CATHODE MATERIALS FOR SECONDARY BATTERIES
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 .
Information Disclosure Statement
The information disclosure statement (IDS) submitted on 5/23/2024 is in compliance with the provisions of 37 CFR 1.97. Accordingly, the information disclosure statement is being considered by the examiner.
Claim Objections
Claims 2-10 and 12-20 are objected to because of the following informalities: amend each to “The process of claim…”. Appropriate correction is required.
Claim Rejections - 35 USC § 103
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
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 1-7 and 11-17 are rejected under 35 U.S.C. 103 as being unpatentable over Sun et al. (US 2014/0027670 A1) and Endo et al. (JP 5871186 B2) and further in view of Carroll et al. (US 2018/0034042 A1).
Regarding claims 1, 3, 4, 7, 11, 13, 14, and 17, Sun et al. teach a process of preparing a cathode active material (Abstract; Examples) the process comprising:
providing a first aqueous metal ion solution (Examples; Claim 11 discloses a first step of preparing a metal salt aqueous solution for forming a center part of the positive electrode active material.);
providing a second aqueous metal ion solution (Examples; Claim 11 discloses preparing a metal salt aqueous solution for forming a surface part of the positive electrode active material.);
combining the first aqueous metal ion solution with the second aqueous metal ion solution and with a precipitating agent to form a precipitate (Claim 11 discloses mixing the two metal salt solutions with a chelating agent.); isolating the precipitate (Paragraph 0074); mixing the precipitate with a lithium or a sodium salt to form a mixture (Paragraph 0075 discloses adding lithium nitrate to the precipitate.); and heating-treating the mixture to form the cathode active material (Paragraph 0075 discloses calcinating the active material.) that is expressed as
a core portion comprising Li1+β(NixMnyCoz)M1O2; and a surface portion comprising Li1+β (Nix′Mny′Coz′)M2O2; or a core portion comprising Na1+β(NixMnyCoz) M1O2; and a surface portion comprising Na1+β(Nix′Mny′Coz′)M2O2; wherein: M1 represents a core composition comprising of Ni, Mn, and/or Co or a combination of at two of thereof; 0≤x≤1, 0≤y≤0.5, 0≤z≤1, 0≤x′≤0.5, 0≤y′≤0.5, 0.5≤z′≤1, −0.1≤β≤0.1, and −0.1≤β’≤0.1; the sum of x, y and z is 0.9-1.1, and the sum of x′, y′ and z′ is 0.9-1.1 (Claim 1 discloses a positive electrode active material for a lithium secondary battery, a positive electrode active material with whole particle concentration gradient for a lithium secondary battery, wherein the concentration of a metal making up the positive electrode active material for a lithium secondary battery shows continuous concentration gradient in the entire region, from the center part to the surface part of the particle, which comprises: the center part expressed by the following formula 1; and the surface part expressed by the following formula 2, wherein the concentration of the M1 is constant from the center part to the surface part; and the concentration of the M2 and the concentration of the M3 have continuous concentration gradient from the center part to the surface part. Lia1M1xM2y1M3z1M4wO2+δ [Formula 1] Lia2M1xM2y2M3z2M4wO2+δ [Formula 2] (in the formulas 1 and 2, M1, M2 and M3 are selected from the group consisting of Ni, Co, Mn and a combination thereof; M4 is selected from the group consisting of Fe, Na, Mg, Ca, Ti, V, Cr, Cu, Zn, Ge, Sr, Ag, Ba, Zr, Nb, Mo, Al, Ga, B and a combination thereof; 0<a1≦1.1, 0<a2≦1.1, 0≦x≦1, 0≦y1≦1, 0≦y2≦1, 0≦z1≦1, 0≦z2≦1, 0≦w≦0.1, 0.0≦δ≦0.02, 0<x+y1+z1≦1, 0<x+y2+z2≦1, and y1≦y2, z2≦z1.);
the cathode active material comprises particles having a vector radius defined from a core of each particle to the surface of each particle (Abstract and claim 1 disclose a concentration gradient from core to surface.)
the surface composition comprising at least 50% Co, (0≦x≦1, 0≦y1≦1, 0≦y2≦1, 0≦z1≦1, 0≦z2≦1 which represent Co, Ni, and Mn which can be between 0 and 1.), Sun further teaches the addition of a dopant material comprising a transition metal (See materials for M4 in claim 1.); and wherein the Ni concentration continuously decreases along the vector radius of each particles; the Co concentration continuously increases along the vector radius of each particle (Claim 3 discloses wherein the concentration of the M2 (Co) is increased with continuous concentration gradient from the center part to the surface part; and the concentration of the M3 (Ni) is decreased with continuous concentration gradient from the center part to the surface part. Further, claim 6 discloses wherein the M1 is Mn (constant), the M2 is Co (increases) and the M3 is Ni (decreases).).
However, Sun et al. do not teach the cathode comprising spherical morphology, wherein a structure of M2 may be a composite structure and comprises a disordered rock-salt phase, or wherein the Mn concentration continuously decreases along the vector radius of each particle.
Endo et al. teach discloses a lithium transition metal active material of a metal composite oxide with a Mn concentration at the surface “coating portion” lower than at the center “core”. (Paragraph 0018) The core has a Co concentration which decreases from the surface “Point 8” to the central part “Point 1”. (Paragraph 0090) Fig. 3 is reproduced herein:
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As can be seen, the Mn concentration decreases from core to surface and the Co concentration increases from core to surface. Further, the surface (point 8) forms a concentration of 63% Co {Co/(Co+Ni+Mn)=0.7/(0.7+0.2+0.2) x 100=63%) (See fig. 3 above).
Further the particles are spherical in nature (Paragraphs 0038-0039) and a rock-salt structure is formed (Paragraph 0065).
Therefore, it would have been obvious to one of ordinary skill in the art to modify Sun with Endo in order to prevent separation at the two- phase boundary between the core and the covering portion and improve cycle characteristics and high rate discharge.
However, neither Sun nor Endo et al. specifically teach the materials comprise a disordered rock-salt phase.
Carroll discloses various oxides for high energy cathode materials (Abstract) having a disordered rock salt crystallographic structure. Further, the oxide can be comprised of lithium nickel cobalt manganese oxides (Paragraph 0010).
Therefore, it would have been obvious to one of ordinary skill in the art to modify the oxides of Sun and Endo with Carroll in order to improve performance.
Regarding claims 2 and 12, the combination of Sun, Endo, and Carroll et al. teach the processes of claims 1 and 11. Further, Sun et al. teach wherein: the heat-treating comprises at least one calcination step at a heating rate to a temperature of about 680°C to about 1200°C the calcination step is conducted in an oxygen atmosphere, an air atmosphere, or in an oxygen-enriched air atmosphere (Paragraphs 0064; 0075 disclose the calcination step occurs between 700-1100°C under oxygen or air.).
Regarding claims 5 and 15, the combination of Sun, Endo, and Carroll et al. teach the processes of claims 1 and 11. Further, Endo et al. teach discloses a lithium transition metal active material of a metal composite oxide with a Mn concentration at the surface “coating portion” lower than at the center “core”. (Paragraph 0018) The core has a Co concentration which decreases from the surface “Point 8” to the central part “Point 1”. (Paragraph 0090) Fig. 3 is reproduced herein:
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As can be seen, the Mn concentration decreases from core to surface and the Co concentration increases from core to surface. Further, the surface (point 8) forms a concentration of 63% Co {Co/(Co+Ni+Mn)=0.7/(0.7+0.2+0.2) x 100=63%) (See fig. 3 above).
Further the particles are spherical in nature (Paragraphs 0038-0039) and a rock-salt structure is formed (Paragraph 0065).
Therefore, it would have been obvious to one of ordinary skill in the art to modify Sun with Endo in order to prevent separation at the two- phase boundary between the core and the covering portion and improve cycle characteristics and high rate discharge.
Regarding claims 6 and 16, the combination of Sun, Endo, and Carroll et al. teach the processes of claims 1 and 11. Further, Sun teaches wherein a concentration of any metals change by one or more slopes (See figs. 1-10).
Claims 8, 9, 18, and 19 are rejected under 35 U.S.C. 103 as being unpatentable over Sun et al. (US 2014/0027670 A1) and Endo et al. (JP 5871186 B2) and Carroll et al. (US 2018/0034042 A1) as applied to claims 1 and 11 above, and further in view of Wu et al. (US 2016/0260965 A1).
Regarding claims 8, 9, 18, and 19, Sun, Endo, and Carroll et al. teach the cathode active material of claims 1 and 11. However, they do not teach further comprising a surface coating on the particle; wherein the surface coating comprises a metal oxide, a metal fluoride, a metal phosphate, a conductive carbon coating, a conductive polymer (such as PEDOT), or a combination of any two or more thereof.
Wu et al. teach a coated lithium metal oxide cathode (Abstract) which further comprises a surface coating on the particle; wherein the surface coating comprises a metal oxide, a metal fluoride, a metal phosphate, a conductive carbon coating, a conductive polymer (such as PEDOT), or a combination of any two or more thereof (Abstract, claims 13-17).
Therefore, it would have been obvious to one of ordinary skill in the art to modify Sun with Wu in order to improve cycle life and safety.
Claims 10 and 20 are rejected under 35 U.S.C. 103 as being unpatentable over Sun et al. (US 2014/0027670 A1), Endo et al. (JP 5871186 B2), Carroll et al. (US 2018/0034042 A1) and of Wu et al. (US 2016/0260965 A1) as applied to claims 9, and 19 above, further in view Ishii et al. (US 2019/0334166 A1).
Regarding claims 10 and 20, the combination of Sun, Endo, Carroll, and Wu et al. teach the process of claims 9 and 19. However, they do not teach wherein the surface coating comprises a conductive polymer comprising poly(3,4-ethylenedioxythiophene).
Ishii et al. a surface coating comprises a conductive polymer comprising poly(3,4-ethylenedioxythiophene) (Claim 1).
Therefore, it would have been obvious to one of ordinary skill in the art to modify the combination of Sun, Endo, Carroll, and Wu with Ishii in order to improve low temperature properties.
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to DANIEL S GATEWOOD whose telephone number is (571)270-7958. The examiner can normally be reached M-F 8:00-5:30.
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Daniel S. Gatewood, Ph.D.
Primary Examiner
Art Unit 1729
/DANIEL S GATEWOOD, Ph. D/Primary Examiner, Art Unit 1729 May 19th, 2026
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