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 . If status of the application as subject to 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 a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
Status of Claims
Claims 1-19 are pending in the application and are presently examined.
Claim Objections
Claim 8 is objected to because of the following informalities. Claim 8 has parentheses “)” after the period. It seems that this is a typographical error and that this parentheses should be removed.
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.
Claims 3-5, 7, 9-11, & 16-17 are rejected under 35 U.S.C. 112(b) as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor(s) regard as the invention.
Claim 4 states “the proportion”. There is insufficient antecedent basis for this limitation in this claim.
Claims 3-5, 7, 9, 11, & 16-17 state “the surface portion”. There is insufficient antecedent basis for this limitation in these claims.
Claims 4-5, 7, 9, 11, & 16-17 state “the central portion”. There is insufficient antecedent basis for this limitation in these claims.
Claim 10 states:
the mole fractions of M3, M4 and P, calculated by Expression 1 below, in the positive electrode active material is 1.0 to 30.0, [Expression 1] P (mol%)/(M3 (mol%) + M4 (mol%))
It is unclear whether the mol% is based on the formula (e.g. mol% Al in Al2O3 is 2/5) or whether the mol% is based on the total number of moles of all compounds, ions, and solvents in the positive electrode active material. For present examination, Examiner presumes that the mol% is based on the formula.
Also, there are no examples in the specification for how to achieve this 1 to 30 mole fraction. If the mol% is based on the formula, then it is unclear what combination of compounds, taught in the specification, would achieve the claimed 1 to 30 mole fraction.
Claim 11 is rejected due to its dependance on claim 10.
Claim 16 states “the spinel phase and spinel-like phase” and “the entire crystal structure”. There is insufficient antecedent basis for these limitations in this claim.
Claim 16 states “the spinel phase and spinel-like phase” and “the entire crystal structure”. There is insufficient antecedent basis for these limitations in this claim.
Claim 16 states “than that”. “that” should be replaced by whatever “that” refers to.
Claim 17 is rejected due to its allowance on claim 16.
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.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
Determining the scope and contents of the prior art.
Ascertaining the differences between the prior art and the claims at issue.
Resolving the level of ordinary skill in the pertinent art.
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.
The claims are in bold font, the prior art is in parentheses.
Claims 1-3, 6, 12-15, & 18-19 are rejected under 35 U.S.C. 103 as being unpatentable over “Enhanced electrochemical performance of Al(NO3)3 and NH4H2PO4 co-modified Li1.11(Ni0.19Co0.07Mn0.6)O2” (Qiu) in view of US20220238871A1 (Lee), together “modified Qiu”.
With regard to claim 1, Qiu teaches the following claim limitations:
A positive electrode active material (abstract: cathode material) comprising
a lithium manganese based oxide (abstract: Li1.11(Ni0.19Co0.07Mn0.6)O2) in which a phase belonging to a C2/m space group and a phase belonging to an R3-m space group (page 9465. page 9467, left column) are dissolved or complexed, in which the lithium manganese-based oxide comprises… a plurality of primary particles (figure 1; page 9465)…
a coating layer comprising a first oxide containing at least one selected from a metal element and a metalloid element (abstract: Al2O3 coating layer) and a second oxide containing phosphorus (P) (abstract; page 9467, left column: NH4H2PO4) is formed on at least a part of the surface of the primary particle
Qiu, however, fails to teach the following claim 1 limitations, which are taught by Lee:
the lithium manganese-based oxide comprises a secondary particle formed by aggregating a plurality of primary particles (paragraph 47),
an average value of the minor axis lengths (paragraph 98) of the primary particles… is 130 nm or more and less than 850 nm (Table 1, Example 1: 0.2 μm = 200 nm)
Lee is directed to a lithium manganese oxide, with specifically-sized primary and secondary particles (paragraph 47; Table 1, Example 1), for a positive electrode (paragraphs 11-12, 33, & 54-56) with improved capacity, rate capability, and cycle characteristics (paragraph 15). It would have been obvious, to one of ordinary skill in the art, before the effective filing date of the invention, for Qiu’s particles to include a secondary particle formed by aggregating primary particles, and for the primary particles to have 200 nm minor axis length, as taught by Lee, for improved capacity, rate capability, and cycle characteristics.
Claim 1 also recites the following method for calculating the primary particle minor axis length:
the primary particles calculated from 20 primary particles selected in the order from longest-to-shortest minor axis lengths from the primary particles exposed on a surface of the secondary particle from the SME image of the secondary particle
Claim 1 is an apparatus claim – not a method of measurement or calculation claim. This method of measuring or calculating lengths does not limit this apparatus claim for examination.
With regard to claim 2, modified Qiu teaches the limitations of claim 1 as described above. Qiu also teaches the following claim 2 limitation:
the lithium manganese-based oxide is represented by Formula 1… Li(LiaM1xM2y)O2-bXb Wherein, M1 is at least one selected from Ni and Mn, M2 is at least one selected from Ni, Mn, Co, Al, P, Nb, B, Ti, Zr, Ba, K, Mo, Si, Fe, Cu, Cr, Zn, Na, Ca, Mg, Pt, Au, Eu, Sm, W, V, Ta, Sn, Hf, Ce, Gd and Nd, and M2 does not overlap with M1, X is a halogen that can substitute for at least some of the oxygen present in the lithium manganese-based oxide, 0<a≤0.7, 0≤b≤0.1, 0<x≤1, 0≤y<1, and 0<x+y≤1
Qiu teaches Li1.11Ni0.19Co0.07Mn0.6O2, which meets the requirements of Formula 1 with a=0.11; M1 = Ni and Mn with x=0.19 for Ni and x=0.6 for Mn; M2 = Co with y=0.07; and b=0 (title & abstract).
With regard to claim 3, modified Qiu teaches the limitations of claim 1 as described above. Modified Qiu also teaches the following claim 3 limitation:
the coating layer is formed on at least a part of the surface of the primary particle present in the surface portion of the secondary particle
Qiu’s primary particles, modified by Lee, aggregate into a secondary particle, as discussed above. Because the primary particles form the secondary particle, the primary particles and their coatings would be at a surface of the secondary particle.
With regard to claim 6, modified Qiu teaches the limitations of claim 1 as described above. Qiu also teaches the following claim 6 limitation:
the first oxide is represented by Formula 2 below, [Formula 2] LicM3dOe Wherein, M3 is at least one selected from Ni, Mn, Co, Al, Nb, B, Ti, Zr, Ba, K, Mo, Si, Fe, Cu, Cr, Zn, Na, Ca, Mg, Pt, Au, Eu, Sm, W, V, Ta, Sn, Hf, Ce, Gd and Nd, 0≤c≤10, 0≤d≤8, 0<e≤13, and the case in which c and d are 0 at the same time is excluded
Qiu teaches Al2O3, which meets the requirements of Formula 2 with c=0, M3=Al, d=2, and e=3 (abstract).
With regard to claims 12-14, modified Qiu teaches the limitations of claim 1 as described above. Qiu also teaches the following limitations of claims 12-14 (figure 1; page 9465, left column):
Claim 12
the lithium manganese-based oxide further comprises at least one phase selected from a spinel phase and a spinel-like phase
Claim 13
the spinel phase or spinel-like phase is dissolved or complexed with at least one selected from the primary particle and the coating layer
Claim 14
the spinel phase or spinel-like phase is present at at least a part of the interface between the primary particle and the coating layer
With regard to claim 15, modified Qiu teaches the limitations of claim 1 as described above. Claim 15 states:
when a lithium secondary battery using the positive electrode active material as a positive electrode and a lithium foil as a negative electrode is charged/discharged under the following charge/discharge conditions, [Charge/discharge conditions]
- Cut off voltage : 2.0V - 4.6V
- Charge : 1.0C (CC) / discharge : 1.0C (CC)
In a graph that uses a voltage (V) and a battery capacity (Q) for initial discharging and is plotted by a value (dQ/dV) obtained by differentiating the battery capacity (Q) with respect to the voltage (V), in which the X-axis is the voltage (V) and the Y-axis is the battery capacity (Q), there is a peak in at least one region selected from a first voltage region (3.0V or more and less than 3.3V) and a second voltage region (2.7V or more and less than 3.0V)
Modified Qiu teaches the positive electrode active material of claim 1; therefore, the graph of claim 15 would result from using that positive electrode active material.
With regard to claims 18 & 19, modified Qiu teaches the limitations of claim 1 as described above. Modified Qiu also teaches the following limitations of claims 18 & 19 (Qiu abstract: cathode. Lee abstract: positive electrode active material for a secondary battery):
Claim 18
A positive electrode comprising the positive electrode active material according to claim 1.
Claim 19
A lithium secondary battery using the positive electrode of claim 18.
Claim 4 is rejected under 35 U.S.C. 103 as being unpatentable over “Enhanced electrochemical performance of Al(NO3)3 and NH4H2PO4 co-modified Li1.11(Ni0.19Co0.07Mn0.6)O2” (Qiu) in view of US20220238871A1 (Lee), as applied to claim 1, and further in view of US20180145323A1 (Yoo).
Qiu fails to teach the following claim 4 limitation, which is taught by Yoo:
a gradient in which the proportion of at least one selected from x and y in Formula 1 changes from the surface portion to the central portion of the secondary particle is formed (paragraphs 56-60)
Yoo is directed to a lithium secondary battery with improved electrical and mechanical reliability and stability (paragraph 8). This battery includes a cathode active material particle with the following formula: LixM1aM2bM3cOy (paragraph 59). Ni, Co, or Mn can be M1 (paragraph 60). M1 (Ni, Co, or Mn) concentration gradient can continuously decrease from particle center to the surface (paragraph 56).
It would have been obvious, to one of ordinary skill in the art, before the effective filing date of the invention, for Ni, Co, or Mn in Qiu’s Li1.11Ni0.19Co0.07Mn0.6O2 to have a concentration gradient from particle center to the surface, as taught by Yoo, as part of a battery with improved electrical and mechanical reliability and stability.
Claim 7 is rejected under 35 U.S.C. 103 as being unpatentable over “Enhanced electrochemical performance of Al(NO3)3 and NH4H2PO4 co-modified Li1.11(Ni0.19Co0.07Mn0.6)O2” (Qiu) in view of US20220238871A1 (Lee), as applied to claim 1, and further in view of US20240047667A1 (Eom).
Modified Qiu also teaches the following claim 7 limitation:
the coating layer is formed on at least a part of the surface of the primary particle present in the surface portion of the secondary particle
Qiu’s primary particles, modified by Lee, aggregate into a secondary particle, as discussed above. Because the primary particles form the secondary particle, the primary particles and their coatings would be at a surface of the secondary particle.
Qiu, however, fails to teach the following claim 7 limitation, which is taught by Eom:
a gradient in which the concentration of M3 (M3=Al as discussed under claim 6 above) decreases from the surface portion to the central portion of the secondary particle is formed (paragraph 79: Al concentration decreases from primary particle’s surface to the center)
Eom teaches that the aluminum concentration gradient improves secondary battery high-temperature characteristics (paragraph 44). It would have been obvious, to one of ordinary skill in the art, before the effective filing date of the invention, for aluminum in modified Qiu’s secondary particles to have an aluminum concentration gradient, as taught by Eom, for improved high-temperature characteristics.
Claims 8-10 are rejected under 35 U.S.C. 103 as being unpatentable over “Enhanced electrochemical performance of Al(NO3)3 and NH4H2PO4 co-modified Li1.11(Ni0.19Co0.07Mn0.6)O2” (Qiu) in view of US20220238871A1 (Lee), as applied to claim 1, and further in view of US20150024280A1 (Uchiyama).
With regard to claim 8, Qiu fails to teach the following limitation, which is taught by Uchiyama:
the second oxide is represented by Formula 3… LifM4g(PhOi)j Wherein, M4 is at least one selected from Ni, Mn, Co, Al, Nb, B, Ti, Zr, Ba, K, Mo, Si, Fe, Cu, Cr, Zn, Na, Ca, Mg, Pt, Au, Eu, Sm, W, V, Ta, Sn, Hf, Ce, Gd and Nd, 0≤f≤10, 0≤g≤8, 0<h≤4, 0<i≤10, and 0<j≤13
Formula 3 can be Li3PO4 with f=3, g=0, h=1, i=4, and j=1.
In order to reduce interface resistance between active material and electrolyte, Uchiyama coats a positive electrode active material particle with a reaction suppressing layer (paragraphs 8-11). This reaction suppressing layer can be Li3PO4 (paragraph 42).
It would have been obvious, to one of ordinary skill in the art, before the effective filing date of the invention, for aluminum in modified Qiu’s second oxide to include Li3PO4, as taught by Uchiyama, for reduce interface resistance.
Claim 9 states:
the coating layer is formed on at least a part of the surface of the primary particle present in the surface portion of the secondary particle, and a gradient in which at least one of the concentrations of M4 and P decreases from the surface portion to the central portion of the secondary particle is formed
M4 is optional in Formula 3, because the stoichiometric coefficient for M4 can equal zero (g=0). In Uchiyama’s formula, Li3PO4, discussed under claim 8 above, there is no M4 (i.e. g=0). Claim 9 merely further defines optional M4, but does not require M4.
With regard to claim 10, Qiu fails to teach the following limitation, which is taught by Uchiyama:
Qiu teaches the following claim 10 limitation:
the coating layer comprises a first oxide represented by Formula 2… LicM3dOe Wherein, M3 is at least one selected from Ni, Mn, Co, Al, Nb, B, Ti, Zr, Ba, K, Mo, Si, Fe, Cu, Cr, Zn, Na, Ca, Mg, Pt, Au, Eu, Sm, W, V, Ta, Sn, Hf, Ce, Gd and Nd, 0≤c≤10, 0≤d≤8, 0<e≤13, and the case in which c and d are 0 at the same time is excluded,
Qiu teaches Al2O3, which meets the requirements of Formula 2 with c=0, M3=Al, d=2, and e=3 (abstract).
Qiu fails to teach the following claim 10 limitation, which is taught by Uchiyama:
the coating layer comprises… a second oxide represented by Formula 3… LifM4g(PhOi)j Wherein, M4 is at least one selected from Ni, Mn, Co, Al, Nb, B, Ti, Zr, Ba, K, Mo, Si, Fe, Cu, Cr, Zn, Na, Ca, Mg, Pt, Au, Eu, Sm, W, V, Ta, Sn, Hf, Ce, Gd and Nd, 0≤f≤10, 0≤g≤8, 0<h≤4, 0<i≤10, and 0<j≤13
Formula 3 can be Li3PO4 with f=3, g=0, h=1, i=4, and j=1. Uchiyama teaches Li3PO4 for coating a positive electrode active material particle (paragraph 42).
Claim 10 also states:
the mole fractions of M3, M4 and P, calculated by Expression 1 below, in the positive electrode active material is 1.0 to 30.0, [Expression 1] P (mol%)/(M3 (mol%) + M4 (mol%))
For Formula 2, Qiu teaches Al2O3, in which M3=Al. Thus, M3 mol%=2/5. For Formula 3, Uchiyama teaches Li3PO4, in which (a) there is no M4, because g=0; and (b) P mol%=1/8.
E
x
p
r
e
s
s
i
o
n
1
=
1
8
*
5
2
=
0.31
.
Modified Qiu discloses 0.31 mole fraction whereas claim 10 requires 1 to 30 mole fraction. MPEP 2144.05 (I) provides the law for this issue:
“Similarly, 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 America v. Banner, 778 F.2d 775, 783, 227 USPQ 773, 779 (Fed. Cir. 1985)… ‘The proportions are so close that prima facie one skilled in the art would have expected them to have the same properties.’”
Given that there is only a slight difference between modified Qiu’s 0.31 mole fraction and 1 to 30 mole fraction in claim 10, and further given the fact that no criticality is disclosed for the claimed range, the claimed range is an obvious variant of modified Qiu’s range.
Claim 11 is rejected under 35 U.S.C. 103 as being unpatentable over “Enhanced electrochemical performance of Al(NO3)3 and NH4H2PO4 co-modified Li1.11(Ni0.19Co0.07Mn0.6)O2” (Qiu) in view of US20220238871A1 (Lee) and US20150024280A1 (Uchiyama), as applied to claims 1 & 10, and further in view of US20180331362A1 (Niwata).
Claim 11 states:
the coating layer is formed on at least a part of the surface of the primary particle present in the surface portion of the secondary particle
Qiu’s primary particles, modified by Lee, aggregate into a secondary particle, as discussed above. Because the primary particles form the secondary particle, the primary particles and their coatings would be at a surface of the secondary particle.
Claim 11 also states:
a gradient in which at least one of the concentrations of M3, M4 and P decreases from the surface portion to the central portion of the secondary particle is formed
Qiu fails to teach phosphorus for M2. As discussed under claim 10, Uchiyama teaches Li3PO4 for coating a positive electrode active material particle (paragraph 42). Uchiyama, however, fails to teach the phosphorus concentration gradient.
Niwata teaches LixCo1-yMyO2-z, where M can be phosphorus (P), 0≤x≤1, 0<y<0.5, and −0.1≤z≤0.2, as a positive electrode active material (paragraphs 43-44 & claim 1). With M=P, x=1, y=0.4, and z=0, this formula is LiCo0.6P0.4O2. Niwata also teaches a gradient (increase or decrease) of element M from surface to center (paragraph 53). This concentration gradient can improve secondary battery cycle characteristics (paragraphs 5-6).
It would have been obvious, to one of ordinary skill in the art, before the effective filing date of the invention, for phosphorous, in Qiu’s particle modified with Uchiyama’s Li3PO4, to have a decreased concentration from the surface to the center.
Claims 16-17 are rejected under 35 U.S.C. 103 as being unpatentable over “Enhanced electrochemical performance of Al(NO3)3 and NH4H2PO4 co-modified Li1.11(Ni0.19Co0.07Mn0.6)O2” (Qiu) in view of US20220238871A1 (Lee), as applied to claim 1, and further in view of US20250279422A1 (Jeong). Claims 16-17 state:
Claim 16
the proportion of the spinel phase and spinel-like phase in the entire crystal structure present in the surface portion of the secondary particle is larger than that of the entire crystal structure present in the central portion of the secondary particle
Claim 17
a gradient in which the proportion of the spinel phase or spinel-like phase in the entire crystal structure decreases from the surface portion to the central portion of the secondary particle is formed
Qiu teaches a spinel phase (figure 1; page 9465, left column). Qiu, however, fails to teach a spinel gradient.
Jeong teaches a spinel gradient for improved battery initial resistance and storage characteristics (paragraphs 10, 29, 46-47, & 126). It would have been obvious, to one of ordinary skill in the art, before the effective filing date of the invention, for modified Qiu’s spinel to have a gradient from particle surface to core, as taught by Jeong, for improved battery initial resistance and storage characteristics.
Allowable Subject Matter
Claim 5 is 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 statement of reasons for allowable subject matter:
The closest prior art is “Enhanced electrochemical performance of Al(NO3)3 and NH4H2PO4 co-modified Li1.11(Ni0.19Co0.07Mn0.6)O2” (Qiu) in view of US20220238871A1 (Lee), as applied to claims 1-2, and further in view of US20180331362A1 (Niwata).
Claim 2 requires the following claim 2 compound:
Formula 1… Li(LiaM1xM2y)O2-bXb… 0<a≤0.7, 0≤b≤0.1, 0<x≤1, 0≤y<1, and 0<x+y≤1
Qiu teaches Li1.11Ni0.19Co0.07Mn0.6O2, which meets the requirements of Formula 1 with a=0.11; M1 = Ni and Mn with x=0.19 for Ni and x=0.6 for Mn; M2 = Co with y=0.07; and b=0 (title & abstract).
Claim 5 states:
M2 comprises phosphorus (P), and a gradient in which the concentration of phosphorus (P) decreases from the surface portion to the central portion of the secondary particle is formed
Qiu fails to teach phosphorus for M2. Qiu also fails to teach the phosphorus concentration gradient.
Niwata teaches LixCo1-yMyO2-z, where M can be phosphorus (P), 0≤x≤1, 0<y<0.5, and −0.1≤z≤0.2, as a positive electrode active material (paragraphs 43-44 & claim 1). With M=P, x=1, y=0.4, and z=0, this formula is LiCo0.6P0.4O2.
Niwata also teaches a gradient (increase or decrease) of element M from surface to center (paragraph 53). This concentration gradient can improve secondary battery cycle characteristics (paragraphs 5-6).
Niwata differs from claim 5 in that Niwata’s stoichiometric coefficient for lithium must be less than or equal to 1, but in Formula 1 it must be greater than 1.
Furthermore, it would not have been obvious, to one of ordinary skill in the art, to replace Mn in Qiu’s Li1.11Ni0.19Co0.07Mn0.6O2 with P because Mn is a metal and P is a nonmetal.
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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/R.G.W./Examiner, Art Unit 1721
/ALLISON BOURKE/Supervisory Patent Examiner, Art Unit 1721