DETAILED ACTION
Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Claim Rejections - 35 USC § 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 3 is 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.
Claim 3 recites the limitation "the positive active material according to claim 2" in line 1. There is insufficient antecedent basis for this limitation in the claim, because claim 2 has been cancelled. Appropriate correction is required.
Claim Rejections - 35 USC § 102
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 the appropriate paragraphs of 35 U.S.C. 102 that form the basis for the rejections under this section made in this Office action:
A person shall be entitled to a patent unless –
(a)(1) the claimed invention was patented, described in a printed publication, or in public use, on sale, or otherwise available to the public before the effective filing date of the claimed invention.
Claims 1, 3, 16 and 20-22 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Choi et al. (US 20160276658 A1).
Regarding claim 1, Choi teaches a cathode active material for a lithium secondary battery including a compound capable of reversibly intercalating and deintercalating lithium (core material) and a coating layer (cladding layer) positioned on at least a portion of a surface of the compound [0035]. The compound capable of reversibly intercalating and deintercalating lithium may be selected as LiaA1-bXbD2 (0.90≤a≤1.8, 0≤b≤0.5), where A is selected from the group consisting of Ni, Co, Mn or a combination thereof, X is selected from the group consisting of Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, rare earth elements or a combination thereof and D is selected from the group consisting of O, F, S, P or a combination thereof (lithium rich manganese-based positive electrode material can be obtained) [0052]. The coating layer (cladding layer) contains Li3PO4 (lithium ion conductor), LiF and may further comprise ZrO2 (fluorite type oxygen ion conductor) [0043].
Regarding claim 3, Choi teaches all the elements of the current invention in claim 1. From the discussion of claim 1, the feature “the fluorite-type oxygen-ion conductor comprises at least one of ZrO2, CeO2 or GeO2” is met.
Regarding claim 16, Choi teaches all the elements of the current invention in claim 1. Choi further teaches that the composite coating layer containing Li3PO4 and LiF which may further comprise ZrO2 (fluorite type oxygen type ion conductor) is formed on the surface of the compound capable of reversibly intercalating and deintercalating lithium (core material) by a heat treatment [0055].
Regarding claims 20 and 21, Choi teaches all the elements of the current invention in claim 1. Choi further teaches that its cathode active material is for a lithium secondary battery [0014 and claim 16]. The cathode active material is prepared as a slurry and applied onto an aluminum thin film (current collector) [0106].
Regarding claim 22, Choi teaches all the elements of the current invention in claim 21. Choi further teaches as part of its background that in accordance with the recent trend toward miniaturization and lightness of portable electronic devices, the necessity for high performance and large capacity of a battery used as a power source of these devices has increased [0002]. Because its invention has been made in an effort to provide a cathode active material for a lithium secondary battery having high capacity and excellent cycle life characteristics [0013], it would be reasonable to employ its lithium secondary battery on an arbitrary electrical device.
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 non-obviousness.
Claims 5 and 9 are rejected under 35 U.S.C. 103 as being unpatentable over Choi et al. (US 20160276658 A1) as applied to claim 1 above, further in view of Marrero-López, D., et al. (Synthesis and characterization of La2Mo2O9 obtained from freeze-dried precursors. Journal of Solid State Chemistry 177.7 (2004): 2378-2386, see NPL documents for citation) and Liu et al. (CN 108878794 A, see machine translation for citation).
Regarding claim 5, Choi teaches all the elements of the current inventio in claim 1, except where “the oxygen-ion conductor comprises La2Mo2O9, and the lithium-ion conductor comprises LiLaO2 and Li2MoO4”.
Marrero-Lopez teaches the preparation the preparation of La2Mo2O9 ceramics, which are oxide ion conductors (same field of endeavor of Choi) [p. 2378; par. 2 and p. 2379; par. 3]. It is taught that the structure of La2Mo2O9 possesses a significant fraction of vacant intrinsic oxygen sites, which allows accommodation of oxygen excess in the structure, contrary to traditional oxide ion conductors (such as fluorite-type), which have been related with the high conductivity of this material [p. 2378; par. 3].
Liu teaches a positive electrode material with a composite coating layer, which sequentially comprises the following layers from inside to outside: a core layer, a transition layer and a shell layer [010]. The core layer is a spinel lithium manganate and the transition layer is an oxide having ion transport capability and/or a lithium-containing oxide [011-012]. The positive electrode material with a composite coating layer of Liu is on the same field of endeavor of Choi. The transition layer may contain ZrO2 (fluorite-type oxygen- ion conductor), LiLaO2 and Li2MoO4 [019]. It is taught that with the introduction of the transition layer, the electrochemical performance of the positive electrode material is ensured, the contact between the positive electrode core and an electrolyte is also effectively reduced, and the problem of Mn dissolving is reduced [Abstract].
It would have been prima facie obvious to one of ordinary skill in the art before the
effective filing date of the claimed invention to modify the positive active material of Choi to include the feature where “the oxygen-ion conductor comprises La2Mo2O9, and the lithium-ion conductor comprises LiLaO2 and Li2MoO4”, because Marrero-Lopez teaches that the structure of La2Mo2O9 possesses a significant fraction of vacant intrinsic oxygen sites, which allows accommodation of oxygen excess in the structure, contrary to traditional oxide ion conductors (such as fluorite-type), which have been related with the high conductivity of this material. In addition, Liu teaches that with the introduction of a transition coating layer (comprising LiLaO2 and Li2MoO4), the electrochemical performance of the positive electrode material is ensured, the contact between the positive electrode core and an electrolyte is also effectively reduced, and the problem of Mn dissolving is reduced.
Regarding claim 9, Choi, Marrero-López and Liu teach all the elements of the current invention in claim 5. From claim 5 discussion, if the positive active material of Choi was modified to include La2Mo2O9 as the oxygen-ion conductor and the lithium-ion conductor comprising LiLaO2 and Li2MoO4, and because the oxygen-ion and lithium-ion conductors were identified on claim 1 discussion to be positioned on at least a portion of a surface of the compound capable of reversibly intercalating and deintercalating lithium (core material) of Choi, the feature “a surface of the core material is doped with a lanthanum atom and a molybdenum atom” could be considered met.
Claims 11 and 12 are rejected under 35 U.S.C. 103 as being unpatentable over Choi et al. (US 20160276658 A1) as applied to claim 1 above, further in view of Park et al. (US 20170018767 A1).
Regarding claims 11 and 12, Choi teaches all the elements of the current invention in claim 1, except “a thickness of the cladding layer is 0.01 to 4 µm” (claim 11) and “a thickness of the cladding layer is 0.02 to 1 µm” (claim 12).
Park teaches a composite cathode active material for a lithium battery that includes a lithium composite oxide (10) and a coating layer (12) including a metal oxide and a lithium fluoride disposed on at least a portion of a surface of the lithium composite oxide [0036 and Fig. 1]. The lithium composite oxide may include 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 V, Mg, Ga, Si, W, Mo, Fe, Cr, Cu, Zn, Ti, Al and B; and A is at least one anion element selected from F, S, Cl and Br [0044-0045]. The metal oxide of the coating layer (12) may include CeO2 and ZrO2 among other materials [0042]. The composite cathode active material taught by Park is on the same field of endeavor of Choi, therefore the coating layer (12) can be considered analogous to the cladding layer. Park further teaches that the total thickness of the coating layer (cladding layer analogous) may be in a range of about 1 nm to about 1 µm (overlaps both claim 11 and 12 ranges), because when the total thickness of the coating layer (cladding layer analogous) is within the above ranges, a lithium battery having excellent capacity retention rates and high rate characteristics may be manufactured [0073].
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to have selected the overlapping portion of the coating layer (cladding layer analogous) thickness range disclosed by Park because overlapping ranges have been held to be a prima facie case of obvious. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990). See MPEP § 2144.05. In addition Park teaches that when the total thickness of the coating layer (cladding layer analogous) is within the above ranges, a lithium battery having excellent capacity retention rates and high rate characteristics may be manufactured.
Claim 13 is rejected under 35 U.S.C. 103 as being unpatentable over Choi et al. (US 20160276658 A1) as applied to claim 1 above.
The Office realizes that all of the claimed effects or physical properties are not positively stated by Choi. However, Choi teaches all of the claimed ingredients, claimed amounts, and substantially similar process of making. According to the original specification, in the positive active material according to this application, a cladding layer that contains both the oxygen-ion conductor and the lithium-ion conductor is formed on the outer surface of the core material containing the lithium-rich manganese-based positive electrode material. Relatively concentrated oxygen vacancies exist inside the oxygen-ion conductor, and are highly capable of absorbing and storing oxygen, thereby effectively suppressing the release of lithium-rich manganese-based lattice oxygen, reducing extraction of lithium ions, and in turn, improving the first-cycle Coulombic efficiency of the positive active material [0052]. In some embodiments, a peak intensity ratio between IO22- and IO2- in the cladding layer is 0.5 to 1, and optionally 0.7 to 0.9, where IO22- is a peak intensity value of an oxygen vacancy corresponding to 531 eV in an X-ray photoelectron spectroscopy test, and IO2- is a peak intensity value of lattice oxygen corresponding to 529 eV in the X-ray photoelectron spectroscopy test. By controlling the peak intensity ratio between IO22- and IO2- in the cladding layer to fall within the specified range, the cladding layer includes an appropriate amount of oxygen vacancies, and can effectively suppress the release of oxygen from the material, improve stability of the structure of the lithium-rich manganese-based positive electrode material in the positive active material, and suppress the phase transition of the lithium-rich manganese-based positive electrode material [0063].
Because of the reasons above, the claimed effects and physical properties, i.e. “the positive active material according to claim 1, characterized in that a peak intensity ratio between IO22- and IO2- in the cladding layer is 0.5 to 1, and optionally 0.7 to 0.9, wherein IO22- is a peak intensity value of an oxygen vacancy corresponding to 531 eV in an X-ray photoelectron spectroscopy test, and IO2- is a peak intensity value of lattice oxygen corresponding to 529 eV in the X-ray photoelectron spectroscopy test” would expectedly be achieved by a composition with all the claimed ingredients, claimed amounts, and substantially similar process of making. See MPEP § 2112.01. If it is the applicant' s position that this would not be the case: (1) evidence would need to be provided to support the applicant' s position; and (2) it would be the Office' s position that the application contains inadequate disclosure that there is no teaching as to how to obtain the claimed properties with only the claimed ingredients, claimed amounts, and substantially similar process of making.
Claim 14 is rejected under 35 U.S.C. 103 as being unpatentable over Choi et al. (US 20160276658 A1) as applied to claim 1 above, further in view of Nakano et al. (JP 2012129166 A, see machine translation for citation).
Choi teaches all the elements of the current invention in claim 1, except “the positive active material according to claim 1, characterized in that a molecular formula of the lithium-rich manganese-based positive electrode material is xLi2MnO3(1-x) LiNiyCozMnaM1-y-z-aO2, wherein 0<x<1, 0≤y≤1, 0≤z≤1, 0≤a≤1, 0<y+z+a≤1; and M is at least one of Mg, B, Al, V, Ti, Zr, Sn, or Mo”.
Nakano teaches a lithium ion secondary battery comprising a positive electrode having formula xLi2MnO3(1-x)LiMnaCobNicO2 (0.2≤x≤0.5, 0.3≤a≤0.5, 0.1≤b≤0.3, 0.3≤c≤0.5 and a+b+c=1 ) [0015-0016]. The positive electrode of Nakano is on the same field of endeavor of Choi. From Nakano teachings if x=0.5, a=c=0.4 and b=0.2, 0.5Li2MnO3*0.5LiMn0.4Co0.2Ni0.4O2 is obtained. This compound can be obtained as well from claim 14 limitations if x=0.5, y=a=0.4 and z=0.2. It is taught that such a solid solution is capable of increasing the capacity by reorganization of the crystal structure by performing high voltage charging [0016].
It would have been prima facie obvious to one of ordinary skill in the art before the
effective filing date of the claimed invention to modify the positive active material of Choi to include the feature where it is “characterized in that a molecular formula of the lithium-rich manganese-based positive electrode material is xLi2MnO3(1-x) LiNiyCozMnaM1-y-z-aO2, wherein 0<x<1, 0≤y≤1, 0≤z≤1, 0≤a≤1, 0<y+z+a≤1; and M is at least one of Mg, B, Al, V, Ti, Zr, Sn, or Mo”, because Nakano teaches the referred feature and that such a solid solution is capable of increasing the capacity by reorganization of the crystal structure by performing high voltage charging.
Claim 15 is rejected under 35 U.S.C. 103 as being unpatentable over Choi et al. (US 20160276658 A1) as applied to claim 1 above, further in view of Choi et al. (US 20210119208 A1).
Regarding claim 15, Choi (‘658 A1) teaches all the elements of the current invention in claim 1, except where the positive active material of claim 1 is “characterized in that a particle type of the lithium-rich manganese-based positive electrode material is a secondary particle, a single crystal, or a quasi-single crystal; and/or a specific surface area of the lithium-rich manganese-based positive electrode material is less than 2.0 m2/g, and optionally is 0.1 to 1 m2/g; and a Dv50 particle diameter of the lithium-rich manganese-based positive electrode material is 1 to 20 µm, and optionally 3 to 15 µm”.
Choi (‘208 A1) teaches a positive electrode active material for lithium secondary batteries [Abstract]. The positive electrode active material includes an overlithiated layered oxide represented by rLi2MnO3.(1−r)LiaNixCoyMnzM11−(x+y+z)O2, where 0<r≤0.6, 0<a≤1, 0≤x≤1, 0≤y<1, 0≤z<1, 0<x+y+z<1, and M1 is at least one or more selected from Na, K, Mg, Al, Fe, Cr, Y, Sn, Ti, B, P, Zr, Ru, Nb, W, Ba, Sr, La, Ga, Mg, Gd, Sm, Ca, Ce, Fe, Al, Ta, Mo, Sc, V, Zn, Nb, Cu, In, S, B and Bi [0009-0010]. The positive electrode active material of Choi (‘208 A1) is on the same field of endeavor of Choi (‘658 A1). Choi (‘208 A1) teaches that its positive electrode active material is adjusted to have a single crystal structure [0084]. It is taught that as portions corresponding to the single crystal structure increases, the problem of voltage decay that may occur in polycrystals may be improved [0086].
It would have been prima facie obvious to one of ordinary skill in the art before the
effective filing date of the claimed invention to modify the positive active material of Choi (‘658 A1) to include the feature where the positive active material of claim 1 is “characterized in that a particle type of the lithium-rich manganese-based positive electrode material is a single crystal”, because Choi (‘208 A1) teaches that it may improve the problem of voltage decay that may occur in polycrystals.
Allowable Subject Matter
Claims 6-8, 10 and 17-19 are objected to as being dependent upon a rejected base claim but would be allowable if rewritten in independent form including all of the limitations of the base claim and any intervening claims.
The following is a statements of reasons for the indication of allowable subject matter:
The present invention is related to, inter alia, a positive electrode active material comprising a lithium-rich manganese core and a cladding layer covering an outer surface of the core material, wherein the cladding layer comprises an oxygen-ion conductor and a lithium-ion conductor. The oxygen-ion conductor comprises at least one of La2Mo209 or a fluorite-type oxygen- ion conductor; the lithium-ion conductor comprises at least one of LiLaO2, Li2MoO4, Li3PO4, Li3BO3 or LiTaO3.
Choi et al. (US 20160276658 A1) is considered the closest relevant prior art to independent claim 1 and dependent claims 3, 15, 16 and 20-22. Choi discloses a cathode active material for a lithium secondary battery including a compound capable of reversibly intercalating and deintercalating lithium (core material) and a coating layer (cladding layer) positioned on at least a portion of a surface of the compound [0035]. The compound capable of reversibly intercalating and deintercalating lithium may be selected as LiaA1-bXbD2 (0.90≤a≤1.8, 0≤b≤0.5), where A is selected from the group consisting of Ni, Co, Mn or a combination thereof, X is selected from the group consisting of Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, rare earth elements or a combination thereof and D is selected from the group consisting of O, F, S, P or a combination thereof (lithium rich manganese-based positive electrode material can be obtained) [0052]. The coating layer (cladding layer) contains Li3PO4 (lithium ion conductor), LiF and may further comprise ZrO2 (fluorite type oxygen type ion conductor) [0043].
However, Choi do not disclose, teach, fairly suggest, nor render obvious the employment of La2Mo2O9 as a coating for its cathode active material. To the contrary Choi teaches that cathode active material including the composite coating layer containing Li3PO4 and LiF and further containing the lithium metal compound, the metal oxide (ZrO2), the fluorite type oxygen type ion conductor compound and/or the combination thereof may improve battery characteristics of a lithium secondary battery. In more detail, it is possible to provide a cathode active material of which efficiency and cycle life characteristics are improved as compared to an existing cathode active material [0038 and 0043]. The composite coating layer contains the lithium metal compound and the metal oxide, such that it is possible to improve ion conductivity, stabilize a surface structure, and suppress side reactions with the electrolyte [0044]. Furthermore, from the Examples 1-6, the cathode active material preparation was a dry mixing of the materials followed by heat treating the mixture at 800° C. for 6 hours [0096-0101].
Accordingly, there does not appear to be any reasonable basis for the skilled artisan to abandon the cathode active material preparation method taught by Choi and be directed toward a preparation method involving “mixing a molybdenum salt, a lanthanum salt, and a lithium-rich manganese-based precursor in a solvent, and performing a hydrothermal reaction at 100 °C to 200 °C for 8 to 12 hours to obtain a lithium-rich manganese-based precursor, wherein, La2Mo2O9 is deposited in situ on a surface of the precursor; and mixing a lithium salt with the lithium-rich manganese-based precursor containing the La2Mo2O9 deposited in situ on the surface, and then calcining the mixture to obtain a positive active material compositely coated with the oxygen-ion conductor and the lithium-ion conductor” (claim 17), because the prior art method already accomplishes a cathode active material of which efficiency and cycle life characteristics are improved as compared to an existing cathode active material, with simpler and known methods.
Liu et al. (CN 108878794 A, see machine translation for citation) as applied to claim 5, is also considered relevant to independent claim 1. Liu a positive electrode material with a composite coating layer, which sequentially comprises the following layers from inside to outside: a core layer, a transition layer and a shell layer [010]. The core layer is a spinel lithium manganate and the transition layer is an oxide having ion transport capability and/or a lithium-containing oxide [011-012]. The transition layer may contain ZrO2 (fluorite-type oxygen- ion conductor), LiLaO2 and Li2MoO4 [019].
However, Liu do not disclose, teach, fairly suggest, nor render obvious the employment of La2Mo2O9 as a coating for its cathode active material. To the contrary Liu teaches that with the introduction of the transition layer, the electrochemical performance of the positive electrode material is ensured, the contact between the positive electrode core and an electrolyte is also effectively reduced, and the problem of Mn dissolving is reduced [Abstract].
Accordingly, there does not appear to be any reasonable basis for the skilled artisan to abandon the positive active material preparation method taught by Liu and be directed toward a preparation method involving “mixing a molybdenum salt, a lanthanum salt, and a lithium-rich manganese-based precursor in a solvent, and performing a hydrothermal reaction at 100 °C to 200 °C for 8 to 12 hours to obtain a lithium-rich manganese-based precursor, wherein, La2Mo2O9 is deposited in situ on a surface of the precursor; and mixing a lithium salt with the lithium-rich manganese-based precursor containing the La2Mo2O9 deposited in situ on the surface, and then calcining the mixture to obtain a positive active material compositely coated with the oxygen-ion conductor and the lithium-ion conductor” (claim 17), because the prior art method already ensure the electrochemical performance of the positive electrode material, effectively reduce the contact between the positive electrode core and an electrolyte, and the problem of Mn dissolving, with simpler and known methods.
Any comments considered necessary by applicant must be submitted no later than the payment of the issue fee and, to avoid processing delays, should preferably accompany the issue fee. Such submissions should be clearly labeled “Comments on Statement of Reasons for Allowance.”
Conclusion
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/G.R./Examiner, Art Unit 1725
/JAMES M ERWIN/Primary Examiner, Art Unit 1725 01/14/2026