least one element selected from the group of Mn, Al, B, Mg, Ti, Sn, Zn, and Zr; a is a number of -0.1 to 0.2; b is a number of 0.05 to 0.5; and c is a number of 0.01 to 0.4 (abstract). They teach the active material includes a coating compound Y comprising at least one element selected from the group consisting of Al, Mg, Zr, Ti, and Si; and a coating compound Z comprising an Li element (abstract). They teach that a content of LiOH in the positive electrode active substance particles is not more than 0.40% by weight, a content of lithium carbonate in the positive electrode active substance particles is not more than 0.65% by weight, and a weight ratio of the content of lithium carbonate to the content of lithium hydroxide is not less than 1 (abstract). They teach that lithium nickelate composite oxide particles comprise a more than necessary amount of lithium carbonate or lithium hydroxide as an impurity phase (0006). They teach that the unreacted lithium compounds are main factors causing increase in a powder pH value, and tend to induce not only gelation of an electrode slurry upon production of the slurry, but also generation of gases from the batteries upon storage under high-temperature conditions when the resulting battery is subjected to charging and discharging cycles (0006). They teach forming the coating compound Y on a surface of the core particle X by a vapor phase epitaxy method and then subjecting the resulting particle to humidification treatment and heat treatment in atmospheric air to form the coating compound Z on the particle or vice versa (0025-0029). They teach that by forming the coating, direct contact between an electrolyte solution and the lithium nickelate-based positive electrode active substance particles can be inhibited, and occurrence of side reactions therebetween can be suppressed (0031). They teach that the lithium hydroxide or the lithium carbonate may be a part of the aforementioned coating compound Z comprising an Li element (0043). They teach that the coating compound Y comprises a compound such as Al in the form of an oxide (0044). They teach that the compound Y and the coating compound Z may be present in the form of either an island-shaped coating covering a part of the surface of the core or an overcoat covering a whole part of the surface of the core particle (0045). They teach exposing the lithium nickelate composite oxide particles to atmospheric air to transform LiOH included in the particles into LiOH.H2O and then to lithium carbonate to form the coating compound Z (0077). They teach forming the coating compound Y on the lithium nickelate composite oxide produced with coating compound Z by ALD using TMA and water (0078). They teach that the coating Y was constituted of Al2O3 and the coating compound Z was constituted of LiOH and Li2CO3 (0097 and Table 1). Therefore, Watanabe provides a method of controlling an amount of soluble base content (LiOH or Li2CO3) in a material by adding a coating to provide LiOH and Li2CO3 in the material at a desired weight percentage, where the material comprises LiOH, Li2CO-3, and a lithiated metal oxide, i.e., lithium nickelate composite oxide particles. They provide the material comprising a surface with the lithium carbonate and lithium hydroxide, i.e., coating compound Z, and deposit, using ALD, an oxide on the material. Therefore, they provide an oxide coating on the surface.
They do not teach depositing two or more of an oxide, a nitride, or a fluoride.
Park teaches a composite cathode active material for a lithium battery including a lithium composite oxide, and a coating layer including a metal oxide and a lithium fluoride, wherein the coating layer is disposed on at least a portion of a surface of the lithium composite oxide (abstract). They teach that during charging/discharging of the lithium battery, a side reaction between an electrolyte and a cathode active material may occur resulting in changing the structure of the cathode active material causing the capacity and cycling characteristics of the battery to deteriorate (0037). They teach that a coating layer including the metal oxide and lithium fluoride on a surface of the composite oxide minimizes direct contact between and electrolyte and the cathode active material suppressing the side reaction and change in the structure of the cathode active material so that high-rate characteristics and cycle characteristics are improved (0037). They teach that the metal oxide is at least one selected from Al2O3, B2O3, ZrO2, MgO, SiO2, SnO2, TiO2, etc. (0042). They teach that the lithium composite oxide is selected from materials including LiaNixCoyMnzMcO2-eAe, where 1.0<a≤1.4, 0<x<1, 0≤y<1, 0<z<1, 0≤c<1, 0<x+y+z+c<1, and 0≤e<1, M is at least one selected from Mg, Zn, Ti, Al, B, etc., and A is at least one anion element selected from F, S, Cl, and Br (0044-0045). Therefore, the lithium composite oxide includes a formula overlapping the range of those of Watanabe. They teach that the total thickness of the coating layer may be in the range of about 1 nm to about 1 micrometer (0073). They teach that the coating layer containing lithium fluoride and a coating layer containing aluminum oxide are stacked on a surface of an overlithiated layered oxide (0076).
Xiao teaches an electroactive material for use in an electrochemical cell, like a lithium-ion battery (abstract). They teach that the electroactive material comprises a multifunctional hybrid protective coating system formed over an electroactive material (abstract). They teach that the coating system includes a first oxide-based coating disposed on one or more surfaces of the electroactive material, followed by a second coating deposited by a non-aqueous process (abstract). They teach that the second coating may be a fluoride-based, nitride-based, or carbide-based coating (abstract). They teach that the first and second coatings may be applied by ALD to form conformal ultrathin layers over the electroactive materials (abstract). They teach that the multifunctional hybrid protective coating system can suppress formation of gases within the electrochemical cell and also minimize formation of solid electrolyte interface layers on the electrode to improve battery performance (abstract). They teach that the applied surface coatings are ultra-thin having a thickness of less than or equal to about 100 nm, less than or equal to about 50 nm, less than or equal to 10 nm, or less than or equal to about 5 nm (0044). They teach that the thickness of the oxide coating is less than or equal to about 15 nm, less than or equal to about 5 nm, less than or equal to about 0.5 nm (0046). They teach that the surface coating system is applied to any region of a surface of the electrode material that may be exposed to electrolyte or solvent within the electrochemical cell to minimize deposition, adsorption, or reaction of chemical species (0053). They teach that the oxide-based coating comprises TiO2, Al2O3, tin, ZrO2, and ZnO, in addition to oxides of tin (0054). They teach that the oxide coating provides mechanical protection form the volume change that can occur during lithium-ion battery cycling due to a higher elastic modulus and fracture strength where the second coating disposed over the oxide surface coating provides chemical protection from the chemical side reactions within the electrolyte or other components within the electrochemical cell (0056). They teach that the fluoride coating is an aluminum fluoride coating, a lithium fluoride coating, or a combination thereof (0059 and 0071). They teach that the nitride-based coating may be aluminum nitride, titanium nitride, silicon nitride, vanadium nitride, etc. (0079). Therefore, Xiao teaches forming ultra-thin protective layers on electroactive materials by ALD, where a first oxide coating provides mechanical protection and a second nitride or fluoride-based coating provides chemical protection.
From the teachings of Park and Xiao, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have modified the process of Watanabe to have formed compound Z and then to have deposited the first oxide coating Y and then a second ALD coating of a nitride and/or fluoride because Watanabe teaches forming the coating to inhibit direct contact between an electrolyte solution and the lithium nickelate-based positive electrode particles so as to suppress the occurrence of side reactions therebetween, Park teaches applying oxide and fluoride coatings to positive active materials having compositions similar to those of Watanabe for suppressing side reactions by minimizing contact, and Xiao teaches that ALD provides ultra-thin protective coatings on electroactive materials, where a first oxide coating provides mechanical protection and a second fluoride or nitride-based coating provides chemical protection such that that it will be expected to provide a protective coating layer for the positive electroactive materials of Watanabe so as to provide both mechanical and structural protection as well as chemical protection from potential side reactions. Specifically, Park indicates that the combination of an oxide and fluoride provide protection, where Xiao indicates that the fluoride or nitride-based coating can provide chemical protection such that a nitride or fluoride coating is also expected to provide chemical protection to the particles of Watanabe. Therefore, the particles will be provided with an ALD coating of an oxide layer and a nitride or fluoride layer.
They do not teach that the nitride is a metalloid nitride. Watanabe teaches depositing an Al2O3 coatings (0097). They teach that the coating compound Y is selected from an oxide of Al, Mg, Zr, Ti, and Si (0016), suggesting that coatings include MgO, SiO2, TiO2, ZrO2 in addition to Al2O3 so as to provide oxides of the listed metals.
Park also teaches that the metal oxide is at least one selected from Al2O3, B2O3, ZrO2, MgO, SiO2, SnO2, TiO2, etc. (0042).
Xiao teaches that the oxide-based coating comprises TiO2, Al2O3, tin, ZrO2, and ZnO, in addition to oxides of tin (0054). They teach that the nitride coating may be TiN, VN, or AlN (0071).
Kim teaches a method for repairing an anode of a lithium battery (abstract). They teach that the anode includes an inorganic protection layer (0030). They teach that the inorganic protection layer is substantially pin-hole-free so that an electrolyte solution cannot contact the second anode layer through the inorganic protection layer (0063). They teach that this prevent a side reaction between the second anode layer and the electrolyte solution (0063). They teach depositing the inorganic protection layer by ALD (0084). They teach that the material of the inorganic protection layer is selected from oxides such as alumina, silica, titania, SnO2, MgO, ZnO, ZrO2, nitrides such as VN, BN, AlN, and TiN, etc. (0066).
From the teachings of Kim, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have selected boron nitride as the nitride of the protective nitride coating because Kim teaches that such a material is a desirable protective coating for anode materials, as an alternative to the nitrides of Xiao and the oxides of Watanabe, Park, and Xiao, where it can be deposited by ALD, and where it is indicated as preventing a reaction between the anode material and the electrolyte such that it will also be expected to prevent reactions between the cathode material and the electrolyte such that it will be expected to be a simple substitution of one known protective nitride material for another while still providing the desired result of protecting the cathode material by preventing reactions with the electrolyte.
As to the number of cycles, Watanabe teaches repeating the ALD steps 1 to 100 times, preferably 2 to 50 times, and more preferably 2 to 10 times (0059), where they provide an example of using 2, 3.5, 4, and 7 (0078, 0099, 0107, 0108, 0110). They teach that a surface coating having a thickness of 17 nm is excessive to merely suppress the occurrence of side reactions at an interface between a positive electrode active substance and an electrolyte solution (0015). They teach that the coating Y is provided to have a very thin film having a thickness of several nm (0061).
As noted above, Park teaches a thickness in the range of 1 nm to 1 micron, about 5 nm to about 500 nm, or about 10 nm to about 100 nm (0073). Xiao teaches a total thickness of less than or equal to 100 nm and down to a total thickness of less than or equal to about 5 nm, where the oxide thickness can be less than or equal to about 15 nm and down to less than or equal to about 0.5 nm (0044 and 0046). Xiao teaches that the ALD process is repeated to grow a film layer by layer on the surface (0067), indicating that as the cycles are repeated, the thickness is increased. Kim teaches that the thickness of the inorganic protective layer is 20 nm or less, or about 10 nm or less, or in a range of about 5-10nm (0069).
From this, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have optimized the number of ALD cycles to be the ranges of claims 1 and 5-6 when using ALD to deposit the oxide and nitride-based coatings because Watanabe teaches that the film thickness should be several nm, where it is desirably very thin, and 17 nm is indicated as being excessively thick, and they teach using 2 to 10 ALD cycles, Park teaches that a suitable film thickness can be 1 nm to 1 micron, Xiao also indicates that the films can be very thin, i.e., less than or equal to 5 nm, where the thickness increases as the number of cycles increases, and Kim teaches using a thickness of 10 nm or less or 5-10 nm, such that by optimizing the number of cycles in the process to have a thin film as desired by Watanabe or a thickness in the range of less than 5 nm as suggested by Xiao, it will be expected to provide a coating having desirable protection while minimizing changes in electrochemical properties. According to MPEP 2144.05 II A, “[W]here the general conditions of a claim are disclosed in the prior art, it is not inventive to discover the optimum or workable ranges by routine experimentation.” In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955).
As to providing the material within a reaction chamber, Xiao teaches that ALD is typically conducted in an apparatus having a vacuum deposition chamber with a holder for the substrate (0062). They teach that the ALD process for deposition of a surface coating onto regions of the electrode material involves reaction of the surface in a deposition chamber with vapor of precursor materials (0062). Therefore, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have provided the material within a reaction chamber because Xiao teaches that ALD is performed in a reaction chamber such that it will be expected to provide the precursor vapor and deposition as desired.
Further, they do not teach that the coating is selectively deposited on LiOH (the other material as required by claim 9) compared to lithium carbonate, however, since they suggest the claimed method, including using the claimed materials, i.e., depositing oxides and nitrides, the film is also expected to selectively deposit on LiOH compared to lithium carbonate. According to MPEP 2112.01 I, “Where the claimed and prior art products are identical or substantially identical in structure or composition, or are produced by identical or substantially identical processes, a prima facie case of either anticipation or obviousness has been established. In re Best, 562 F.2d 1252, 1255, 195 USPQ 430, 433 (CCPA 1977)”.
Alternatively, Watanabe teaches depositing the oxide layer using trimethyl aluminum and water (0078 and 0099). The instant specification at page 8, lines 15-21 indicates using TMA and water as precursors and boron trichloride and ammonia as precursors.
They do not teach the precursors used for depositing boron nitride.
Tang teaches method for providing a boron nitride layer by ALD (abstract). They teach that examples of boron precursors include boron trichloride and an example nitridizing agent is ammonia (0052). They teach that these precursors allow for a low process temperature (0052).
From the teachings of Tang, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have selected boron trichloride and ammonia as the boron nitride precursor for ALD because Tang teaches that such precursors are suitable and they allow for a low process temperature. Therefore, the material is also expected to deposit on the LiOH (the other material as required by claim 9) selectively compared to lithium carbonate because Watanabe in view of Park, Xiao, Kim, and Tang teach using the same precursors for depositing the oxide layer and the boron nitride layer, such that the reaction between the precursors and the LiOH and lithium carbonate are expected to show the same selective deposition. According to MPEP 2112.01 I, “Where the claimed and prior art products are identical or substantially identical in structure or composition, or are produced by identical or substantially identical processes, a prima facie case of either anticipation or obviousness has been established. In re Best, 562 F.2d 1252, 1255, 195 USPQ 430, 433 (CCPA 1977)”.
As to determining an amount of the lithium carbonate in the material and basing the number of ALD cycles performed on the amount of lithium carbonate in the material, Watanabe teaches analyzing the surface composition of samples using XPS (0087). They teach that the XPS data indicates that the outermost surface is enriched in compound Y and the surface below that is enriched in compound Z for the sample that was humidified prior to ALD (0097). They teach controlling the amount of lithium carbonate and lithium hydroxide to be within a desired weight percentage of the particles (abstract). They provide data of the weight percentage of lithium carbonate in the samples present as the covering compound, understood to be part of the surface composition (Table 1). Therefore, since they teach determining the surface composition using XPS, where the data provides concentration of lithium carbonate at the surface as indicated in Table 1 and Fig. 6, they provide a step of determining the amount of lithium carbonate by XPS.
Park also teaches performing XPS characterizations to analyze chemical compositions the composite active materials (0194-0197).
From this, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have determined the amount of lithium carbonate by XPS and to have determined the number of cycles based on the amount of lithium carbonate because Watanabe indicates that the surface composition is analyzed by XPS, where the data provides concentration of the elements and Watanabe teaches controlling the amount of lithium carbonate to be within a desired range such that by increasing or decreasing the amount of the ALD coating it will be expected to control the amount of lithium carbonate to be within a desired weight percentage range for the particles, i.e., by increasing the weight of the ALD coating, it will decrease the weight of the lithium carbonate in the particle.
Regarding claims 2 and 3, Watanabe in view of Park, Xiao, and Kim and alternatively Tang suggest the process of claim 1. As discussed above, Watanabe teaches depositing an Al2O3 coatings (0097). They teach that the coating compound Y is selected from an oxide of Al, Mg, Zr, Ti, and Si (0016), suggesting that coatings include MgO, SiO2, TiO2, ZrO2 in addition to Al2O3 so as to provide oxides of the listed metals.
Park also teaches that the metal oxide is at least one selected from Al2O3, B2O3, ZrO2, MgO, SiO2, SnO2, TiO2, etc. (0042).
Xiao teaches that the oxide-based coating comprises TiO2, Al2O3, tin, ZrO2, and ZnO, in addition to oxides of tin (0054).
Therefore, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have selected Al2O3, B2O3, ZrO2, MgO, SiO2, SnO2, or TiO2 as the metal oxides because Watanabe and Xiao indicate that such oxides are desirable where the yare deposited by ALD such that it will be expected to provide desirable oxides for the protective layer.
Regarding claim 4, Watanabe in view of Park, Xiao, and Kim and alternatively Tang suggest the process of claim 1. As noted above it is suggested to deposit boron nitride as the nitride layer.
Regarding claims 10 and 11, Watanabe in view of Park, Xiao, and Kim and alternatively Tang suggest the process of claim 1, where Watanabe teaches that the oxide is aluminum oxide (0097). Watanabe teaches that the coating compound Z includes LiOH and Li2CO3 (0097). Therefore, when performing the step of forming the coating Z and then applying the aluminum oxide/niobium oxide coating Y, the surface of the material will comprise LiOH and Li2CO3 at a first ratio prior to ALD. Since they teach performing ALD to provide the alumina coating, where they teach using TMA and water, i.e., the same precursors taught in the specification (note the discussion above in claim 1 regarding selectivity), the resulting process is also expected to change the ratio of LiOH and lithium carbonate to a second ratio, where the first ratio is larger than the second ratio. Further, the resulting surface is also expected to comprise lithium carbonate and Li-Al-oxide because they suggest providing the claimed process using the claimed precursors. According to MPEP 2112.01 I, “Where the claimed and prior art products are identical or substantially identical in structure or composition, or are produced by identical or substantially identical processes, a prima facie case of either anticipation or obviousness has been established. In re Best, 562 F.2d 1252, 1255, 195 USPQ 430, 433 (CCPA 1977)”.
Regarding claims 12 and 13, Watanabe in view of Park, Xiao, and Kim and alternatively Tang suggest the process of claim 1. Watanabe further teaches that the material is represented by Li1+aNi1-b-cCobMcO2, wherein M is at least one element selected from the group of Mn, Al, B, Mg, Ti, Sn, Zn, and Zr; a is a number of -0.1 to 0.2; b is a number of 0.05 to 0.5; and c is a number of 0.01 to 0.4 (abstract), such that it includes a range that covers a nickel-rich lithium manganese cobalt oxide such as NCM 811, NCM 523, and NCM 111 and a range in which the nickel content is greater than 20.2 wt. % (note the instant specification at pg. 3, lines 30-32). According to MPEP 2144.05, “in the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists.” In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976).
Regarding claim 23, Watanabe in view of Park, Xiao, and Kim and alternatively Tang suggest the process of claim 1. Watanabe teaches that the material comprises an NMC cathode material (abstract) and note the discussion above for claims 12 and 13. Park also teaches using lithium nickel cobalt manganese oxide as a cathode active material (0044-0045).
Watanabe teaches using a lithium nickelate composite oxide particle formed from Li1.02Ni0.81Co0.15Al0.04O2 (0076), converting LiOH to Li2CO3 for forming compound Z, and then exposing it to 4 cycles to form an alumina coating (0078 and 0097) for example 1 (0076). For example 2, they teach depositing alumina using 4 cycles and then converting the LiOH to lithium carbonate (0099). They teach that in comparative example 1, the Li1.02Ni0.81Co0.15Al0.04O2 compound is used without any surface treatment (0101). They teach that comparative example 3 is done as in example 1, however, no ALD coating is applied (0104). The carbonate concentration for comparative example 1 (without any surface treatment) is 0.42 wt. %, for comparative example 3 (with humidification and no ALD) is 0.61 wt. %, and the sample of example 1 (with humidification and ALD) the carbonate is 0.55 wt. % (Table 1). Therefore, the carbonate percentage decreases by less than 50% after ALD compared to both the sample having surface treatment with no ALD and the sample having no surface treatment. From this, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention that the process of Watanabe in view of Park, Xiao, and Chen will result in decreasing the carbonate concentration by less than 50% because Watanabe teaches that when coating by ALD the change in carbonate concentration is within such a range. Further, since Watanabe in view of Park, Xiao, and Chen provide the process of claim 1, the resulting carbonate change is also expected to be within the claimed range. According to MPEP 2112.01 I, “Where the claimed and prior art products are identical or substantially identical in structure or composition, or are produced by identical or substantially identical processes, a prima facie case of either anticipation or obviousness has been established. In re Best, 562 F.2d 1252, 1255, 195 USPQ 430, 433 (CCPA 1977)”.
Regarding claims 15 and 24, Watanabe in view of Park, Xiao, and Kim and alternatively Tang suggest the process of claims 1 and 23. Watanabe further teaches providing a non-aqueous electrolyte secondary battery with a high-energy density produced by using the positive electrode active substance particles (0016 and 0067). They teach producing a positive electrode sheet using the positive electrode active substance particles according to the invention, where a conducting agent, a binder, and the positive electrode active particles are mixed (0068). They teach forming the mixture into a positive electrode slurry and applying it onto a current collector followed by drying and calendaring to produce a positive electrode sheet (0068). They teach assembling the positive electrode sheet, negative electrode, and a separator into a battery (0090-0092).
Park teaches forming a battery including a cathode having the composite cathode active material (0099). They teach forming the cathode by mixing cathode active material, a binder, and a solvent (0101-0105). They teach that the cathode active material may be the composite cathode active material (0105). They teach that a conducting agent may be further added to the cathode active material composition (0103). They teach that the cathode active material composition may be directly coated on a current collector and then dried to prepare a cathode (0104). They teach that a separator is disposed between the cathode and an anode (0124). Therefore, they teach forming cathode material and a battery comprising the cathode material.
Therefore, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have formed a cathode using the material of Watanabe in view of Park and Xiao using typical slurry-making methods as described by Watanabe and then to have form a battery using the material because it will result in forming a battery with a desirable cathode material.
Claim 14 is rejected under 35 U.S.C. 103 as being unpatentable over Watanabe in view of Park, Xiao, and Chen or Watanabe in view of Park, Xiao, and Kim and alternatively Tang as applied to claim 1 above, and further in view of Cui, WO 2018/222366 A2.
Regarding claim 14, Watanabe in view of Park, Xiao, and Chen or Watanabe in view of Park, Xiao, and Kim and alternatively Tang suggests the process of claim 1. Watanabe teaches that the coating can be in the form of an island-shaped coat covering a part of the surface of the core particle or an overcoat covering a whole part of the surface of the core particle (0045).
They do not teach determining the number of ALD cycles based on one of the listed features.
Cui teaches a coated cathode material that includes a cathode active material and an interfacial layer coating the cathode active material (abstract). They teach that the interfacial layer includes a lithium-containing fluoride which includes at least one additional metal different from lithium (abstract). They teach a method of forming the coated cathode material by providing the cathode active material and forming, via atomic layer deposition, an interfacial layer coating the cathode active material (0006). They teach that the cathode active material is a layered lithium transition metal oxide such as a lithium nickel manganese cobalt oxide represented as LiNixMnyCozO2, where x+y+z = 1 (e.g., LiNi0.8Mn0.1Co0.1O2) (0027). They teach that the interfacial layer includes a lithium-containing compound such as a lithium-containing fluoride (0028). Cui teaches that a thickness of the interfacial layer is in a range of about 1 nm to about 10 nm (0031). They teach that when using LiOtBu with TiF4, the growth rate is about 0.5 A/cycle at about 250°C for LiF and using AlF3 and TiF4 the growth rate of AlF3 is 1 A/cycle at 250°C (0051). Therefore, Cui teaches that a specific growth rate is provided with various precursors at a specific temperature.
From this, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have further determined the number of ALD cycles based on the precursors used during ALD and the temperature to provide the desired thickness because Watanabe teaches that the thickness can range from island-like to an overcoating, where Watanabe in view of Park, Xiao, and Chen or Watanabe in view of Park, Xiao, and Kim and alternatively Tang suggest optimizing the number of ALD cycles to provide a desirable thickness, and Cui indicates that specific precursors provide different growth rates at a specific temperature such that by providing a desired number of ALD cycles for the particular precursors used at the specific temperature used, it will be expected to provide the desired thickness.
Claim 22 is rejected under 35 U.S.C. 103 as being unpatentable over Watanabe in view of Park, Xiao, and Chen or Watanabe in view of Park, Xiao, and Kim and alternatively Tang as applied to claim 1 above, and further in view of Ein-Eli, WO 2017/025957 A1.
Regarding claim 22, Watanabe in view of Park, Xiao, and Chen or Watanabe in view of Park, Xiao, and Kim and alternatively Tang suggest the process of claim 1. Watanabe teaches that particles are coated (abstract), such that the material will comprise particles. Xiao also teaches coating particles (0056).
They do not teach using one of the listed reaction chambers.
Ein-Eli teaches a method of reducing the charge/discharge capacity fade rate of a rechargeable LIB during cycling and extending the life and the number of discharge/recharge cycles thereof, effected by coating particles of lithium intercalation materials used for making electrodes of the LIB, with a uniform layer of a metal fluoride effected by atomic layer deposition (abstract). They teach forming the ALD layer by exposing the particles of a lithium intercalation material to a source of the metal while moving the particles relative to themselves, exposing the particles to a source of fluoride while moving the particles relative to themselves, and repeating the steps for n cycles, wherein n is greater than or equal to 2 (pg. 8, lines 23-32). They teach that the lithium intercalation cathode material is selected from a list including LiMn1.5Ni0.5O4, LiNi1/3Mn1/3Co1/3O2, Li[Li0.1305Ni0.3043Mn0.5652]O2 (pg. 8, lines 12-14). They teach that the metal used for the metal fluoride layer can be any one of a variety of metals, including transition metals, noble metals, post-transition metals, base metals, poor metals, alkaline earth metals, lanthanides, actinides, and any combination thereof (pg. 21, lines 1-4). They teach that alkali metals include lithium and that post-transition metals include aluminum (pg. 21, lines 5-7 and pg. 21, lines 29-31), such that the coating can include LiAlF3. They teach that the ALD process is designed to achieve a uniform layer of the metal fluoride over the surface of particles, wherein the uniformity is afforded by exposing the particles to the various precursors of the metal and the fluoride while moving the particles with respect to themselves, namely by agitating, stirring, or otherwise having all facets of the particles accessible to the precursors for at least some time during the exposure steps (pg. 25, lines 11-17). They teach that powder coating by ALD became possible by a uniquely developed fluidized bed reactor (FBR), in which the powder particles are floated in the chamber by means of a flow of an inert gas jetted towards the sample from below (pg. 33, lines 4-8).
From the teachings of Ein-Eli, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have modified the process of Watanabe in view of Park, Xiao, and Chen or Watanabe in view of Park, Xiao, and Kim and alternatively Tang to have deposited the coatings on to the particles using an ALD fluidized bed reactor because Ein-Eli teaches that such a reactor moves the particles relative to one another when depositing a coating on cathode particles by ALD for improving coating uniformity such that it will be expected to successfully deposit on the particles while also providing a more uniform coating. Therefore, the material will be in the form of particles and they will be coated in a fluidized bed reaction chamber by ALD.
Response to Arguments
Applicant’s arguments dated 7/27/2026 have been fully considered, and are persuasive. Therefore, the rejection has been modified as indicated above.
In light of the amendment to claim 14, the previous 112(b) rejection is withdrawn, however, new 112(b) rejections have been made as indicated above.
Conclusion
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to CHRISTINA D MCCLURE whose telephone number is (571)272-9761. The examiner can normally be reached Monday-Friday, 8:30-5:00 EST.
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, Gordon Baldwin can be reached at 571-272-5166. 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.
/CHRISTINA D MCCLURE/Examiner, Art Unit 1718 /GORDON BALDWIN/Supervisory Patent Examiner, Art Unit 1718
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