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 Claims
Claims 1-20, as filed 21 June 2023, are examined herein. No new matter is included.
Claim Objection
Claims 6 and 17 are objected to because of the following informalities. Claims 6 and 17 include the formula LiaNO2+b, where N is selected from Al, Mg, Ti, Mn, Fe, Ni, Zn, Cu, Nb, Cr, Zr, and Y. The use of “N” in a chemical composition typically represents nitrogen, Applicant is requested to amend the formula to avoid confusion with any element. 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.
Claim(s) 1-9 and 11-20 is/are rejected under 35 U.S.C. 103 as being unpatentable over Saito (US 20160351901 A1) in view of Kang (US 20170317342 A1).
Regarding claims 1-3 and 12-14, Saito teaches an electrochemical apparatus (abstract), comprising:
a positive electrode, wherein the positive electrode comprises a positive electrode active material layer; ([0015] positive electrode active material layer)
when the electrochemical apparatus is fully discharged, the positive electrode active material layer comprises a lithium cobalt oxide with a P63mc structure ([0006] space group P63mc; [0024] the lithium composite oxide A contains at least Co) and a lithium-containing metal oxide. ([0022-0023] “lithium composite oxide A” may further include other metal compounds in the form of a mixture or a solid solution. Examples include Li1.2Mn0.54Ni0.13Co0.13O) which is a lithium-containing metal oxide.
Regarding the limitation a ratio of a molar concentration of element Li to a molar concentration of other metal elements in the lithium-containing metal oxide is a, wherein 0<a<0.5. Saito further discloses [0022-0023] that the surface of “lithium composite oxide A” may have fine particles of an inorganic compound, e.g. alumina. While Saito discloses that “lithium composite oxide A” may further include other metal compounds in the form of a mixture or a solid solution, or may be surface coated with fine particles, Saito does not disclose any specific embodiment where the Li:a molar concentration of other metal elements ratio a is > 0 and <0.5.
Kang, in the field of (abstract) positive electrode active material comprising LCO particles, discloses [0057] the surface treatment layer comprising LiMn2O4 and other candidates, each of which has a Li:other metal elements ratio of 0.5, which is just above the claimed range of 0<a<0.5. Kang discloses at [0024] that by choosing a lithium deficient surface treatment, a side reaction with an electrolyte may be restrained, high packing density and high-capacity property may be attained, improved rate characteristic and initial capacity property may be obtained, good lithium ion conductivity may be attained, and good output property and life property may be obtained.
A person of ordinary skill in the art would have been motivated, as of before the effective filing date of the instant invention, to modify the positive active material having a fine particulate surface coating of Saito by selecting Kang’s LiMn2O4 for Saito’s “fine particles of an inorganic compound”, with a reasonable expectation of successfully improving battery capacity and life.
For the purpose of clarity, Examiner notes that the proposed modification of Saito with Kang creates a secondary particle where the core is “lithium composite oxide A” having a surface comprising fine particles of Kang’s inorganic compound, e.g. LiMn2O4, thus meeting the instant claim limitation.
Examiner further notes that a = 0.5 is so close to the claimed range of 0<a<0.5 such that the skilled artisan would have expected it to have substantially the same properties and thus render obvious before the effective filing date of the claimed invention the selection of 0<a<0.5 in view of Kang’s teachings for that reason.
Regarding claim 12, Saito does not explicitly teach an electronic apparatus comprising the electrochemical apparatus of claim 1. Kang at [0008] discloses the use of lithium secondary batteries in mobile phones and tablet computers. A person of ordinary skill in the art would have been motivated, as of before the effective filing date of the instant invention, to select the battery of modified Saito for the mobile phones and tablet computers of Kang, with a reasonable expectation of success.
This also teaches the limitations of claims 2 and 13, wherein the positive electrode active material layer comprises a first powder and a second powder, wherein the first powder comprises the lithium cobalt oxide with the P63mc structure; and the second powder comprises the lithium-containing metal oxide, and the limitations of claims 3 and 14, wherein the lithium-containing metal oxide is provided on a surface of the lithium cobalt oxide, and the limitation of claims 6 and 17, wherein the lithium-containing metal oxide comprises a compound represented by a general formula LiaNO2+b, wherein 0<a<0.5, 0<b<6, and N comprises at least one selected from the group consisting of Al, Mg, Ti, Mn, Fe, Ni, Zn, Cu, Nb, Cr, Zr, and Y.
Regarding claims 4 and 15, Saito in view of Kang teaches all of the limitations as set forth above. Saito teaches [0022] "lithium composite oxide A … more preferably not less than 70 vol% relative to the total volume of the positive electrode active material” however, Saito is silent on wherein a mass ratio of the second powder to the first powder is m, wherein 0 < m ≤ 0.3.
Kang at [0048] discloses that the second lithium cobalt oxide (the shell) should be present in an amount from 10 to 30 wt% relative to the total weight amount of the positive electrode. (Examiner notes that this is equivalent to a weight ratio of about 0.9 to 0.23, which falls within the claimed range.) Kang contemplates that if the shell amount is too small, the improving effect due to the formation of the lithium deficient structure may be trivial, and if the amount is greater than 30 wt %, capacity may decrease.
A person of ordinary skill in the art would have been motivated, as of before the effective filing date of the instant invention, to select Kang’s mass ratio for the core shell secondary particle of modified Saito based on the weight range disclosed by Kang, with a reasonable expectation of achieving improved properties while maintaining capacity.
Regarding claims 5 and 16, Saito in view of Kang teaches all of the limitations as set forth above. Saito is silent on the particle size of the LCO core of the secondary particle and is silent on the thickness of the lithium-containing metal oxide layer on the surface of the lithium cobalt oxide. Therefore, Saito does not explicitly teach wherein an average thickness of the lithium-containing metal oxide on the surface of the lithium cobalt oxide is h, and an average particle size of the lithium cobalt oxide is D, wherein 0<h/D≤0.05.
Kang discloses at [0047] a core/shell ratio from 1:0.01 to 1:0.1 (encompasses the claimed range) and a shell thickness of 10 to 450 nm. “Where the radius of the core part deviates the upper limit and is excessively large, the increasing effect of the mobility of lithium ions according to the formation of the shell part including the lithium deficient lithium cobalt oxide and the resultant improving effect of battery properties may be trivial, and in the case where the thickness of the shell part deviates the
upper limit and is excessively large, the core part may be relatively decreased, and the structural stabilizing effect in the active material particle may be trivial. Kang at [0053] discloses an average particle diameter D50 of 10 µm to 50 µm. Examiner notes that the combination of Kang’s suggested particle diameter with Kang’s suggested shell thickness creates a shell/core ratio h/D of from 0.0002 to 0.045, which falls within the claimed range. At [0048] Kang contemplates that if the shell amount is greater than 30 wt%, capacity may decrease.
A person of ordinary skill in the art would have been motivated to select core and shell thicknesses as suggested by Kang for the secondary particle of modified Saito, with a reasonable expectation of balancing improved battery properties and structural stability with maintaining capacity of the battery.
Regarding claims 7 and 18, Saito in view of Kang teaches all of the limitations as set forth above. Saito further teaches [0031] LiaNabCoz1Mnz2M(1-z1-z2)O(2±y) where M is a metal element (except Li, Na, Co, Mn) and …0≤y<0. [Examiner notes that the text at [0031] reads LiaNabCz1Mnz2M(1-z1-z2)O(2±y) which is an obvious typographical error.] At Table 1 example 2, Saito discloses Li0.899Na0.028Co0.917Mn0.083, which meets the following conditions: (e) ratio of nLi to nCo+M is x, wherein 0.6<x<0.95; and (f) the lithium cobalt oxide is further doped with an element Na, a ratio of nNa to nCo+M is z, wherein 0<z<0.03, Regarding limitation (g) a ratio of nM to nCo+M is y, wherein 0<y<0.15; a molar concentration of element Co is nCo and a ratio of nCo to nCo+M is1-y, Examiner notes that the “y” of claims 7 and 18 is the sum of z2 and 1-z1-z2 in the above formula, and for Example 2, y = 0.083, which falls within the claimed range.
Examiner notes that the conditions of claims 7, 8, 18 and 19 are listed in the alternative, and the limitations of each claim can be met when only one of the conditions is taught or disclosed.
Regarding claims 8 and 19, Saito in view of Kang teaches all of the limitations as set forth above, and (as set forth in claim 7, above) teaches wherein the lithium cobalt oxide satisfies condition (h) the lithium cobalt oxide comprising a compound represented by a general formula LixNazCo1-yMyO2, wherein 0.6<x<0.95, 0<y<0.15, 0<z<0.03; ( [0024] Table 1 Example 2: Li0.899Na0.028Co0.917Mn0.083). Regarding condition (i) a main XRD peak of the lithium cobalt oxide corresponding to (002) crystal plane is in a range of 17.5° to 19°, this is shown at Saito FIG. 1.
Regarding claim 9, Saito in view of Kang teaches all of the limitations as set forth above. Saito is silent on the particle size of the LCO core of the secondary particle and is silent on the particle size of the “fine particles of inorganic compounds” of Saito at [0023]. Therefore, Saito does not explicitly teach wherein an average particle size of the second powder is D0, an average particle size of the first powder is D1, wherein D1 is in a range of 15 µm to 30 µm, 0<D0/D1<0.05. Kang [0053] 3 -50 microns
Kang at [0053] discloses an average particle diameter D50 of 10 µm to 50 µm. (This encompasses the claimed range of D1.) At [0048] Kang contemplates that if the shell amount is greater than 30 wt%, capacity may decrease. At [0047] Kang contemplates that “Where the radius of the core part deviates the upper limit and is excessively large, the increasing effect of the mobility of lithium ions according to the formation of the shell part including the lithium deficient lithium cobalt oxide and the resultant improving effect of battery properties may be trivial, and in the case where the thickness of the shell part deviates the upper limit and is excessively large, the core part may be relatively decreased, and the structural stabilizing effect in the active material particle may be trivial.
A person of ordinary skill in the art would have been motivated, as of before the effective filing date of the instant invention, to optimize the core diameter of the secondary particle of Saito in view of Kang, in order to balance battery capacity with improved battery performance, with a reasonable expectation of selecting a value within the claimed range.
Examiner notes that the shell of the core/shell secondary particle of modified Saito comprises the “fine particles of inorganic compounds” of Saito at [0023]. Kang discloses at [0047] a shell thickness of 10 to 450 nm. “Where the radius of the core part deviates the upper limit and is excessively large, the increasing effect of the mobility of lithium ions according to the formation of the shell part including the lithium deficient lithium cobalt oxide and the resultant improving effect of battery properties may be trivial, and in the case where the thickness of the shell part deviates the upper limit and is excessively large, the core part may be relatively decreased, and the structural stabilizing effect in the active material particle may be trivial.” A person of ordinary skill in the art would have been motivated to select a shell thickness as suggested by Kang for the secondary particle of modified Saito, in order to balance improved battery properties and structural stability with maintaining capacity of the battery.
The maximum particle size of the “fine particles of inorganic compounds” is less than the thickness of the shell. Therefore, the average particle size D0 is also less than the thickness of the shell (10 to 450 nm) as has been rendered obvious above. This creates a D0/D1 ratio of 0.03 or less, which falls within the claimed range.
Regarding claim 11, Saito in view of Kang teaches all of the limitations as set forth above, and Saito further teach wherein a charge cut-off voltage of the electrochemical apparatus is in a range of 4.6 V-4.8 V. ([0018] 4.6 V … "preferably not more than 5.0V")
Claim(s) 10 is/are rejected under 35 U.S.C. 103 as being unpatentable over Saito (US 20160351901 A1) in view of Kang (US 20170317342 A1) as set forth in claim 1, above, and in further view of Feng (Feng, L., Lu, X., Zhao, T., & Dillon, S. (2019). The effect of electrochemical cycling on the strength of LiCoO2. Journal of the American Ceramic Society, 102(1), 372-381.)
Regarding claim, 10 Saito in view of Kang teaches all of the limitations as set forth above. Examiner notes that the size of internal pores is not specified in the instant claim and that Claim 1 requires that the positive active material be “fully discharged”. However, Saito does not explicitly teach wherein particles of the lithium cobalt oxide with the P63mc structure have internal pores or cracks.
Feng, in the field of (abstract) LiCoO2 positive active materials, discloses (page 372 col. 2) “Many commercially relevant cathode materials, such as LiCoO2 or LiMn2O4, tend to fracture during cycling.” At (page 373 col. 1) It is known that line defects can accumulate in single‐ crystalline particles during cycling and that these particles are subject to fracture and failure. Line defects presumably evolve to accommodate the ≈1.9 vol% average strain that accumulates during cycling between Li0.5CoO2 and LiCoO2. In light of the teaching of Feng, a person of ordinary skill in the art would have expected to find internal cracks in the particles of lithium cobalt oxide of Saito in view of Kang, thus rendering obvious the instant claim limitation.
Conclusion
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CLAIRE A. RUTISER
Examiner
Art Unit 1751
/C.A.R./Examiner, Art Unit 1751
/JONATHAN G LEONG/Supervisory Patent Examiner, Art Unit 1751 1/8/2026