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 .
Response to Amendment
This is a final Office action in response to Applicant’s remarks and amendments filed on 08/17/2026. Claims, 14, and 16 are amended. Claim 13 is canceled. Claims 11, 17, and 18 remain withdrawn. Claims 1 – 2, 4 – 8, and 14 – 16 are pending in the current Office action.
A new grounds of rejection, necessitated by applicant’s amendment, is presented below.
Response to Arguments
Applicant’s arguments with respect to claim(s) 1 have been considered but are moot because the arguments do not apply to the new combination of prior art being used in the current rejection. Specifically, in the new grounds of rejection below, the previously cited prior art is further modified by new teaching reference Kim (US PG Pub. 2017/0092932 A1) to address the new limitation of amended claim 1.
Furthermore, applicant’s arguments regarding Zhang teaching away from a barrier layer comprising a spinel-phase compound based on [0002] is unpersuasive as [0002] only teaches that lithium-rich manganese-based cathode materials are coated to protect against corrosion by electrolyte, the dissolution of transition metals, and phase transition of the surface and does not mention anything regarding the use of coatings having a spinel phase. Furthermore, the examiner respectfully notes that Zhang is a teaching reference relied upon to render obvious the claimed concentration gradient of Mn, and that the primary reference, Ahn, does not appear to make any teaching/suggestion against using a coatings having a spinel-phase . Additionally, the examiner notes, in the current rejection, that Kim, the new teaching reference relied upon by the examiner to address the limitation regarding the barrier coating, suggests that such coatings are applicable to lithium-rich manganese-based cathode materials (See Kim: [0036 – 0038] and [0091 – 0093]).
Claim Rejections - 35 USC § 103
The text of those sections of Title 35, U.S. Code not included in this action can be found in a prior Office action.
Claim(s) 1 – 2, 14 and 16 are rejected under 35 U.S.C. 103 as being unpatentable over Ahn (US PG Pub. 2016/0336594 A1), as evidenced by Yamamoto (US PG Pub. 2012/0217435 A1) and in view of Modeki (US PG Pub. 2013/0327979 A1), Zhang (CN112624207A) and Kim (US PG Pub. 2017/0092932 A1). {Examiner Note: All prior art except for Kim was cited in previous O.A. mailed 05/18/2026.}
Regarding Claim 1, Ahn discloses a lithium secondary battery using a positive electrode active material comprising a lithium manganese-based oxide ([0052 – 0054];[0110]).
Ahn teaches that the positive electrode active material may be a composite with a layered structure or solid solution, and further specifically teaches an exemplary embodiments where the lithium manganese-oxide has a structure in which a LiM’O2 phase and a Li2MO3 phase are intermixed ([0056]).
For a lithium manganese-based oxide active material, Yamamoto teaches that LiMxMn1-xO2 wherein M is Ni and/or Co; 0 < x ≤ 1 has a crystal system belonging to a space group of R-3m and Li2M′(1-y)MnyO3 wherein M′ is Ni and/or Co; 0 < y ≤ 1 has a crystal system belonging to a space group of C2/m ([0029 – 0032];[0053]).
By including a phase that corresponds to a crystal system belonging to a space group of R-3m {i.e. LiM’O2} intermixed with a phase that corresponds a crystal system belonging to a space group of C2/m {i.e. Li2MO3}, one with ordinary skill in the art would reasonably expect the active material of Ahn to necessarily and inherently have a phase belonging to a C2/m space group {i.e. Li2MO3} and a phase belonging to an R-3m space group {i.e. LiM’O2} that are complexed.
In one exemplary embodiment, the lithium manganese-based oxide is particularly represented by xLi2MnO3-(1−x)LiNiaCobMncO2 where 0<x<1, 0<a<1, 0<b<1, 0<c<1, and a+b+c=1 (Formula 2; [0058 – 0059]); therefore, Ahn discloses a lithium manganese-oxide that overlaps the scope of the claimed Chemical Formula 1-1: rLi2MnO3-b’’X’b’’·(1−r)Lia’M1X’M2y’O2-b’Xb’. That is, in Ahn, M1 is Ni and Mn, which is within the claimed scope of at least one selected from Ni and Mn, M2 is Co, which is within the claimed selection of metals, and M2 does not overlap with M1. Furthermore, in Formula 2 of Ahn, there is no halogen corresponding to X and X’; thus, Formula 2 of Ahn is within the claimed scope of Chemical Formula 1-1 where b’ = 0 and b’’ = 0, which are within the claimed ranges of 0 ≤ b’ ≤ 0.1 and 0 ≤ b’’ ≤ 0.1. The corresponding a’ subscript in Ahn is equal to 1 ([0058 – 0059]), which is within the claimed range 0 < a’ ≤ 1. The corresponding x’ {i.e. “a” and “c” in Formula 2} and y’ {“b” in Formula 2} subscripts of Ahn are within the range of greater than 0 and less than 1 and have a sum of 1 ([0059]), and thus are within the claimed ranges of 0 < x’ ≤ 1, 0 < y’ < 1, and 0 < x’ + y’ ≤ 1. The corresponding r subscript in Ahn is taught to be within the range of greater than 0 and less than 1 ([0059]), which encompasses the claimed range of 0 < r ≤ 0.7.
Modeki teaches a lithium manganese-based positive electrode material with a formula of xLi4/3Mn2/3O2+(1−x)LiMnαCoβNiγO2 , where in the formula: 0.2≦α≦0.6, 0≦β≦0.4, and 0.2≦γ≦0.6 ([0015 – 0021]). The molar ratio of Li4/3Mn2/3O2 and LiMnαCoβNiγO2 in the formula {i.e. the “x” subscript} is taught to be equal to or more than 0.36 and less than 0.50 for the purpose of achieving gas generation suppression during initial cycling ([0022 – 0023]).
Since Ahn’s lithium manganese-oxide is similar in composition to the one taught in Modeki, it would have been obvious to one with ordinary skill in the art, before the effective filing date of the claimed invention to control the molar ratio {i.e. the subscript “r” in Formula 2} of the phases taught in Ahn {i.e. Li2MnO3 and LiNiaCobMncO2} to be within the range taught by Modeki, and thus be within the claimed range, with a reasonable expectation of success in achieving the capability of suppressing gas generation in an initial cycle of the active material.
Ahn further discloses wherein the lithium manganese-based oxide is a core-shell particle (Fig. 1; [0052];[0071]).
Ahn does not explicitly disclose wherein the manganese exhibits a decreased concentration gradient from the core to the shell.
Zhang teaches a lithium-rich manganese-based oxide having a concentration gradient where the Mn content gradually decreases from the inside of the particle to the particle surface and the Ni element content gradually increases, and the lithium-rich manganese also includes Co ([0003];[0007]; [0014]). The concentration gradient of Ni and Mn allows for a high manganese content inside the particle that provides high discharge capacity and a high Ni content on the surface/outer part of the particle that provides high operating voltage and structural stability ([0014]). Furthermore, the concentration gradient as taught by Zhang allows for the material to maintain a high operating voltage and energy density while effectively suppressing capacity/voltage degradation during cycling ([0014]).
Since Ahn also teaches a lithium-rich manganese based positive electrode active material and is concerned with obtaining a high capacity active material with improved lifespan characteristics during high voltage operation of a lithium battery ([0006];[0011]), it would have been obvious to one with ordinary skill in the art, before the effective filing date of the claimed invention, to modify the core-shell active material particles of Ahn to have a concentration gradient of Ni and Mn from the core to the shell, as taught by Zhang, and thus obtain a core-shell particle where the content of Mn decreases from the core to the shell, with a reasonable expectation of success in obtaining an active material with a high operating voltage and energy density and effectively suppressing capacity/voltage degradation during cycling.
Ahn teaches the active material particles having a core-shell structure and further, in Figs. 3A and 4, Ahn shows that the active material particles are in the form of secondary particles (Fig. 1; [0052];[0071]).
Modified Ahn does not explicitly disclose wherein there is a barrier layer covering at least a part of the core-shell particle, and the barrier layer comprises a spinel-phase compound.
Kim teaches composite active material including a core of lithium transition metal oxide and a surface treatment layer that includes a lithium-free oxide having a spinel structure ([0037];[0083]; [0087]). The surface treatment layer is taught by Kim to function as a protective layer for the core material that can suppress a side reaction between the core and an electrolyte and prevent a transition metal from flowing out of the core, which is capable of intercalating/deintercalation lithium ([0040]). Furthermore, Kim’s taught selection of core materials include within its scope lithium manganese-based composite metal oxides and, based on Chemical Formulas 10 – 11, compounds such as the active material as taught by Ahn ([0087 – 0093]).
Since Ahn is also concerned with reducing reactivity with electrolyte ([0066]), it would have been obvious to one with ordinary skill in the art, before the effective filing date of the claimed invention, to further modify the active material of Ahn to include the lithium free oxide coating layer as taught in Kim, and thus obtain the claimed barrier layer comprising a spinel-phase compound (Kim: [0038 – 0039]), with a reasonable expectation of success in achieving reduced side reactions with electrolyte, as desired by Ahn, in addition to the prevention of the flowing out of transition metal from the core {i.e. the core-shell particle of Ahn}.
Regarding Claim 2, modified Ahn discloses all limitations as set forth above. For evaluating working examples that are in the form of coin-half cells, Ahn teaches a formation operation charging voltage of 4.7V and a discharging voltage of 2.5V, and further teaches, following the formation operation, subjecting the cells to a voltage of 4.6V for charging and discharging to a voltage of 2.5V ([0149 – 0150]).
Based on the instant specification, the claimed voltage profile appears to be derived from the operating conditions of a lithium secondary battery using the claimed positive electrode active material ([0030 – 0031]). The lithium secondary battery of the instant invention is further taught to include: a negative electrode comprising a current collector ([0188 – 0189]) and a negative electrode active material layer ([0190]), a separator ([0195]), and an electrolyte including an organic solvent and lithium salt ([0197 – 0200]) or a solid electrolyte that is preferably a sulfide-solid electrolyte ([0201]).
The lithium secondary battery of modified Ahn, as established above, includes, in addition to a positive electrode including the an active materials corresponding to the claimed active material, a negative electrode having a current collector material and active material within the scope taught in the instant specification ([0113 – 0120]), a separator ([0121];[0130]) within the scope taught in the instant specification, and further an electrolyte comprising solvents and salts or solid electrolytes also within the scope taught in the instant specification ([0122 – 0126]).
Modified Ahn does not explicitly disclose wherein the first cycle during formation of the lithium secondary battery has a formation voltage range in which the upper voltage limit (fv1) is 4.4 or more and 4.6V or less; however, in light of the battery of modified Ahn being significantly similar in structure to the battery as claimed and/taught by the instant specification, and in light of Ahn already teaching obtaining half-cells utilizing their lithium-rich manganese-based active material with a formation voltage range with an upper limit of 4.7V and a lower limit of 2.6V and an operation charging voltage of 4.6V; one with ordinary skill in the art would reasonably expect (given the same test/operation conditions), the first cycle, during the formation of the secondary battery of modified Ahn, to have a formation voltage range in which the upper voltage limit (fv1) is of 4.4V or more and 4.6V or less. Furthermore, the courts have found where the claimed and prior art products are identical or substantially identical in structure or composition, or are produced by identical or substantially identical processes, a prima facie case of either anticipation/obviousness has been established. In re Best, 562 F.2d 1252, 1255, 195 USPQ 430 433 (CXPA 19771).
Regarding Claim 14, modified Ahn discloses all limitations as set forth above. Ahn further discloses wherein the lithium manganese-based oxide is present as a secondary particle in which a plurality of primary particles agglomerate, that is in Figs. 3A and 4, Ahn shows an example active material particle that is comprised of a plurality of smaller particles, which one with ordinary skill in the art would recognize to be a secondary particle comprised of a plurality of agglomerated primary particles.
Furthermore, as established above, the active material of modified Ahn includes the barrier layer on a surface of the primary particles that make up the secondary particles of the active material (Kim: [0070 – 0073]); therefore, modified Ahn provides the claimed structure of wherein the barrier layer covers at least a part of the surfaces of the primary particle and the secondary particle.
Regarding Claim 16, modified Ahn discloses all limitations as set forth above. Modified Ahn includes the lithium-free oxide coating as taught by Kim (Kim: [0038 – 0039]); therefore, the barrier layer of modified Ahn is an oxide represented by AM2O4-aXa wherein 0 < a ≤ 1 where A includes at least one selected from tin (Sn), magnesium (Mg), molybdenum (Mo), copper (Cu), zinc (Zn), titanium (Ti), nickel (Ni), calcium (Ca), iron (Fe), vanadium (V), lead (Pb), cobalt (Co), germanium (Ge), cadmium (Cd), mercury (Hg), strontium (Sr), manganese (Mn), aluminum (Al), tungsten (W), and beryllium (Be); M includes at least one selected from Mg, Zn, Al, V, Mn, gallium (Ga), chromium (Cr), Fe, rhodium (Rh), Ni, indium (In), and Co; X includes at least one of F, S, B, and P; and A is different from M (Kim: [0048 – 0051]). As such, modified Ahn’s oxide overlaps in scope with claimed first oxide represented by Chemical Formula 2.
Specifically, when X is B, Chemical Formula 1 of Kim corresponds to claimed Chemical Formula 2 where: c = 0, which is within the claimed scope of 0≤c≤9; M {i.e. Refer to A and M in Kim’s formula} is selected from a list of metals overlapping the claimed scope ([0050 – 0051]), d {i.e. refer to a in Kim’s formula} is 0 < d ≤ 0.1 ([0049]), which is within the claimed range 0<d≤8; and f {i.e. refer to “4-a” in Kim’s formula} is 3.9≤f≤4 ([0049]), which is within the claimed scope of 2≤f≤13.
Therefore, when modifying Ahn to include the lithium-free oxide coating of Kim, selection of a lithium-free oxide within the overlapping portion of the claimed scope and the scope taught by Kim would have been obvious before the effective filing date of claimed invention because such a selection would be a selection of oxide from a finite selection of oxides exemplified by Kim (Kim: [0054]), and thus would have a reasonable expectation of success in being a suitable coating oxide for the active material of Ahn and further achieving the desired benefit of reduced side reactions with electrolyte [See MPEP2143(I)(E)].
Claim(s) 4 – 8 are rejected under 35 U.S.C. 103 as being unpatentable over Ahn (US PG Pub. 2016/0336594 A1), Yamamoto (US PG Pub. 2012/0217435 A1), Modeki (US PG Pub. 2013/0327979 A1), Zhang (CN112624207A) and Kim (US PG Pub. 2017/0092932 A1), as applied to claim 1 above, and further in view of Morita (JP2010080407A, cited in previous Office action mailed 11/06/2025) and Yang (“Understanding Voltage Decay in Lithium-Rich Manganese-Based Layered Cathode Materials by Limiting Cutoff Voltage”, Applied Materials & Interfaces; vol. 8; 2-17; pp. 18867 – 1877, cited in previous Office action mailed 11/06/2025).
Regarding Claims 4 – 8, modified Ahn discloses all limitations as set forth above. For evaluating working examples that are in the form of coin-half cells, Ahn teaches a formation operation charging voltage of 4.7V and a discharging voltage of 2.5V, and further teaches, following the formation operation, subjecting the cells to a voltage of 4.6V for charging and discharging to a voltage of 2.5V ([0149 – 0150]).
Modified Ahn does not explicitly disclose wherein the upper voltage limit (ov1) of the operating voltage range during operation of the lithium secondary battery has a range of greater than 4.3 V and 5.0V or less (Claim 4), 4.6V or more (Claim 6), 4.5V or more and less than 4.6V (Claim 7), or less than 4.5 V (Claim 8); and the lower voltage limit (ov2) has a range of 2.0 V or more and less than 3.0V (Claim 5 – 8).
Morita teaches a nonaqueous electrolyte secondary battery with a lithium transition metal composite oxide as the positive electrode active material ([0033];[0042][0073 – 0075]). Morita further teaches controlling the upper limit charging voltage of the battery to preferably be higher than 4.20V and most preferably be 4.35V to 4.65V for the purpose of the optimizing the amount of lithium released per unit mass and improving electrode energy density ([0074]). As the charging voltage is increased; however, the reactivity between the positive electrode active material and electrolyte increases, resulting in deterioration of the active material, eluted metals being precipitated on the negative electrode side, inhibiting Li absorption/release, accelerating the decomposition reaction of the electrolyte at the interface, forming a film on the surface, and causing gas generation ([0025]). The lower limit discharge voltage is taught to be set to 2.00V or more and 3.30 V or less ([0074]).
Yang teaches, for a lithium-rich manganese-based layered (LRMO) cathode material, that upon high charge and/or low discharge voltages, severe structural variations such as formation of the spinel phase and migration of transition metal ions inside the particles occur on the LRMO electrode, and that moderate voltages in a range of 4.4 – 2.8V shows stable structure during cycling (Refer to Abstract and the Conclusion section paragraph).
Since Ahn teaches a battery with a lithium-rich manganese-based positive electrode active material, it would have been obvious to one with ordinary skill in the art, before the effective filing date of the claimed invention, to control the upper voltage limit and lower voltage limit of the operating voltage of Ahn’s lithium secondary battery to be within overlapping portion the claimed ranges and the ranges taught by Morita and Yang to optimize the reactivity between the positive electrode material and battery electrolyte, the structural stability of active material, and the electrode energy density, with a reasonable expectation of success and without undue experimentation [MPEP 2144.05(II)]).
Claim(s) 15 is rejected under 35 U.S.C. 103 as being unpatentable over Ahn (US PG Pub. 2016/0336594 A1), Yamamoto (US PG Pub. 2012/0217435 A1), Modeki (US PG Pub. 2013/0327979 A1), Zhang (CN112624207A) and Kim (US PG Pub. 2017/0092932 A1), as applied to claim 1 above, and further in view of Park (US PG Pub. 2019/0006669 A1).
Regarding Claim 15, modified Ahn discloses all limitations as set forth above. In Figs. 3A and 4, Ahn shows the active material particles being secondary particles comprised of a plurality of primary particles, as such, one with ordinary skill in the art would reasonably expect boundaries to necessarily and inherently be included between adjacent primary particles of the active material in modified Ahn.
Furthermore, the active material of modified Ahn has a core-shell structure and includes a coating layer of lithium-free oxide (Refer to rejection of claim 1; Ahn: [0011]; and Kim: [0037];[0039];[0058 – 0054]).
Modified Ahn does not explicitly disclose wherein the barrier layer is present in a state of being diffused from the surface portion of the secondary particle to the central portion thereof along the grain boundary.
Park, also directed to composite, core-shell cathode active materials including lithium transition metal oxides ([0035 – 0036]), teaches the core-shell active material having grain boundaries and further teaches the grain boundaries including a first composition having a spinel crystal structure ([0036 – 0038]). Park further teaches that including a composition having a spinel crystal structure in the grain boundary between adjacent primary particles provides allow for lithium ion conduction within the core, suppresses the elution of Ni ions from primary particles of the core, and suppresses side reactions of the primary particles and the electrolyte solution within the core ([0038]). Furthermore, such a configuration is taught to improve cycle characteristics, suppress deterioration of the active material, and decrease gas occurrence ([0038]). Park additionally teaches that the grain boundary may also include may further include a lithium transition metal oxide, a lithium-free transition metal oxide, or a mixture thereof, which is a second composition ([0054]).
Therefore, as the active material of Ahn is a core-shell active material that includes Ni (Refer to Ahn: Chemical Formula 2; [0018]) and a lithium-free oxide having a spinel structure on the core-shell surface, it would have been obvious to one with ordinary skill in the art, before the effective filing date of the claimed invention, to include some of the lithium-free oxide coating layer in, and thus along, the grain boundaries of Ahn’s active material, as suggested by Park, with a reasonable expectation of success in obtaining a cathode active material particle with improved ion conduction in the core, suppressed Ni ion elution from the core, suppressed electrolyte reactivity in the core, and further an active material with improved stability and cycle characteristics.
Conclusion
THIS ACTION IS MADE FINAL. 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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/A.Y.O./Examiner, Art Unit 1751
/Haroon S. Sheikh/Primary Examiner, Art Unit 1751
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