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 .
Continued Examination Under 37 CFR 1.114
A request for continued examination under 37 CFR 1.114, including the fee set forth in 37 CFR 1.17(e), was filed in this application after final rejection. Since this application is eligible for continued examination under 37 CFR 1.114, and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114. Applicant's submission filed on 26 June 2025 has been entered.
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 is incorrect, any correction of the statutory basis 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 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.
Claims 1-2, 5, 7-8 and 10-19 are rejected under 35 U.S.C. 103 as being unpatentable over Kondo et al (JP 2012156055 A1) in view of Lee et al (KR 20170046114 A) and Fukasawa et al (US 20150086870 A1). These prior art references cited as Kondo, Lee, and Fukasawa, respectively, in this Office Action hereinafter.
Regarding claim 1, Kondo discloses a negative electrode active material (“negative electrode active material” [0024]) comprising:
a first particle (“negative electrode active material particles” [0025]), and a second particle (“other negative electrode active materials already known (for example, graphite, Sn, Si, or the like) may be added and used” [0034]),
wherein,
the first particle comprises:
a silicon core (“core portion 1 is composed of a silicon compound” [0026]);
an oxide layer including SiOx (0<x≤2) (“an SiO2 phase” [0026]), which is on the silicon core (“the plurality of fine Si phases are coated with the SiO 2 phase” [0026]), and
a coating layer (“coating 2” [0026]) covering at least a portion of a surface of the oxide layer (“covers the core portion 1” [0026]) and consisting of LiF (“the film containing lithium fluoride (LiF)” [0062]), and
the second particle is graphite (“for example, graphite” [0034]).
Kondo does not disclose the negative electrode active material comprising a carbonaceous matrix, wherein,
the carbonaceous matrix directly or indirectly covers all of the first and the second particle,
the first particle comprises:
the oxide layer including lithium silicate and has a thickness of 0.01 nm to 20 nm; and
the second particle is flaky graphite.
However, Lee discloses a negative electrode active material (“negative active material (1)” [0029]) comprising a first particle (“the second particle (12) includes the crystalline flaky graphite fragment particles (12b) and silicon (Si) particles (12a) bonded to the surface thereof” [0029]) and a second particle (“the first particle (11) includes crystalline flaky graphite fragment particles” [0029]).
Lee teaches the negative electrode active material comprising a carbonaceous matrix (“matrix (13)” [0029]),
wherein,
the carbonaceous matrix directly or indirectly covers all of the first and the second particle (“wherein the first particle (11) and the second particle (12) are randomly distributed and bonded within the matrix (13), and ii) a spherical assembled particle including a surface layer in which the first particle (11) and the second particle (12) are laminated and bonded together with the matrix in a concentric direction of the core on the surface portion of the assembled particle core” [0029]), and
the second particle is flaky particle (“The flake graphite particles included in the first particle (11) may be in the shape of exfoliated flake graphite particles or flakes” [0033]).
Furthermore, Lee teaches the carbonaceous matrix acts as a buffer to the volume expansion of silicon ions generated during charge and discharge, and enables a structurally stable negative electrode active material that does not decrease lithium storage capacity and can exhibit characteristics such as improved charge and discharge capacity and cycle life ([0037]). Lee also teaches that graphite as the second particle with a flake shape enables lamination in a concentric direction from the core of the matrix to form a bonded surface layer ([0032]), which prevents a decrease in stability that may occur due to repeated charging and discharging of the spherical assembled negative electrode active material particles ([0062]).
Therefore, it would have been obvious for a person having ordinary skill in the art to add a carbonaceous matrix to the negative electrode active material of Kondo, wherein, the carbonaceous matrix directly or indirectly covers all of the first and the second particle, and to select the graphite as the second particle of Kondo to be flaky graphite. The person of ordinary skill in the art would then be able to achieve a buffer to the volume expansion of silicon ions generated during charge and discharge, a structurally stable negative electrode active material that does not decrease lithium storage capacity and can exhibit characteristics such as improved charge and discharge capacity and cycle life, and a negative electrode active material with a bonded surface layer that prevents a decrease in stability that may occur due to repeated charging and discharging of the spherical assembled negative electrode active material particles.
Additionally, Fukasawa discloses a negative electrode active material (20 Fig. 2; “a composite negative electrode material 20” [0031]) comprising a carbonaceous matrix (21 Fig. 2; “a carbonaceous Substance phase 21” [0031]) and a first particle (10 Fig. 2; “a negative electrode material 10” [0031]) wherein the carbonaceous matrix directly or indirectly covers all of the first particle (“coating with the carbonaceous substance phase 21 may be performed to a single negative electrode material 10, or may be performed to a particle having a composite structure in which a plurality of negative electrode materials 10 is concurrently included (hereinafter, referred to as composite particle), and the first particle comprises a silicon core (“silicon nanoparticle 11 serves as a core” [0019]) and an oxide layer including SiO2 (“silicon oxide 12 … and the core is coated with the silicon oxide 12” [0019]). A part of the negative electrode material 10 may be exposed on a surface of the carbonaceous Substance 21.” [0034]).
Fukasawa teaches the first particle comprises:
the oxide layer including lithium silicate (“lithium silicate such as Li4SiO4 may be dispersed … on a surface of the negative electrode material 10” [0037]) and has a thickness of 0.01 nm to 20 nm (“the silicon oxide 12 coats the surface portion of the silicon nanoparticle 11 with the thickness of 10 nm or less on average” [0024]).
Furthermore, Fukasawa teaches that lithium silicate in the oxide layer enables lithium conductivity at the time of charging and discharging ([0025]) and that the thickness of 0.01 nm to 20 nm of the oxide layer maintains charge and discharge efficiency ([0025]).
Therefore, it would have been obvious for a person having ordinary skill in the art to add lithium silicate to the oxide layer of Kondo and to change the oxide layer of Kondo so that it has a thickness of 0.01 nm to 20 nm, in order to achieve lithium conductivity in the oxide layer and an oxide layer with optimum charge and discharge efficiency.
Regarding claim 2, modified Kondo discloses the negative electrode active material with all the features set forth in claim 1 above, but does not wherein the silicon core has an average particle diameter (D50) of 40 nm to 400 nm.
However, Fukasawa teaches to relax the stress, it is favorable to use the silicon core having a size as fine as possible. To be specific, an average primary particle diameter is favorably from 10 to 100 nm ([0020]). Furthermore, Fukasawa teaches silicon having the average primary particle diameter less than 10 nm has strong aggregation, but dispersion is difficult and too fine silicon is easily oxidized, which causes a possible decrease in capacity, and silicon having the average primary particle diameter larger than 100 nm can be cracked and pulverization is more likely to occur due to repetition of volume expansion/contraction ([0020]).
Therefore, it would have been obvious to select the average particle diameter of the silicon core of the first particle of modified Kondo in further view of Fukasawa to be of 40 nm to 400 nm, in order to achieve efficiency in negative electrode active material capacity and charge/discharge, which causes the expansion and contraction in the negative electrode active material.
Regarding claim 5, modified Kondo discloses the negative electrode active material with all the features set forth in claim 1 above, and wherein the coating layer has a thickness of 0.01 nm to 50 nm (Kondo “it can be seen that the thickness of the coating film is thin, and the core portion existing inside the coating film is located within or near a predetermined depth H from the surface of the negative electrode active material particle” [0015] and “The generation position of photoelectrons emitted from the surface of the negative electrode active material when a current of 15 KV and 10 mA is applied to the X-ray tube is set to a depth Hof about 5 to 50 nm from the outermost surface of the negative electrode active material.” [0031]).
Regarding claim 7, modified Kondo discloses the negative electrode active material, but does not disclose wherein a weight ratio of the first particle to the second particle is in a range of 1:9 to 9:1.
However, Lee teaches a mixture configured to include the first particles and the second particles in a weight ratio of 10:90 to 90:10 ([0054]), and that this ratio range exhibits excellent charge/discharge capacity ([0054]).
Therefore, it would have been obvious to select a weight ratio of the first particle to the second particle in the negative electrode active material of modified Kondo, in further view of Lee, to be in a range of 1:9 to 9:1, in order to achieve excellent charge/discharge capacity in the negative electrode active material.
Regarding claim 8, modified Kondo discloses the negative electrode active material with all the features set forth in claim 1 above, and wherein the carbonaceous matrix is included in an amount of 5 wt% to 50 wt% based on a total weight of the negative electrode active material (Kondo “the matrix is characterized in that it contains 5 to 70 wt% of amorphous carbon or soft carbon based on the total weight of the spherical assembled particles” [0013]).
Regarding claim 10, modified Kondo discloses the negative electrode active material with all the features set forth in claim 1 above, and wherein the lithium silicate comprises at least one of Li2SiO3, Li4SiO4, or Li2Si2O5 (Fukasawa “lithium silicate such as Li4SiO4” [0037]).
Regarding claim 11, modified Kondo discloses the negative electrode active material with all the features set forth in claim 1 above, but does not disclose wherein the first particle and the second particle are in contact with each other.
However, Lee teaches the first particle and the second particle are randomly distributed and bonded ([0029]), and that this maintains electrical contact within the negative electrode active material for a lithium secondary battery to have a higher charge and discharge capacity and a longer cycle life than conventional negative electrode active materials ([0042]).
Therefore, it would have been obvious to change the negative electrode active material of modified Kondo in further view of Lee, wherein the first particle and the second particle are in contact with each other, in order to achieve electrical contact within the negative electrode active material for a lithium secondary battery to have a higher charge and discharge capacity and a longer cycle life than conventional negative electrode active materials.
Regarding claim 12, modified Kondo discloses a negative electrode (Kondo “The negative electrode has negative electrode active material particles. It is common that the negative electrode active material is crimped to the current collector as a negative electrode active material layer.” [0024]) comprising the negative electrode active material of claim 1.
Regarding claim 13, modified Kondo discloses a secondary battery (Kondo “lithium ion secondary battery” [0023]) comprising:
the negative electrode of claim 12;
a positive electrode (Kondo “a positive electrode” [0023]);
a separator between the positive electrode and the negative electrode (Kondo “separator is sandwiched between the positive electrode and the negative electrode” [0041]); and
an electrolyte (Kondo “an electrolyte” [0023]).
Regarding claim 14, modified Kondo discloses the negative electrode active material with all the features set forth in claim 1 above, and wherein the carbonaceous matrix comprises at least one of amorphous carbon or crystalline carbon (Lee “matrix (13) including amorphous carbon or soft carbon” [0029]).
Regarding claim 15, modified Kondo discloses the negative electrode active material with all the features set forth in claim 14 above, and wherein the crystalline carbon comprises at least one selected from the group consisting of fullerene, carbon nanotubes, and graphene (the alternative of the disclosed carbonaceous matrix in Lee is not crystalline carbon that this claim sets limitations on).
Regarding claim 16, modified Kondo discloses the negative electrode active material with all the features set forth in claim 14 above, and wherein the amorphous carbon comprises at least one carbide selected from the group consisting of tar, pitch and other organic materials (Kondo [0040]).
Regarding claim 17, modified Kondo discloses the negative electrode active material with all the features set forth in claim 1 above, and wherein the carbonaceous matrix is included in an amount of 10 wt% to 45 wt% based on a total weight of the negative electrode active material (Kondo “the matrix is characterized in that it contains 5 to 70 wt% of amorphous carbon or soft carbon based on the total weight of the spherical assembled particles” [0013]).
Regarding claim 18, modified Kondo discloses the negative electrode active material with all the features set forth in claim 1 above, and wherein the carbonaceous matrix is included in an amount of 12 wt% to 40 wt% based on a total weight of the negative electrode active material (Kondo “the matrix is characterized in that it contains 5 to 70 wt% of amorphous carbon or soft carbon based on the total weight of the spherical assembled particles” [0013]).
Regarding claim 19, modified Kondo discloses the negative electrode active material with all the features set forth in claim 1 above, but does not disclose wherein a weight ratio of the first particle to the second particle is in a range of 2:8 to 8:2.
However, Lee teaches a mixture configured to include the first particles and the second particles in a weight ratio of 10:90 to 90:10 ([0054]), and that this ratio range exhibits excellent charge/discharge capacity ([0054]).
Therefore, it would have been obvious to select a weight ratio of the first particle to the second particle in the negative electrode active material of modified Kondo, in further view of Lee, to be in a range of 2:8 to 8:2, in order to achieve excellent charge/discharge capacity in the negative electrode active material.
Claim 6 is rejected under 35 U.S.C. 103 as being unpatentable over Kondo (JP 2012156055 A1) in view of Lee (KR 20170046114 A) and Fukasawa (US 20150086870 A1), and further in view of Nagayama et al (US 2016/0276668 A1). The latter reference cited as Nagayama hereinafter.
Regarding claim 6, modified Kondo discloses the negative electrode active material with all the features set forth in claim 1 above, but does not discloses wherein the flaky graphite has a Brunauer-Emmett-Teller (BET) specific surface area of 1 m2/g to 200 m2/g.
However, Nagayama discloses a negative electrode active material (“carbon material for negative electrodes” [0034]) comprising a carbonaceous matrix (“amorphous composite graphite particles (B)” [0034]) including a first particle (“elemental silicon … particle” [0037]) and a second particle (“elemental … carbon particle” [0037]) wherein the first particle comprises a coating layer (“the Si composite carbon particles (A) preferably contain a carbonaceous material, and as a more specific aspect, at least a part of the surface thereof is more preferably coated with the carbonaceous material (hereinafter, such Si composite carbon particles (A) are also referred to as “carbonaceous material-coated Si composite carbon particles”)” [0204]), and wherein the second particle is flaky graphite (“when the Si composite carbon particles (A) of (I) or (III) described above are produced, examples thereof include graphite particles of natural graphite,” [0095] where “natural graphite is classified into flake graphite, …” [0096]). Nagayama teaches wherein the flaky graphite has a Brunauer-Emmett-Teller (BET) specific surface area of 1 m2/g to 200 m2/g (“specific surface area of the carbon material used as the raw material by the BET method is typically 1 m2/g to 40 m2/g, preferably 2 m2/g to 35 m2/g, and more preferably 3 m2/g to 30 m2/g.” [0104]), and that this range of BET specific surface area for the second particle that is flaky graphite prevents a decrease in battery capacity when an increase in irreversible capacity of the first particle occurs ([0104]).
Therefore, it would have been obvious for a person having ordinary skill in the art to replace the second particle of the negative electrode active material of modified Kondo in view of Nagayama wherein the flaky graphite has a Brunauer-Emmett-Teller (BET) specific surface area of 1 m2/g to 200 m2/g, in order to achieve a negative electrode active material that prevents a decrease in battery capacity when an increase in irreversible capacity of the first particle occurs with a reasonable expectation of success.
Claim 22 is rejected under 35 U.S.C. 103 as being unpatentable over Kondo (JP 2012156055 A1) in view of Lee (KR 20170046114 A) and Fukasawa (US 20150086870 A1), and further in view of Yamamoto et al (US 2017/0324083 A1). The latter reference cited as Yamamoto hereinafter.
Regarding claim 22, modified Kondo discloses the negative electrode active material with all the features set forth in claim 1 above, but does not disclose wherein the lithium silicate comprises Li2SiO3.
However, Yamamoto discloses a negative electrode active material (“a negative - electrode active material” [0034]) comprising a first particle (10 Fig. 1; “a negative electrode active material particle 10” [0035]) that comprises a silicon core (12 Fig. 1; “silicon particles 12” [0035]) and an oxide layer (11 Fig. 1; “a lithium silicate phase 11” [0035]) including SiO2 (“a third component in addition to the lithium silicate phase 11 and the silicon particles 12 . The amount of SiO2 , if any , in the form of a natural oxidation film contained in the base particle 13” [0036]) and lithium silicate (“a lithium silicate phase 11” [0035]).
Yamamoto teaches wherein the lithium silicate comprises Li2SiO3 (“The lithium silicate phase 11 is formed of a lithium silicate represented by Liz SiO2 + z ) ( 0 < z < 2 ) . In other words , Li4 SiO4 ( Z = 2 ) does not constitute the lithium silicate phase 11 … The lithium silicate phase 11 is preferably composed mainly of Li2SiO3 ( Z = 1 ) or Li2Si2O5 ( Z = 1 / 2 )” [0039]), and that this lithium silicate is preferred in terms of stability, manufacturability, and lithium ion conductivity ([0039]).
Therefore, it would have been obvious for a person having ordinary skill in the art to replace the lithium silicate of modified Kondo wherein the lithium silicate comprises Li2SiO3, in view of Yamamoto, in order to achieve an oxide layer of the first particle that is stable, manufacturable, and has maximum lithium ion conductivity with a reasonable expectation of success.
Claim 23 is rejected under 35 U.S.C. 103 as being unpatentable over Kondo (JP 2012156055 A1) in view of Lee (KR 20170046114 A) and Fukasawa (US 20150086870 A1), and further in view of Wu et al (US 2016/0118652 A1). The latter reference cited as Wu hereinafter.
Regarding claim 23, modified Kondo discloses the negative electrode active material with all the features set forth in claim 1 above, but does not disclose wherein the LiF is present in an amount of 0.5 wt% to 15 wt% based on a total weight of the negative electrode active material.
However, Wu discloses a negative electrode active material (“an anode material” [0018]) comprising a first particle that comprises a silicon core (10 Fig. 1; “core 10” [0020]), an oxide layer (12 Fig. 1; “a first shell layer 12” [0020]), and a coating layer (14 Fig. 1; “a second shell layer” [0020]) consisting of LiF (“the second shell layer 14 includes at least one of lithium, lithium fluoride (LiF)…” [0037]).
Wu teaches wherein the LiF is present in an amount of 0.5 wt% to 15 wt% based on a total weight of the negative electrode active material (“the anode active material consists mainly of a carbon material, based on 100 parts by weight of the anode active material, the organic modified layer accounts for about 0.5 to 1 parts by weight, and the lithium-containing inorganic layer accounts for about 3 to 6 parts by weight.” [0039] with italics added for emphasis), and that this amount of LiF in the coating layer is optimum for maximum capacitance and reduced resistance (“When the usage range is outside the range of the disclosure (such as the samples of Comparative Examples 6 to 8), the capacitance is reduced and the resistance is increased.” [0060] and Tables 3 and 4).
Therefore, it would have been obvious for a person having ordinary skill in the art to change the coating layer of modified Kondo wherein the LiF is present in an amount of 0.5 wt% to 15 wt% based on a total weight of the negative electrode active material, in view of Wu, in order to achieve a negative electrode active material that exhibits maximum capacitance and reduced resistance with a reasonable expectation of success.
Response to Arguments
Applicant’s arguments with respect to claim 1 has been considered but are moot because the new ground of rejection does not rely on any reference applied in the prior rejection of record for any teaching or matter specifically challenged in the argument.
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to CHARLENE BERMUDEZ whose telephone number is (571)272-0610. The examiner can normally be reached Wednesdays generally from 7 AM to 7 PM.
Examiner interviews are available via telephone, in-person, and video conferencing using a USPTO supplied web-based collaboration tool. To schedule an interview, applicant is encouraged to use the USPTO Automated Interview Request (AIR) at http://www.uspto.gov/interviewpractice.
If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Allison Bourke can be reached at (303) 297-4684. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
Information regarding the status of published or unpublished applications may be obtained from Patent Center. Unpublished application information in Patent Center is available to registered users. To file and manage patent submissions in Patent Center, visit: https://patentcenter.uspto.gov. Visit https://www.uspto.gov/patents/apply/patent-center for more information about Patent Center and https://www.uspto.gov/patents/docx for information about filing in DOCX format. For additional questions, contact the Electronic Business Center (EBC) at 866-217-9197 (toll-free). If you would like assistance from a USPTO Customer Service Representative, call 800-786-9199 (IN USA OR CANADA) or 571-272-1000.
/CHARLENE BERMUDEZ/Examiner, Art Unit 1721
/ALLISON BOURKE/Supervisory Patent Examiner, Art Unit 1721