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 § 103
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
Claims 1-2 and 4-7 are rejected under 35 U.S.C. 103 as being unpatentable over Pullen (US 10501335 B1) and further in view of Endoh (US 20150044513 A1) and Kuzuoka (US 20200235397 A1) and further in view of Li et al. (Li, Yunjiao, et al. “Surface in-situ reconstruction of LiNi0.8Co0.1Mn0.1O2 cathode materials interacting with antimony compounds and the electrochemical performances.” Journal of Electroanalytical Chemistry, vol. 854, Dec. 2019, p. 113582.).
Regarding claim 1, Pullen teaches a process for the manufacture of a coated (col. 2, lines 38-39, [some aspects of a particles include an outer coating on a surface of the particle]) cathode active material (col. 25, example 5, producing LiNi0.079Co0.11Mn0.09Al0.006O2) comprising the steps of:
(a) providing a particulate electrode active material according to general formula Li(1+x)TM(1-x)02 (col. 25, line 5, [LiNi0.8Co0.01Mn0.1O2] (NCM 811)), wherein TM comprises Ni and, optionally, at least one of Co and Mn and wherein at least 50 mole % of the transition metal of TM is Ni (col. 25, Ni is 80%)
(c) removing the water by spray drying (col. 25, line 31).
(e) treating the residue obtained thermally (col.18, lines 32 – 36) residue was thermal treated to about 770 deg. C)
Modified Pullen does not teach (b) treating said particulate electrode active material with an aqueous solution of at least one heteropoly acid selected from the group consisting of phosphotungstic acid, phosphomolybdic acid, tungstosilicic acid, molybdosilicic acid, their respective ammonium salts, and their respective lithium salts in an amount of 0.05 to 1.5 mol %, referring to TM, thereby depositing at least one element selected from the group consisting of Mo, W, Si and P on the surface of said particulate electrode active material, wherein said treatment is supported by mixing operations selected from the group consisting of shaking, stirring and shearing.
Endoh, in the same field of endeavor, making cathode active materials, teaches (b) treating the electrode active material with a heteropoly acid (Endoh, para. 0136, [the cathode active material layer … may contain at least one of a heteropoly acid compound]) selected from the group consisting of phosphotungstic acid (Endoh, para. 0143, [specific examples of the heteropoly acid contained in the heteropoly acid compound may include … tungstophosphoric acid]) thereby depositing at least one element selected from the group consisting of Mo and W (Endoh, para. 0137, [each of the heteropoly acid compound and the heteropoly acid configuring the heteropoly acid compound is a compound containing polyatoms selected from the following element group (a)], … para. 0137, [Mo and W]). Examiner notes that the elements of Mo and W would be deposited on the cathode active material since the elements are a part of the heteropoly acid compound.
It would have been obvious to a person of ordinary skill in the art, before the effective filing date of the claimed invention, to have treated Pullen’s cathode active material with tungstophosphoric acid, as taught by Endoh, in order to achieve higher effects for the cell (Endoh, para. 0145). Examiner notes that the higher effects are explained in para. 0136 of Endoh (the coat derived from the heteropoly acid compound capable of inserting and extracting lithium ions has superior lithium ion permeability. Therefore, while a reaction between the electrodes and the electrolytic solution is suppressed, generation of gas … resulting from a decomposition reaction of the cathode active material … is allowed to be suppressed without lowering cycle characteristics).
Endoh does not teach that the heteropoly acid is added in an amount of 0.05 to 1.5 mol %.
Endoh teaches that the heteropoly acid (para. 0145, [3 wt.%]) is added in an amount equating to 0.02 mol% (Endoh, para. 0145, [preferable, since thereby, higher effects are obtained. Further, the content of the heteropoly acid … in the cathode active material layer may be preferably from 0.01 wt. % to 3 wt. % both inclusive]), referring to TM (Endoh, para. 0145, referring to treating the cathode active material layer).
Examiner notes that 3 wt. %
Mass of tungstophosphoric acid = 3g/ 100g of solution in water
Mass of water = 100g – 3 g = 97 g
Moles of tungstophosphoric acid = 3g/ 2880.05 g/mol = 0.00104 mol
Moles of water = 97 g/ 18.015 g/mol = 5.3844 mol
Mol % of tungstophosphoric acid = (mol tungstophosphoric acid / [moles tungstophosphoric acid + mol water]) = 0.00193 x 100 = 0.02 mol % tungstophosphoric acid
It would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to have optimized for the heteropoly acid amount, based on specific needs for treating the cathode material. A prima facie case of obviousness exists where the claimed ranges or amounts do not overlap with the prior art but are merely close. Titanium Metals Corp. of Americav. Banner, 778 F.2d 775, 783, 227 USPQ 773, 779 (Fed. Cir. 1985) (Court held as proper a rejection of a claim directed to an alloy of “having 0.8% nickel, 0.3% molybdenum, up to 0.1% iron, balance titanium” as obvious over a reference disclosing alloys of 0.75% nickel, 0.25% molybdenum, balance titanium and 0.94% nickel, 0.31% molybdenum, balance titanium.
Modified Pullen does not teach removing water by filtration.
Kuzuoka, in the same field of endeavor, batteries, teaches a [specific] metal oxide can be washed, left to stand, and then undergo solid-liquid separation by a known method such as filtration … and collecting the [specific] metal oxide (para. 0141).
It would have been obvious to a person of ordinary skill in the art, before the effective filing date of the claimed invention, to have utilized filtration in lieu of the spray drying method, as taught by Kuzuoka, in order to separate and collect the metal oxide using a known technique (para. 0140).
Modified Pullen does not teach (d) treating the solid residue obtained from step (c) with at least one water-soluble compound of Al, B, or Sb or at least one heteropoly acid or its respective ammonium or lithium salt by adding least one compound of Al, B, or Sb as a particulate solid or by adding the at least one compound of Al, B, or Sb or heteropoly acid as aqueous slurry or solution, thereby depositing at least one element selected from the group consisting of Al, B, Sb, Mo, W, Si, and P, on the surface of said solid residue from step (c).
Li, in the same field of endeavor, cathode materials, teaches treating an NCM based cathode material by adding Sb as a particulate solid or by adding the at least one compound of Sb (Sb2O5) (Li, abstract), thereby depositing Sb on the surface of said solid residue (Li, abstract, [Sb2O5 can react with … partial surface lattice lithium on the NCM811 surface to further construct Li-Sb-NCM-O mixed coating layers]).
It would have been obvious to a person of ordinary skill in the art, before the effective filing date of the claimed invention, to have treated Pullen’s NCM cathode material with an antimony compound, as taught by Li, in order to construct a cathode material that with higher capacity retentions and enhanced electrochemical performances (Li, abstract).
Modified Pullen teaches, wherein the compound added in step (d) (Li, abstract, Sb2O5) is different from the compound contained in the aqueous solution or slurry (See claim 1 above, Modified Pullen, tungstophosphoric acid, Mo, and W), respectively, in step (b) with respect to the metal.
Regarding claim 2, modified Pullen teaches the process according to claim 1 wherein TM is a combination of metals according to general formula (I) (NiaCobMnc)1-dMd (I) with wherein (Pullen, col. 25, line 5, starting material for NCM is [Ni0.8Co0.01Mn0.1])
a is in the range of from 0.6 to 0.99, (Pullen, col. 25, line 5)
b is zero or in the range of from 0.01 to 0.2, (Pullen, col. 25, line 5)
c is in the range of from zero to 0.2, (Pullen, col. 25, line 5)
d is in the range of from zero to 0.1 (Pullen, col. 25, line 5 , d = 0)
M is at least one of Al, Mg, Nb, Ta, Ti, Ge, Mo, W and Zr, and
a+b+c=1. (Pullen, col. 25, line 5)
Regarding claim 4, modified Pullen teaches the process according to claim 1 wherein said compound of Sb in step (d) is added as particulate solid (Li, abstract, [solid-state method]) (pg. 3, section 2.1, solid-state method of Sb added as a solid powder is further explained).
Examiner notes that antimony pentoxide (Sb2O5) is a solid.
Regarding claim 5, modified Pullen teaches the process according to claim 1 wherein said compound of Sb in step (d) is added as a particulate solid or by at least one compound of Sb (Li, abstract, Sb2O5).
Regarding claim 6, modified Pullen teaches the process according to claim 1 wherein step (e) includes a calcination step at a maximum temperature in the range of 770 deg. C.
Example 5 of Pullen does not teach wherein step (e) includes a calcination step at a maximum temperature in the range from 300 to 700°C.
Pullen’s broader disclosure, as explained in Example 1 of Pullen, teaches wherein step (e) includes a calcination step at a maximum temperature in the range from 300 to 700°C. (Pullen, col. 18, lines 32-39, the max temperature was about 700°C for the calcined materials).
It would have been obvious to a person of ordinary skill in the art, before the effective filing date of the claimed invention, to have utilized the calcination maximum temperature provided in the calcination step to example 5 of Pullen, as taught by example 1 of Pullen, in order to produce cathode particles that result in additional cycle life and reduction in impedance growth, which in turn, significantly improves the electrochemical performance of the material, as taught by Pullen (Pullen, col. 14, lines 14-25).
Regarding claim 7, modified Pullen teaches the process according to claim 1 wherein step (e) includes a drying step at a maximum temperature in the range of from 40 to 250°C (Pullen, col. 25, line 36 [the furnace was then allowed to cool to 130 deg. C and the powder was removed from the furnace]).
Claim 8 is rejected under 35 U.S.C. 103 as being unpatentable over Pullen (US 10501335 B1) and further in view of Endoh (US 20150044513 A1) and Kuzuoka (US 20200235397 A1) and further in view of Li et al. (Li, Yunjiao, et al. “Surface in-situ reconstruction of LiNi0.8Co0.1Mn0.1O2 cathode materials interacting with antimony compounds and the electrochemical performances.” Journal of Electroanalytical Chemistry, vol. 854, Dec. 2019, p. 113582.), and Park (Park, Kwangjin, and Byungjin Choi. “Requirement of high lithium content in NI-rich layered oxide material for Li Ion Batteries.” Journal of Alloys and Compounds, vol. 766, Oct. 2018, pp. 470–476.).
Regarding claim 8, modified Pullen teaches the process according to claim 1. Modified Pullen does not teach comprising an additional step (f), wherein step (f) includes treating the electrode active material provided in step (a) with water and at least partially removing the water before subjecting the electrode active material to step (b).
Park, in the same field of endeavor, NCM cathode materials, teaches treating the electrode active material (NCM precursors) with water (Section 2.1 Synthesis, [for the washing process, the NCM powder was suspended in DI water]) and at least partially removing the water (Section 2.1 Synthesis, [the NCM powder was dried at 120 deg. C until the solvent completely evaporated).
It would have been obvious to a person of ordinary skill in the art, before the effective filing date of the claimed invention, to have added a washing process to the precursor after step (a) and before step (b) of Pullen’s cathode material, as taught by Park, in order to remove lithium residuals, to reduce the potential risk of gas evolution on the surface, as taught by Park, (Park, pg. 470, column. 2).
Response to Arguments
Applicant’s arguments with respect to claim 1 have been considered but are moot because the new ground of rejection does not rely on any reference applied in the prior rejection of record for any teaching or matter specifically challenged in the argument.
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.
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/V.G./ Examiner, Art Unit 1721
/MAYLA GONZALEZ RAMOS/Primary Examiner, Art Unit 1721