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 .
Information Disclosure Statement
The information disclosure statement(s) (IDS) submitted on 12/22/2025 has been considered by the examiner.
Drawings
The drawings were received on 3/21/2023. These drawings are accepted.
Response to Amendment
Examiner notes the following amendments made to the claims:
Claim 17 amended to overcome objection
Response to Arguments
Applicant’s arguments, filed 11/12/2025, with respect to the objection of claim 17 have been fully considered and are persuasive. The objection of claim 17 has been withdrawn.
Applicant's arguments filed 11/12/2025 with respect to the 35 USC 103 rejections of claims 1-4, 11, 12, 16, 17, and additionally, claims 5-10, 13-15, and 18 have been fully considered but they are not persuasive. Specifically, examiner finds that the rejection for claim 1 still holds weight despite the arguments presented. Examiner will respond to the arguments in order:
First, applicant argues that a prima facie case of obviousness is not established, specifically because the Blizanac reference teaches a conductive carbon mixture that is directed toward a cathode, whereas Cho teaches an anode active material including a conductive agent. Examiner does not find this argument persuasive, as in many cases the conductive agent is the same in both the cathode and anode of a lithium secondary battery, and has been shown to form a passivation layer in both low-potential and high-potential electrodes in the case of carbon black (See Liu S, Zeng X, Liu D, Wang S, Zhang L, Zhao R, Kang F and Li B (2020) Understanding the Conductive Carbon Additive on Electrode/Electrolyte Interface Formation in Lithium-Ion Batteries via in situ Scanning Electrochemical Microscopy. Front. Chem. 8:114. doi: 10.3389/fchem.2020.00114), i.e. demonstrating that the same conductive additive can have a desirable effect in both the cathode and anode of a lithium secondary battery. Additionally, Applicant seems to imply that Cho teaches a negative active material and therefore cannot be modified by a conductive additive—however, Cho clearly teaches the use of a conductive additive in its negative electrode (“The negative electrode may further include at least one conductive agent of carbon black, acetylene black, ketjen black, carbon fiber, copper, nickel, aluminum, silver, and a conductive polymer.” Cho [0032]) and therefore this argument is not persuasive. Examiner believes that one of ordinary skill in the art could modify the anode material of Cho, containing a conductive additive, to include the conductive additive material of Blizanac in order to attempt to replicate the beneficial effects found by Blizanac. This would not be outside the realm of routine experimentation/optimization, as the conductive additive used by Blizanac is taught within the same field and has been shown to produce promising results. Examiner understands that the combination of amorphous and crystalline carbon of Cho is directed at specifically, the negative active material, but notes that Cho teaches carbon black as a carbon material, and the beneficial effects taught by Blizanac could apply to the carbon black used as a negative active material in addition to specifically as a conductive agent, as it is the same material.
Second, applicant argues that the cited references fail to teach or suggest the claimed subject matter. Specifically, applicant states that the cited references do not teach a carbon-based material that includes a mixture of amorphous carbon black and crystalline carbon black, having the desired D/G ratios. Examiner does not find this persuasive, as the negative electrode of Cho teaches both an amorphous and crystalline carbon being used together. Examiner would like to state that the definition of “mixture” is not specified. If applicant were to amend the claim and state that the amorphous and crystalline carbon materials were used, for example, in the same layer or mixed prior to being applied as a conductive additive, it could potentially overcome the applied prior art, and warrant further search and consideration. As the claim currently stands, examiner finds that the combination of Cho and Blizanac teaches all of the limitations. Since applicant does not argue the D/G ratios of Blizanac, they are assumed to still anticipate the instant claims.
Lastly, applicant makes no specific arguments regarding the patentability of dependent claims 2-4, 11, 12, 16, 17 and additionally claims 5-10, 13-15, and 18 other than the fact that they depend on claim 1. Therefore, since examiner maintains the rejection of claim 1 barring further amendment, the dependent claims remain rejected as well.
Since no amendments were made to the claims other than to cure an objection to claim 17, and the arguments presented by applicant regarding claim 1 are non-persuasive, the previously presented rejections are all maintained and unchanged, and there is currently not considered to be any allowable subject matter present in the claims.
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) 1-4, 11-12, 16, and 17 is/are rejected under 35 U.S.C. 103 as being unpatentable over Cho (US 20130089784 A1) in view of Blizanac (US 20160293959 A1).
Regarding claim 1, Cho teaches the following elements:
A negative electrode layer (“Referring to FIG. 2, the lithium battery 30 includes a positive electrode 23, a negative electrode 22, and a separator 24 interposed between the positive electrode 23 and the negative electrode 22.” Cho [0096])
for an all-solid secondary battery (“Examples of the non-aqueous electrolyte are a non-aqueous electrolytic solution, an organic solid electrolyte, an inorganic solid electrolyte, etc.” Cho [0088]. In this case, by using a solid electrolyte, the battery would be an all solid secondary battery)
comprising a negative electrode current collector (“completing preparation of a negative active material slurry. The prepared slurry was coated on a copper foil current collector having a thickness of 10 µm to manufacture a negative electrode plate.” Cho [0101])
containing a carbon-based material, (“According to an embodiment of the present invention, the negative active material may further include a carbonaceous particle including at least one of natural graphite, artificial graphite, expandable graphite, graphene, carbon black, fullerene soot, carbon nanotubes, and carbon fiber. Herein, the carbonaceous particle may be in a spherical, tabular, fibrous, tubular, or powder form.” Cho [0028])
Cho is silent on the following elements of claim 1. Specifically, while Cho teaches the use of a more amorphous and more crystalline carbon with differing D/G ratios, it doesn’t explicitly teach the variance in crystallinity of carbon black, which is found in Blizanac (“According to one or more embodiments of the present invention, a negative active material includes a primary particle. The primary particle includes: a crystalline carbonaceous core with silicon-based nanowires disposed on a surface thereof; and an amorphous carbonaceous coating layer that is coated on the crystalline carbonaceous core so as not to expose at least a portion of the silicon-based nanowires.” Cho [0013], “ a D/G ratio of the crystalline carbonaceous core may be 0.3 or less,” Cho [0021] and “According to an embodiment of the present invention, a D/G ratio of the amorphous carbonaceous coating layer 130 may be 3.0 or more” Cho [0065])
wherein the carbon-based material includes a mixture of amorphous carbon black
and crystalline carbon black,
and satisfies that a D peak to G peak intensity ratio of the amorphous carbon black, obtained by Raman analysis, is 1.5 or more,
and a D peak to G peak intensity ratio of the crystalline carbon black, obtained by Raman analysis, is greater than 0.5 and less than 1.5.
Blizanac teaches all of the elements of claim 1 that are not found in Cho:
wherein the carbon-based material includes a mixture of amorphous carbon black (Base carbon black, no (NA) heat treatment, Blizanac Table 1 [0109])
and crystalline carbon black, (Sample B, Base carbon black after 2000 oC heat treatment, Blizanac Table 1 [0109])
and satisfies that a D peak to G peak intensity ratio of the amorphous carbon black, obtained by Raman analysis, is 1.5 or more, (Simultaneously, % crystallinity, also determined from Raman measurements as the ratio of D and G-bands, increases from 33%, typical for conventional carbon blacks, to 46% at 1400° C. (Sample A) [0109], Table 1; The Examiner notes Base Carbon Black with no heat treatment in Table 1 is amorphous carbon black because it is 67% amorphous and 33% crystalline. So, the ratio of D peak to G peak is 67/33= 2.03),
and a D peak to G peak intensity ratio of the crystalline carbon black, obtained by Raman analysis, is greater than 0.5 and less than 1.5. (Simultaneously, % crystallinity, also determined from Raman measurements as the ratio of D and G-bands, increases from 33%, typical for conventional carbon blacks, to 46% at 1400° C. (Sample A) to 68% after heat treatment at 2000° C. (Sample B) [0109], Table 1; The Examiner notes Sample B is crystalline carbon black because it is 68% crystalline and 32% amorphous. So, the ratio of D peak to G peak is 32/68 = 0.47 ≈ 0.5),
Cho and Blizanac are considered to be analogous because they are both within the same field of electrode materials containing mixtures of carbonaceous materials with varying crystallinity. Therefore, it would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to modify the mixture of amorphous and crystalline carbon in Cho to be carbon black with varying degrees of crystallinity which correlate to the claimed D/G ratios, as taught by Blizanac, in order to improve the electrochemical stability of the carbonaceous material, which can positively affect cycle life and durability (“After a 2000° C. heat treatment, oxygen is almost entirely absent from the surface and the temperature was sufficient to smooth out most of the surface imperfections, resulting in close to ideal graphitic termination of the carbon black surface. Consequently, it is believed that the increased level of graphitization beneficially impacts carbon black electrochemical stability at relevant cathode potentials in Li-Ion battery cells which should, in turn positively affect cycle life and durability of Li-Ion systems, e.g., at high charging cut-off voltages.” Blizanac [0116]).
By using the mixture of amorphous and crystalline carbon black of Blizanac within the negative electrode of Cho, the limitations of claims 2-4, 12, 16, and 17 would be met without requiring any further modification or motivation.
Regarding claim 2, modified Cho teaches all of the elements of claim 1, as shown above. Cho is silent on the following elements of claim 2:
The negative electrode layer of claim 1, wherein a mixed weight ratio of the amorphous carbon black and the crystalline carbon black is 1:0.05 to 1:2.5.
However, Blizanac teaches all of the elements of claim 2 not found in Cho:
The negative electrode layer of claim 1, wherein a mixed weight ratio of the amorphous carbon black and the crystalline carbon black is 1:0.05 to 1:2.5. (By using the example carbon black of sample B, after heat treatment at 2000C, there would be a 68:32 ratio of crystalline to amorphous carbon black. This would be a 1:2.125 ratio of amorphous to crystalline, and since all that is changing is the crystallinity, it is assumed that this would also be the weight ratio between the two kinds of carbon black, thus anticipating the claimed range.)
Regarding claim 3, modified Cho teaches all of the elements of claim 1, as shown above. Cho teaches all of the additional elements of claim 3:
The negative electrode layer of claim 1, wherein the first negative electrode active material layer further comprises a metal, a metalloid, or a combination thereof, the metal, metalloid, or combination thereof includes silver, platinum, zinc, silicon, tin, iron, copper, aluminum, indium, bismuth, or a combination thereof. (“As a negative active material, a carbonaceous base material and a non-carbonaceous base material, which enable intercalation or deintercalation of lithium ions, are used and studies thereon have been continuously performed. Examples of a carbonaceous base material are artificial graphite, natural graphite, and hard carbon. An example of a non-carbonaceous base material is Si.” Cho [0008]. In addition to the carbonaceous material, Cho also teaches the inclusion of Silicon into its negative electrode active material.)
Regarding claim 4, modified Cho teaches all of the elements of claim 1, as shown above. Cho teaches all of the additional elements of claim 4:
The negative electrode layer of claim 3, wherein the content of the metal, metalloid, or combination thereof is, based on 100 parts by weight of the total weight of the first negative electrode active material layer, 1 to 40 wt % and the content of the carbon-based material is 60 wt% to 99 wt %. (“According to an embodiment of the present invention, based on a total amount of the crystalline carbonaceous core and the silicon-based nanowires, an amount of the crystalline carbonaceous core may be in a range of about 60 to about 99 wt % and an amount of the silicon-based nanowires may be in a range of about 1 to about 40 wt %.” Cho [0027])
Regarding claim 11, modified Cho teaches all of the elements of claim 1, as shown above. Cho teaches all of the additional elements of claim 11:
The negative electrode layer of claim 1, wherein the first negative electrode active material layer includes a binder, and the binder is styrene butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, carboxymethylcellulose, or a combination thereof. (“According to an embodiment of the present invention, the negative electrode may further include at least one binder selected from the group consisting of polyvinylidenefluoride, polyvinylidenechloride, polybenzimidazole, polyimide, polyvinylacetate, polyacrylonitrile, polyvinylalcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polystyrene, polymethylmethacrylate, polyaniline, acrylonitrilebutadienestyrene, phenol resin, epoxy resin, polyethylenetelethphalate, polytetrafluoroethylene, polyphenylsulfide, polyamideimide, polyetherimide, polyethylenesulfone, polyamide, polyacetal, polyphenyleneoxide, polybutylenetelephthalate, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butadiene rubber, and a fluoride rubber.” Cho [0031])
Regarding claim 12, modified Cho teaches all of the elements of claim 1, as shown above. Cho teaches all of the additional elements of claim 12:
An all-solid secondary battery comprising: a positive electrode layer; a negative electrode layer; and a solid electrolyte layer disposed between the positive electrode layer and the negative electrode layer, wherein the negative electrode layer is the negative electrode layer of any one of claims 1 to 11. (“According to one or more embodiments of the present invention, a lithium battery includes: a negative electrode including the negative active material; a positive electrode that is disposed facing the negative electrode; and an electrolyte disposed between the negative electrode and the positive electrode.” Cho [0029] and “Examples of the non-aqueous electrolyte are a non-aqueous electrolytic solution, an organic solid electrolyte, an inorganic solid electrolyte, etc.” Cho [0088])
Regarding claim 16, modified Cho teaches all of the elements of claim 1, as shown above. Cho teaches all of the additional elements of claim 16:
The all-solid secondary battery of claim 12, wherein the solid electrolyte layer includes a sulfide-based solid electrolyte. (“Examples of the inorganic solid electrolyte are nitrides, halides, and sulfides of Li, such as Li.sub.3N, LiI, Li.sub.5NI.sub.2, Li.sub.3N--LiI--LiOH, LiSiO.sub.4, Li.sub.2SiS.sub.3, Li.sub.4SiO.sub.4, Li.sub.4SiO.sub.4--LiI--LiOH, Li.sub.3PO.sub.4--Li.sub.2S--SiS.sub.2, and the like.” Cho [0091])
Regarding claim 17, modified Cho teaches all of the elements of claim 1, as shown above. Cho teaches all of the additional elements of claim 17:
The all-solid secondary battery of claim 16, wherein the sulfide-based solid electrolyte is one or more selected from Li2S-P2S5, Li2S-P2S5-LiX (where X is a halogen element), Li2S-P2S5-Li2O, Li2S-P2S5-Li2O-Lil, Li2S-SiS2, Li2S-SiS2-Lil, Li2S-SiS2- LiBr, Li2S-SiS2-LiCI, Li2S-SiS2-B2S3-Lil, Li2S-SiS2-P2S5-Lil, Li2S-B2S3, Li2S-P2S5- 5 ZmSn (where m and n are positive numbers, and Z is one of Ge, Zn and Ga), Li2S-GeS2, Li2S-SiS2-Li3PO4, Li2S-SiS2-LipMOq (where p and q are positive numbers, and M is one of P, Si, Ge, B, Al, Ga, and In), Li7-xPS6-xClx (where 0≤x≤2), Li7-xPS6-xBrx (where 0≤ x≤ 2), 7-xPS6-xIx (where 0≤ x≤ 2), (“Examples of the inorganic solid electrolyte are nitrides, halides, and sulfides of Li, such as Li.sub.3N, LiI, Li.sub.5NI.sub.2, Li.sub.3N--LiI--LiOH, LiSiO.sub.4, Li.sub.2SiS.sub.3, Li.sub.4SiO.sub.4, Li.sub.4SiO.sub.4--LiI--LiOH, Li.sub.3PO.sub.4--Li.sub.2S--SiS.sub.2, and the like.” Cho [0091])
Claim(s) 5 is/are rejected under 35 U.S.C. 103 as being unpatentable over Cho (US 20130089784 A1) in view of Blizanac (US 20160293959 A1) and further in view of Hampden-Smith (US 20050221141 A1), Masakazu (JP 2007227368A), and Spahr (US 20180155552 A1).
Regarding claim 5, modified Cho teaches all of the elements of claim 1, as shown above. Cho and Blizanac are silent on the following elements of claim 5, relating to the size and spacing parameters of the amorphous and crystalline carbon black:
The negative electrode layer of claim 1,wherein
the amorphous carbon black has a primary particle size of 15 nm to 60 nm,
a specific surface area of 15 m2/g to 1500 m2/g,
a crystallite size Lc in the c-axis direction of 3.0 nm or less,
and a carbon interlayer spacing (d002) of 0.350 nm to 0.370 nm,
and the crystalline carbon black has a primary particle size of 15 nm to 60 nm,
a specific surface area of 15 m2/g to 500 m2/g,
a crystallite size Lc in the c-axis direction of 2.0 nm to 10.0 nm,
and a carbon interlayer spacing (d002) of 0.335 nm to 0.357 nm.
However, Hampden-Smith teaches that the particle size and surface area parameters for carbon black are normally within the claimed ranges. Therefore, since Blizanac doesn’t state that its particles are of an abnormal size or surface area, they would likely be within the claimed ranges for both particle size and specific surface area. If they weren’t, it is clear that it would be obvious to use these size parameters as they are known in the art to be the general size and surface area of carbon black particles:
wherein the amorphous carbon black has a primary particle size of 15 nm to 60 nm, a specific surface area of 15 m2/g to 1500 m2/g, (“Carbon black particles generally have an average size in the range of 9 to 150 nanometers and a surface area of from about 20 to 1500 m.sup.2/g.” Hampden-Smith [0039]. This anticipates the claimed range for surface area.)
The examiner takes note of the fact that the prior art range of 9-150nm for the primary particle size of carbon black encompasses the claimed range of 15-60nm for the same parameter. Absent any additional and more specific information in the prior art, a prima facie case of obviousness exists. In re Peterson, 315 F.3d 1325, 1330, 65 USPQ2d 1379 (Fed. Cir. 2003). MPEP 2144.05.
and the crystalline carbon black has a primary particle size of 15 nm to 60 nm, a specific surface area of 15 m2/g to 500 m2/g, (“Carbon black particles generally have an average size in the range of 9 to 150 nanometers and a surface area of from about 20 to 1500 m.sup.2/g.” Hampden-Smith [0039] This anticipates the claimed range for surface area.)
The examiner takes note of the fact that the prior art range of 9-150nm for the primary particle size of carbon black encompasses the claimed range of 15-60nm for the same parameter. Absent any additional and more specific information in the prior art, a prima facie case of obviousness exists. In re Peterson, 315 F.3d 1325, 1330, 65 USPQ2d 1379 (Fed. Cir. 2003). MPEP 2144.05.
Hampden-Smith is silent on the following elements of claim 5:
wherein the amorphous carbon black has a crystallite size Lc in the c-axis direction of 3.0 nm or less,
and a carbon interlayer spacing (d002) of 0.350 nm to 0.370 nm,
wherein the crystalline carbon black has a crystallite size Lc in the c-axis direction of 2.0 nm to 10.0 nm,
and a carbon interlayer spacing (d002) of 0.335 nm to 0.357 nm.
However, Masakazu teaches the following elements of claim 5 that are not found in Hampden-Smith or Blizanac:
wherein the crystalline carbon black has a crystallite size Lc in the c-axis direction of 2.0 nm to 10.0 nm, (“Further, the crystallite size (Lc) of the amorphous carbonaceous (002) plane obtained by X-ray diffraction by the Gakushin method is essential to be 80 nm or less, preferably 35 nm or less. Preferably it is 20 nm or less, More preferably, it is 10 nm or less.” Masakazu [62])
The examiner takes note of the fact that the prior art range of less than 10nm for the crystallite size of crystalline carbon black encompasses the claimed range of between 2 and 10nm for the same parameter. Absent any additional and more specific information in the prior art, a prima facie case of obviousness exists. In re Peterson, 315 F.3d 1325, 1330, 65 USPQ2d 1379 (Fed. Cir. 2003). MPEP 2144.05.
and a carbon interlayer spacing (d002) of 0.335 nm to 0.357 nm. (“The spacing (d002) of the (002) plane of the amorphous carbonaceous material used as the negative electrode active material of the lithium ion secondary battery of the present invention by the wide-angle X-ray diffraction method is Although it is essential that it is 0.337 nm or more, it is preferably 0.34 nm or more. As an upper limit, it is 0.39 nm or less normally, “ Masakazu [60]. This anticipates the claimed range.)
Masakazu is silent on the following elements of claim 5:
wherein the amorphous carbon black has a crystallite size Lc in the c-axis direction of 3.0 nm or less,
and a carbon interlayer spacing (d002) of 0.350 nm to 0.370 nm,
However, Spahr teaches all of the remaining elements of claim 5 not found in Masakazu, Hampden-Smith, or Blizanac:
wherein the amorphous carbon black has a crystallite size Lc in the c-axis direction of 3.0 nm or less, (Spahr Table 2 shows that each of the carbon blacks used have a crystalline size of 2nm, which anticipates the claimed range)
and a carbon interlayer spacing (d002) of 0.350 nm to 0.370 nm, (“Alternatively or in addition, the carbon black material may be characterized by an interlayer spacing c/2 of between about 0.3580 and about 0.3640 nm. In certain embodiments, the interlayer spacing c/2 will be between about 0.3590 and about 0.3630 nm, or between about 0.3600 and about 0.36200 nm, or between about 0.3600 and about 0.3615 nm.” Spahr [0040] This anticipates the claimed range.)
In addition to being obvious to use the commonly known/used particle size and surface area of carbon black as taught by Hampden-Smith (see above), The use of the specific crystallite size and interlayer spacing of the crystalline and amorphous carbon blacks as taught by Masakazu and Spahr, respectively, would be obvious as well, for the following reasons:
Regarding the crystalline carbon black—Masakazu is considered to be analogous to Blizanac and Cho because it is within the same field of lithium ion secondary batteries. Therefore, it would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to modify the crystalline carbon black to have the specific crystallite size and interlayer spacing parameters of Masakazu in order to have crystalline particles with high conductivity without sacrificing current density and charge/discharge characteristics (“Although it is essential that it is 0.337 nm or more, it is preferably 0.34 nm or more. As an upper limit, it is 0.39 nm or less normally, Preferably it is 0.38 nm or less, More preferably, it is 0.37 nm or less, More preferably, it is 0.36 or less, Most preferably, it is 0.35 or less. If it exceeds this range, the crystallinity is remarkably lowered, the decrease in conductivity between particles cannot be ignored, and it may be difficult to obtain the effect of improving the high current density charge / discharge characteristics for a short time. On the other hand, below this range, the crystallinity becomes too high and it may be difficult to obtain the effect of improving the high current density charge / discharge characteristics for a short time.” Masakazu [60])
Regarding the amorphous carbon black—Spahr is considered to be analogous to Blizanac because it is related to modifying carbon black to optimize properties in the context of lithium ion batteries. Therefore, it would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to modify the amorphous carbon black to have the specific crystalline size and interlayer spacing properties taught by Stahl in order to provide a portion of the carbonaceous material having low viscosity and low resistivity (“The materials may inter alia be characterized by a low viscosity in dispersions and by exhibiting low electrical resistivity. Such materials can be advantageously used in various applications, for example in the manufacture of electrochemical cells such as lithium ion batteries” Stahl [0001])
Claim(s) 6 is/are rejected under 35 U.S.C. 103 as being unpatentable over Cho (US 20130089784 A1) in view of Blizanac (US 20160293959 A1) and further in view of Watanabe (US 20200203709 A1).
Regarding claim 6, modified Cho teaches all of the elements of claim 1, as shown above. Cho teaches the following elements of claim 6:
The negative electrode layer of claim 1, wherein the D peak/G peak intensity ratio of the amorphous carbon black is 1.6 to 4.0 (“According to an embodiment of the present invention, a D/G ratio of the amorphous carbonaceous coating layer 130 may be 3.0 or more” Cho [0065])
The examiner takes note of the fact that the prior art range of 3.0 or more for the D/G ratio of the amorphous carbon of Cho overlaps the claimed range of between 1.6 and 4.0 for the same parameter. Absent any additional and more specific information in the prior art, a prima facie case of obviousness exists. In re Peterson, 315 F.3d 1325, 1330, 65 USPQ2d 1379 (Fed. Cir. 2003). MPEP 2144.05.
Cho is silent on the following elements of claim 6:
The negative electrode layer of claim 1, wherein the D peak/G peak intensity ratio of the amorphous carbon black is 1.6 to 4.0, and the D peak/G peak intensity ratio of the crystalline carbon black is 0.8 to 1.5.
However, Watanabe teaches all of the elements of claim 6 that are not found in Cho:
The negative electrode layer of claim 1, wherein the D peak/G peak intensity ratio of the amorphous carbon black is 1.6 to 4.0, and the D peak/G peak intensity ratio of the crystalline carbon black is 0.8 to 1.5. (“The average value of ID/IG of the activated carbon black depends on a temperature at the time of an activation reaction, but the activated carbon black is carbon black in which the average value of ID/IG is approximately 1.0 to 1.5. In a case where the activated carbon black is mixed with the natural graphite, ID/IG decreases in accordance with a mixed amount, and thus, it is preferable that the carbon material is synthesized by being mixed with the natural graphite such that 0.5≤ ID/IG ≤1.3 is obtained,” Watanabe [0027])
The examiner takes note of the fact that the prior art range of 0.5-1.3 for the desired D/G ratio of crystalline carbon black overlaps the claimed range of 0.8-1.5 for the same parameter. Absent any additional and more specific information in the prior art, a prima facie case of obviousness exists. In re Peterson, 315 F.3d 1325, 1330, 65 USPQ2d 1379 (Fed. Cir. 2003). MPEP 2144.05.
Watanabe, Cho, and Blizanac are considered to be analogous because they are all related to using carbonaceous materials of different crystallinity in electrode materials. Therefore, it would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to modify the crystalline carbon black of Blizanac used in the negative electrode of Cho to have the specific D/G ratio of Watanabe, in order to improve discharge characteristics (“In a case where the average value of the peak intensity ratios ID/IG satisfies the relationship described above, a graphitization degree of the carbon material is low, and thus, a path of a lithium ion in the positive electrode 11 increases, and pulse discharge characteristics in the order of several tens of mA can be improved.” Watanabe [0026]). Examiner notes that the carbon black of Watanabe is used in a cathode rather than an anode, but affirms that it would still be obvious to use this D/G ratio as it would be desirable in both kinds of electrode and one skilled in the art would understand this.
Claim(s) 7-10, 13, and 18 is/are rejected under 35 U.S.C. 103 as being unpatentable over Cho (US 20130089784 A1) in view of Blizanac (US 20160293959 A1) and further in view of Chang (US 20220158226 A1)
Regarding claim 7, modified Cho teaches all of the elements of claim 1, as shown above. Cho is silent on the following elements of claim 7:
The negative electrode layer of claim 1, further comprising a lithium metal or lithium alloy thin film between the negative electrode current collector and the first negative electrode active material layer.
However, Chang teaches all of the elements of claim 7 that are not found in Cho:
The negative electrode layer of claim 1, further comprising a lithium metal or lithium alloy thin film between the negative electrode current collector and the first negative electrode active material layer. (“A second anode active material layer may further be disposed between the porous anode current collector and the first anode active material layer. The second anode active material layer may include a carbonaceous anode active material or a combination of a carbonaceous anode active material and a second metal.” Chang [0057] and “the second anode active material layer or the third anode active material layer may be a metal layer including lithium or a lithium alloy.” Chang [0069])
Cho and Chang are considered to be analogous because they are both within the same field of negative electrodes for all-solid secondary batteries. Therefore, it would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to modify Cho to include the second anode active material layer in between the current collector and the first anode active material layer, the second layer comprising a lithium metal or lithium alloy layer, in order to improve energy density and cycle characteristics (“When the thickness of the second anode active material layer 24 is within these ranges, an energy density and cycle characteristics of the all-solid battery 1 may be improved. “ Chang [0117]).
By using the second anode active material layer comprising a lithium or lithium alloy film of Chang, the additional limitations of claims 8-10, 13 would be met without requiring any further modification or motivation.
Regarding claim 8, modified Cho teaches all of the elements of claim 1, as shown above. Cho is silent on the following elements of claim 8:
The negative electrode layer of claim 1, further comprising a metal or metalloid thin film between the negative electrode current collector and the first negative electrode active material layer.
However, Chang teaches all of the elements of claim 8 that are not found in Cho:
The negative electrode layer of claim 1, further comprising a metal or metalloid thin film between the negative electrode current collector and the first negative electrode active material layer. (“A second anode active material layer may further be disposed between the porous anode current collector and the first anode active material layer. The second anode active material layer may include a carbonaceous anode active material or a combination of a carbonaceous anode active material and a second metal.” Chang [0057] and “the second anode active material layer or the third anode active material layer may be a metal layer including lithium or a lithium alloy.” Chang [0069])
Regarding claim 9, modified Cho teaches all of the elements of claim 1, as shown above. Cho is silent on the following elements of claim 9:
The negative electrode layer of claim 8, wherein the metal or metalloid thin film includes gold (Au), silver (Ag), magnesium (Mg), zinc (Zn), silicon (Si), tin (Sn), platinum (Pt), palladium ( Pd), aluminum (Al), bismuth (Bi), or a combination thereof,
and the metal or metalloid thin film has a thickness of 1 nm to 800 nm.
However, Chang teaches all of the elements of claim 9 that are not found in Cho:
The negative electrode layer of claim 8, wherein the metal or metalloid thin film includes gold (Au), silver (Ag), magnesium (Mg), zinc (Zn), silicon (Si), tin (Sn), platinum (Pt), palladium ( Pd), aluminum (Al), bismuth (Bi), or a combination thereof, (“A second anode active material layer may further be disposed between the porous anode current collector and the first anode active material layer. The second anode active material layer may include a carbonaceous anode active material or a combination of a carbonaceous anode active material and a second metal.” Chang [0057] and “the second anode active material layer or the third anode active material layer may be a metal layer including lithium or a lithium alloy.” and Chang [0069]) “Examples of the lithium alloy may be a Li—Al alloy, a Li—Sn alloy, a Li—In alloy, a Li—Ag alloy, a Li—Au alloy, a Li—Zn alloy, a Li—Ge alloy, and a Li—Si alloy.”)
and the metal or metalloid thin film has a thickness of 1 nm to 800 nm. (“A thickness of the second anode active material layer 24 may be, for example, in a range of about 1 nm to about 800 nm, about 10 nm to about 700 nm, about 50 nm to about 600 nm, or about 100 nm to about 500 nm.” Chang [0117])
Regarding claim 10, modified Cho teaches all of the elements of claim 1, as shown above. Cho is silent on the following elements of claim 10:
The negative electrode layer of claim 1, further comprising a second negative electrode active material layer, wherein the second negative electrode active material layer includes a metal, a metalloid element, or a combination thereof capable of forming an alloy with lithium, and is a metal layer including lithium or a lithium alloy.
However, Chang teaches all of the elements of claim 10 that are not found in Cho:
The negative electrode layer of claim 1, further comprising a second negative electrode active material layer, wherein the second negative electrode active material layer includes a metal, a metalloid element, or a combination thereof capable of forming an alloy with lithium, and is a metal layer including lithium or a lithium alloy. , (“A second anode active material layer may further be disposed between the porous anode current collector and the first anode active material layer. The second anode active material layer may include a carbonaceous anode active material or a combination of a carbonaceous anode active material and a second metal.” Chang [0057] and “the second anode active material layer or the third anode active material layer may be a metal layer including lithium or a lithium alloy.” and Chang [0069]) “Examples of the lithium alloy may be a Li—Al alloy, a Li—Sn alloy, a Li—In alloy, a Li—Ag alloy, a Li—Au alloy, a Li—Zn alloy, a Li—Ge alloy, and a Li—Si alloy.”)
Regarding claim 13, modified Cho teaches all of the elements of claim 12, as shown above. Cho is silent on the following elements of claim 13:
The all-solid secondary battery of claim 12, wherein the negative electrode layer includes a negative electrode current collector and a first negative electrode active material layer, a second negative electrode active material is disposed on at least one of the first negative electrode active material layer and between the negative electrode current collector and the first negative electrode active material layer, and the second negative electrode active material layer includes lithium or a lithium alloy.
However, Chang teaches all of the elements of claim 13 not found in Cho:
The all-solid secondary battery of claim 12, wherein the negative electrode layer includes a negative electrode current collector and a first negative electrode active material layer, a second negative electrode active material is disposed on at least one of the first negative electrode active material layer and between the negative electrode current collector and the first negative electrode active material layer, and the second negative electrode active material layer includes lithium or a lithium alloy. (“A second anode active material layer may further be disposed between the porous anode current collector and the first anode active material layer. The second anode active material layer may include a carbonaceous anode active material or a combination of a carbonaceous anode active material and a second metal.” Chang [0057] and “the second anode active material layer or the third anode active material layer may be a metal layer including lithium or a lithium alloy.” Chang [0069])
Regarding claim 18, modified Cho teaches all of the elements of claim 12, as shown above. Cho is silent on the following elements of claim 18:
The all-solid secondary battery of claim 12, wherein the sulfide-based solid electrolyte is an argyrodite-type solid electrolyte including one or more selected from Li6PS5CI, Li6PS5Br, and Li6PS5I.
However, Chang teaches all of the elements of claim 18 that aren’t found in Cho:
The all-solid secondary battery of claim 12, wherein the sulfide-based solid electrolyte is an argyrodite-type solid electrolyte including one or more selected from Li6PS5CI, Li6PS5Br, and Li6PS5I. (“Particularly, the sulfide-based solid electrolyte in the solid electrolyte layer 30 may be an argyrodite-type compound including at least one of Li.sub.6PS.sub.5Cl, Li.sub.6PS.sub.5Br, or Li.sub.6PS.sub.5I.” Chang [0128])
Cho and Chang are considered to be analogous for the reasons provided above. It would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to modify the sulfide-based solid electrolyte of Cho to be one of those taught by Chang, as this would be a simple substitution of one sulfide-based solid electrolyte material for another, and the simple substitution of one known element for another is likely to be obvious when predictable results are achieved. (see MPEP § 2143, B.).
Claim(s) 14-15 is/are rejected under 35 U.S.C. 103 as being unpatentable over Cho (US 20130089784 A1) in view of Blizanac (US 20160293959 A1) and further in view of Kim (US 20220045354 A1)
Regarding claim 14, modified Cho teaches all of the elements of claim 12, as shown above. Cho is silent on the following elements of claim 14:
The all-solid secondary battery of claim 12, wherein the negative electrode layer includes a negative electrode current collector and a first negative electrode active material layer, and the negative electrode current collector, the first negative electrode active material layer, and a region therebetween are lithium (Li)-free regions that do not include Li at an initial state or post-discharge state of the all-solid secondary battery.
However, Kim teaches all of the elements of claim 14 that are not found in Cho:
The all-solid secondary battery of claim 12, wherein the negative electrode layer includes a negative electrode current collector and a first negative electrode active material layer, and the negative electrode current collector, the first negative electrode active material layer, and a region therebetween are lithium (Li)-free regions that do not include Li at an initial state or post-discharge state of the all-solid secondary battery. (“Further, when the third anode active material layer 925 is disposed by charging after assembly of the all-solid secondary battery 91, the anode current collector 921, the first anode active material layer 922, the second anode active material layer 923, and an area therebetween are Li-free areas not including lithium (Li) in an initial state or post-discharge state of the all-solid secondary battery.” Kim [0155])
Kim and Cho are considered to be analogous because they are both within the same field of all-solid secondary batteries. Therefore, it would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to modify Cho to include a lithium-free region between the negative electrode current collector and active material layer as taught by Kim in order to reduce the likelihood of short circuit and improve cycle characteristics (“Further, since the first anode active material layer 922 and/or the second anode active material layer 923 are disposed on and cover the third anode active material layer 925, the first anode active material layer 922 and/or the second anode active material layer 923 serve as a protective layer for the third anode active material layer 925, and serve to suppress the precipitation and growth of lithium dendrite. Accordingly, the short circuit and decrease in capacity of the all-solid secondary battery 1 are suppressed, and as a result, the cycle characteristics of the all-solid secondary battery 91 are improved. Further, when the third anode active material layer 925 is disposed by charging after assembly of the all-solid secondary battery 91, the anode current collector 921, the first anode active material layer 922, the second anode active material layer 923, and an area therebetween are Li-free areas not including lithium (Li) in an initial state or post-discharge state of the all-solid secondary battery.” Kim [0155]).
By using the negative electrode active material layers and structure of Kim, the limitations of claim 15 would also be met without requiring any further modification or motivation.
Regarding claim 15, modified Cho teaches all of the elements of claim 12, as shown above. Cho is silent on the following elements of claim 15:
The all-solid secondary battery of claim 12, wherein a lithium precipitation layer is included between the negative electrode current collector and the negative electrode active material during charging or after charging.
However, Kim teaches all of the elements of claim 15 that are not found in Cho:
The all-solid secondary battery of claim 12, wherein a lithium precipitation layer is included between the negative electrode current collector and the negative electrode active material during charging or after charging. (“When the first anode active material layer 922 and/or the second anode active material layer 923 is charged so as to exceed the charging capacity thereof, for example, lithium is precipitated on the rear surface of the second anode active material layer 923, that is, between the anode current collector 921 and the second anode active material layer 923, and a metal layer corresponding to the third anode active material layer 925 may be formed by the precipitated lithium.” Kim [0154]).
Conclusion
THIS ACTION IS MADE FINAL. Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
The following references were found during updated search but were not used in rejection:
Mah (US 20230261202 A1) – teaches a combination of amorphous and crystalline carbon in an anode active material
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/BENJAMIN ELI KASS-MULLET/Examiner, Art Unit 1752
/NICHOLAS A SMITH/Supervisory Primary Examiner, Art Unit 1752