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 Office Action is responsive to the amendment filed on 10/30/2025. Claim 20 is canceled. Claims 1-19 are pending. Claims 9, 10, 16-19 are withdrawn from further consideration as being drawn to a non-elected invention, in accordance with 37 CFR 1.142(b). Applicant’s arguments have been considered. However, upon further consideration, the instant claims are rejected under new grounds of rejections. Claims 1-8, 11-15 are finally rejected for reasons stated herein below.
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 1-7, 11-15 are rejected under 35 U.S.C. 103 as being unpatentable over Konishi (US 2015/0102256) in view of Zhang (CN 112624207) and Choi (US 2021/0057731).
Regarding claims 1, 7, a positive electrode active material comprising a lithium manganese-based oxide in which a phase belonging to a C2/m space group and a phase belonging to an R3-m space group are dissolved or complexed, Konishi discloses a positive electrode active material comprising a composition
xLi2MnO3-(1-x)LiNiaMnbO2,
0.2<x<0.8, 0.5<a<1, 0<b<0.5, and a+b=1. See Abstract. Further,
0.45<x<0.55, 0.6<a<0.65, 0.35<b<0.4, and a+b=1. See [0017].
In Example 1 of Konishi, the composition is
0.5Li2MnO3-(0.5)LiNi0.625Mn0.375O2. See Table.1
Konishi’s formula reads on the Chemical formula 1-1 as disclosed by the Applicants. See [0083] of the instant Specification.
Regarding claim 7, It is noted that a crystalline is an intrinsic property of a chemical composition, and hence Konishi’s formula is also crystalline.
Regarding claim 11, the lithium manganese-based oxide represented by Chemical Formula 1-1 is met by Konishi. For example, see Example 1.
The instant Specification further states:
states:
[0094] The Li/metal molar ratio measured from the lithium manganese-based oxide represented by Chemical Formula 1 or 1-1 may be greater than 1, preferably, 1.1 to 1.6. It is possible to form an overlithiated lithium manganese-based oxide when the Li/metal molar ratio measured from the lithium manganese-based oxide has a value greater than at least 1. In addition, in order for the lithium manganese-based oxide to properly form a solid solution in which a phase belonging to a C2/m space group and a phase belonging to an R3-m space group are dissolved or complexed and also exhibit a high capacity under a high voltage operating environment, the Li/metal molar ratio of the lithium manganese-based oxide is preferably 1.1 to 1.6.
[0095] In addition, to properly form a solid solution in which the phase belonging to the C2/m space group and the phase belonging to the R3-m space group are dissolved or complexed, the content of manganese among all metal elements except lithium present in a lithium manganese-based oxide represented by Chemical Formula 1 or 1-1 is preferably 50 mol % or more.
[0096] In order for the lithium manganese-based oxide to have the characteristics of an OLO exhibiting a high capacity under a high voltage operating environment, the content of manganese among all metal elements except lithium in the lithium manganese-based oxide is more preferably 50 mol % or more and less than 80 mol %, and even more preferably, 55 to 75 mol %. When the content of manganese in the lithium manganese-based oxide is more than 80 mol %, a phase transition may occur due to the migration of a transition metal (particularly, manganese) in the lithium manganese-based oxide during formation and/or operation of a lithium secondary battery. This phase transition forms a spinel phase, and the spinel phase acting as an impurity in the lithium manganese-based oxide may induce a decrease in charge/discharge capacity or voltage decay during the cycling of a lithium secondary battery.
[0097] To properly form a solid solution in which the phase belonging to the C2/m space group and the phase belonging to the R3-m space group are dissolved or complexed, the content of nickel among all metal elements except lithium in the lithium manganese-based oxide represented by Chemical Formula 1 or 1-1 is preferably less than 50 mol %.
[0098] When the content of nickel in the lithium manganese-based oxide is 50 mol % or more, since it is difficult to sufficiently form the C2/m phase, or the phase belonging to the C2/m space group and the phase belonging to the R3-m space group cannot sufficiently form a solid solution, phase separation may be caused during formation and/or operation of a lithium secondary battery.
[0099] In addition, as described below, in order for nickel to be sufficiently present on the surface of the lithium manganese-based oxide provided as a core-shell particle in which a concentration gradient of transition metals is formed in the particle, the content of nickel in the lithium manganese-based oxide is preferably 25 to 45 mol %.
[0104] In the lithium manganese-based oxide represented by Chemical Formula 1-1, when r is more than 0.7, the proportion of Li.sub.2MnO.sub.3-b″X′.sub.b″, which is a C2/m phase oxide, in the lithium manganese-based oxide is excessively large, and as a result, the irreversible capacity and resistance of the positive electrode active material increase, which may lower the discharge capacity. That is, to improve surface kinetics by sufficiently activating a C2/m-phase oxide with relatively high resistance in the lithium manganese-based oxide, the R3-m phase oxide is preferably present in a predetermined proportion or more.
Hence, it is noted that the Example 1 of Konishi reads on Applicant’s “a phase belonging to a C2/m space group and a phase belonging to an R3-m space group are dissolved or complexed”.
Regarding claim 1, 7, wherein the lithium manganese-based oxide is a core-shell particle in which at least one transition metal constituting the lithium manganese-based oxide exhibits a concentration gradient from the core to the shell, and regarding claim 5, the lithium manganese-based oxide of the positive electrode active material is present in at least one form selected from a single primary particle and a secondary particle in which a plurality of primary particles agglomerate, the primary particle is a core-shell particle in which at least one transition metal exhibits a concentration gradient from the central portion of the primary particle to the surface portion thereof, and regarding claim 12, the lithium manganese-based oxide is a core-shell particle in which a concentration of at least one selected from nickel and manganese exhibits a gradient from the core to the shell, Zhang teaches a lithium-rich manganese-based positive electrode material with full-concentration gradient distribution, wherein the Mn element content is linearly reduced from the inside to the surface, and the Ni element content is linearly increased. The prepared material is high in degree of sphericity, narrow in particle size distribution and stable in crystal layered structure, and has relatively high energy density and excellent cycling stability. See Abstract.
It is noted that the outer layer of Zhang [0065] reads on Applicant’s “shell”.
Regarding claim 7, Zhang teaches wherein the lithium manganese-based oxide includes a primary particle in which at least one crystallite is present,
the crystallite has at least one transition metal exhibiting the concentration gradient from the central portion of the crystallite to the surface portion thereof.
It would have been obvious to one of ordinary skilled in the art at the time the invention was made to form the particles of Konishi as primary particles having a concentration gradient within a crystal of Konishi, as taught by Zhang, for the benefit of achieving energy density and excellent cycling stability.
Regarding claims 1, 7, a barrier layer covering at least a part of the shell surface is present, Zhang teaches a surface coating can protect the material from electrolyte erosion, phase change, and crystal structure of materials [0002]. It would have been obvious to one of ordinary skilled in the art at the time the invention was made to add a coating layer to the particle of Konishi, as taught by Zhang, for the benefit of stabilizing the active material particle.
Regarding claim 7, the barrier layer of Konishi modified by Zhang covers at least a part of the surface of the primary particle, and inhibits or mitigates the dissolution of a transition metal from the primary particle.
Regarding claim 13, there is thermogravimetric loss in the lithium manganese-based oxide at 700 °C during thermogravimetric analysis of the lithium manganese-based oxide under an inert gas atmosphere, and
wherein the difference (y-x) between the weight loss rate (x) of the lithium manganese-based oxide at 400 °C and the weight loss rate (y) of the lithium manganese-based oxide at 700 °C is 0.03 wt% or more, the instant Specification states on page 31:
Meanwhile, as defined herein, the lithium manganese-based oxide in which at least a part of the surface of the primary particle and//or the secondary particle is covered with the barrier layer begins to experience thermogravimetric loss at approximately 500° C., and the thermogravimetric loss of the lithium manganese-based oxide may be confirmed at 700° C.
It is noted that the combination of Konishi modified by Zhang reads on Applicant’s claim 13.
Regarding claims 1, 7, a spinel phase is present on at least a part of the shell surface, the instant Specification states on page 30:
However, unlike the spinel phase formed by the phase transition caused by the migration of a transition metal in the lithium manganese-based oxide, when a spinel phase is formed on the surface of the primary particle and/or the secondary particle and a barrier layer is formed on the surface of the lithium manganese-based oxide at the same time, such a spinel phase may not only contribute to the surface stabilization of the lithium manganese-based oxide, but may also serve as a 2D and/or 3D path through which lithium ions in the lithium manganese-based oxide diffuse.
Accordingly, as a spinel-phase compound is present on the surface of the lithium manganese-based oxide by forming the barrier layer present to inhibit the dissolution of a transition metal from the primary particle and/or the secondary particle, even when the surface(s) of the primary particle and/or the secondary particle is(are) covered with the barrier layer, the lithium manganese-based oxide may exhibit an appropriate level of electrical conductivity.
In addition, if needed, the barrier layer may include at least two oxides selected from the first to third oxides in order to effectively inhibit or mitigate the dissolution of a transition metal from the lithium manganese-based oxide, and at the same time, improve the surface kinetics of the lithium manganese-based oxide.
Zhang teaches a barrier layer, but does not teach a barrier layer having a spinel phase. Choi teaches the positive electrode active material may include a coating layer covering at least a part of the surface of the primary particle (e.g., the interface between the primary particles) and/or the surface of the secondary particle formed by agglomerating the primary particles, thereby increasing structural stability [0078]. In addition, when the positive electrode active material is used in a lithium secondary battery, the high-temperature storage stability and lifetime of the positive electrode active material may be improved. In addition, the oxide may reduce residual lithium in the positive electrode active material and also serve as a migration pathway of lithium ions, and therefore, it can have a positive influence on the efficiency of a lithium secondary battery [0087]. The coating includes a lithium boron oxide [0088]. It would have been obvious to one of ordinary skilled in the art at the time the invention was made to use the lithium boron oxide of Choi as the barrier layer of Konishi modified by Zhang, as taught by Choi, for the benefit of stabilizing the positive active material.
It is noted that the lithium boron oxide of Choi meets a first oxide represented by Chemical Formula 2 as disclosed in the Specification page 28, as well as in Applicant’s claim 14. It is further noted that the positive active material of Konishi meets the active material Chemical Formula 1-1 as disclosed in the Specification page 16, as well as in Applicant’s claim 11. Hence, it appears that a spinel phase would exist in the combination of Konishi modified by Zhang and Choi also.
Regarding claim 2, the lithium manganese-based oxide in the positive electrode active material is present as a secondary particle in which a plurality of primary particles agglomerate, the secondary particle is a core-shell particle in which at least one transition metal exhibits a concentration gradient from the central portion of the secondary particle to the surface portion thereof, Choi teaches a positive active material having primary particles enabling lithium intercalation and deintercalation and secondary particles formed by agglomerating the primary particles [0035]. The primary particles have an aspect ratio gradient increasing from the center of the secondary particle to the surface thereof, and here, the aspect ratio gradient satisfies a specific numerical range which will be described below. In addition, as the primary particles having the above-described aspect ratio gradient pattern are present radially from the center of the secondary particle, it is possible to effectively relieve strain caused by the volume expansion of the primary particle during charging/discharging. Therefore, it is possible to improve the lifetime and stability of a lithium secondary battery using the positive electrode active material [0046]. Further, the primary particles have a metal M2 (M2 is at least one selected from Mn, B, Ba, Ce, Hf, Ta, Cr, F, Mg, Al, Cr, V, Ti, Fe, Zr, Zn, Si, Y, Nb, Ga, Sn, Mo, W, P, Sr, Ge, Nd, Gd and Cu [0071]) present at the surface of the secondary particle may exhibit a concentration gradient decreasing toward the center of the secondary particle. That is, the direction of the concentration gradient of M2 may be a direction from the surface of the secondary particle to the center of the secondary particle [0074].
It would have been obvious to one of ordinary skilled in the art at the time the invention was made to form the particles of Konishi modified by Hwang as primary particles having an aspect ratio gradient and a concentration gradient, as taught by Choi, for the benefit of forming a radial pattern to relieve strain caused by volume expansion.
Regarding claim 4, a region in which the concentration gradient of a transition metal is formed is present in the shell of the secondary particle, wherein the average thickness of the shell is 0.1 nm to 5 um, Choi teaches that the concentration gradient occurs from the surface of the secondary particle toward the center of the secondary particle [0074]. The outermost primary particle of Choi’s secondary particle reads on Applicant’s shell. Choi teaches the major axis length of the primary particle is in the range of 0.1 to 2 um [0038].
Regarding claim 2, the barrier layer is present to cover at least a part of the surface of the secondary particle, and inhibits or alleviates the dissolution of a transition metal from the secondary particle, regarding claim 3, a grain boundary is defined between adjacent primary particles, and the barrier layer is present in a state in a state of being diffused from the surface portion of the secondary particle to the central portion thereof along the grain boundary, Choi teaches the positive electrode active material may include a coating layer covering at least a part of the surface of the primary particle (e.g., the interface between the primary particles) and/or the surface of the secondary particle formed by agglomerating the primary particles, thereby increasing structural stability [0078]. In addition, when the positive electrode active material is used in a lithium secondary battery, the high-temperature storage stability and lifetime of the positive electrode active material may be improved. In addition, the oxide may reduce residual lithium in the positive electrode active material and also serve as a migration pathway of lithium ions, and therefore, it can have a positive influence on the efficiency of a lithium secondary battery [0087]. Here, the oxide may exhibit a concentration gradient decreasing from the surface of the secondary particle to the center thereof. Therefore, the concentration of the oxide may decrease from the outermost surface of the secondary particle to the center thereof [0090]. As described above, as the oxide exhibits a concentration gradient decreasing from the surface of the secondary particle to the center thereof, residual lithium present at the surface of the positive electrode active material may be effectively reduced, thereby preventing a side reaction caused by unreacted residual lithium in advance. In addition, a decrease in crystallinity in an inner region from the surface of the positive electrode active material by the oxide may be prevented. In addition, it is possible to prevent the entire structure of the positive electrode active material from collapsing due to the oxide during an electrochemical reaction [0091].
Regarding claim 14, the barrier layer includes a first oxide represented by Chemical Formula 2 as claimed. See Choi [0088].
Regarding claim 15, Choi teaches a gradient in which the concentration of at least one selected from B and M3 decreases from the barrier layer to the core of the lithium manganese-based oxide is formed [0091, 0091].
It would have been obvious to one of ordinary skilled in the art at the time the invention was made to add a barrier layer of Choi to the secondary particles of Konishi modified by Hwang and Choi for the benefit of increasing structural stability.
Regarding claim 4, 6, the average thickness of the barrier layer is 0.1 nm to 1 um, it would have been obvious to one of ordinary skilled in the art at the time the invention was made to form the coating of Choi at an appropriate thickness that would provide good stability to the primary and secondary particles.
Regarding claim 5, the barrier layer is present to cover at least a part of the primary particle, and inhibits or mitigates the dissolution of a transition metal from the primary particle, and regarding claim 7, the barrier layer covers at least a part of the surface of the primary particle, and inhibits or mitigates the dissolution of a transition metal from the primary particle, Choi teaches a coating layer covering at least a part of the surface of the primary particle (e.g., the interface between the primary particles) and/or the surface of the secondary particle formed by agglomerating the primary particles, thereby increasing structural stability [0086]. It is noted that Choi’s coating is capable of inhibiting or mitigating the dissolution of a transition metal from the primary particle.
Regarding claim 6, the region in which the concentration gradient of a transition metal is formed is present in the shell of the primary particle, wherein the average thickness of the shell is 0.1 nm to 2 um, it is noted that several sites at the surface of Hwang’s particle reads on Applicant’s claim 6.
Claim 8 is rejected under 35 U.S.C. 103 as being unpatentable over Konishi (US 2015/0102256) in view of Zhang (CN 112624207) and Choi (US 2021/0057731) as applied to claim 7, further in view of Kim (US 2016/0359165).
Regarding claim 8, Konishi modified by Hwang and Choi teach primary particles having an aspect ratio gradient and a concentration gradient, but does not teach wherein the average thickness of a region in which the concentration gradient of the transition metal is 0.1 to 500 nm, Kim teaches a cathode active material for lithium secondary battery in which a thickness of the concentration gradient layer is controlled and the lithium ion diffusion path in the primary particles is formed to exhibit directivity toward the center direction of the particles, thus the storage of the lithium ion into and release thereof from the primary particles are facilitated, and the capacity, output, and lifespan characteristics of the battery including the cathode active material for lithium secondary battery according to the present invention are significantly improved as a result [0032]. Structural stability and stable lifespan characteristics are exhibited even in a case in which the thickness of the concentration gradient layer is from 10 to 500 nm. It would have been obvious to one of ordinary skilled in the art at the time the invention was made to form the concentration gradient of Konishi modified by Hwang and Choi in the range of 10 to 500 nm, as taught by Kim, for the benefit of possessing good structural stability.
Regarding claim 8, wherein the average thickness of the barrier layer is 0.1 to 1 um, Choi teaches the positive electrode active material may include a coating layer covering at least a part of the surface of the primary particle (e.g., the interface between the primary particles) and/or the surface of the secondary particle formed by agglomerating the primary particles, thereby increasing structural stability [0078]. In addition, when the positive electrode active material is used in a lithium secondary battery, the high-temperature storage stability and lifetime of the positive electrode active material may be improved. In addition, the oxide may reduce residual lithium in the positive electrode active material and also serve as a migration pathway of lithium ions, and therefore, it can have a positive influence on the efficiency of a lithium secondary battery [0087]. Here, the oxide may exhibit a concentration gradient decreasing from the surface of the secondary particle to the center thereof. Therefore, the concentration of the oxide may decrease from the outermost surface of the secondary particle to the center thereof [0090]. As described above, as the oxide exhibits a concentration gradient decreasing from the surface of the secondary particle to the center thereof, residual lithium present at the surface of the positive electrode active material may be effectively reduced, thereby preventing a side reaction caused by unreacted residual lithium in advance. In addition, a decrease in crystallinity in an inner region from the surface of the positive electrode active material by the oxide may be prevented. In addition, it is possible to prevent the entire structure of the positive electrode active material from collapsing due to the oxide during an electrochemical reaction [0091].
It would have been obvious to one of ordinary skilled in the art at the time the invention was made to form the coating of Choi at an appropriate thickness that would provide good stability to the primary and secondary particles.
Response to Arguments
Arguments filed 2/17/2026 are addressed below:
Regarding claims 1, 7, a spinel phase is present on at least a part of the shell surface, the instant Specification states on page 30:
However, unlike the spinel phase formed by the phase transition caused by the migration of a transition metal in the lithium manganese-based oxide, when a spinel phase is formed on the surface of the primary particle and/or the secondary particle and a barrier layer is formed on the surface of the lithium manganese-based oxide at the same time, such a spinel phase may not only contribute to the surface stabilization of the lithium manganese-based oxide, but may also serve as a 2D and/or 3D path through which lithium ions in the lithium manganese-based oxide diffuse.
Accordingly, as a spinel-phase compound is present on the surface of the lithium manganese-based oxide by forming the barrier layer present to inhibit the dissolution of a transition metal from the primary particle and/or the secondary particle, even when the surface(s) of the primary particle and/or the secondary particle is(are) covered with the barrier layer, the lithium manganese-based oxide may exhibit an appropriate level of electrical conductivity.
In addition, if needed, the barrier layer may include at least two oxides selected from the first to third oxides in order to effectively inhibit or mitigate the dissolution of a transition metal from the lithium manganese-based oxide, and at the same time, improve the surface kinetics of the lithium manganese-based oxide.
Zhang teaches a barrier layer, but does not teach a barrier layer having a spinel phase. Choi teaches the positive electrode active material may include a coating layer covering at least a part of the surface of the primary particle (e.g., the interface between the primary particles) and/or the surface of the secondary particle formed by agglomerating the primary particles, thereby increasing structural stability [0078]. In addition, when the positive electrode active material is used in a lithium secondary battery, the high-temperature storage stability and lifetime of the positive electrode active material may be improved. In addition, the oxide may reduce residual lithium in the positive electrode active material and also serve as a migration pathway of lithium ions, and therefore, it can have a positive influence on the efficiency of a lithium secondary battery [0087]. The coating includes a lithium boron oxide [0088]. It would have been obvious to one of ordinary skilled in the art at the time the invention was made to use the lithium boron oxide of Choi as the barrier layer of Konishi modified by Zhang, as taught by Choi, for the benefit of stabilizing the positive active material.
It is noted that the lithium boron oxide of Choi meets a first oxide represented by Chemical Formula 2 as disclosed in the Specification page 28, as well as in Applicant’s claim 14. It is further noted that the positive active material of Konishi meets the active material Chemical Formula 1-1 as disclosed in the Specification page 16, as well as in Applicant’s claim 11. Hence, it appears that a spinel phase would exist in the combination of Konishi modified by Zhang and Choi also.
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.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to CYNTHIA KYUNG SOO WALLS whose telephone number is (571)272-8699. The examiner can normally be reached on M-F until 5pm.
If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Jonathan Leong can be reached at 571-270-1292. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
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/CYNTHIA K WALLS/ Primary Examiner, Art Unit 1751
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