DETAILED ACTION
Claim Rejections - 35 USC § 103
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
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.
Claims 1, 2, 3, 17, and 18 are rejected under 35 U.S.C. 103 as being unpatentable over US 20140332731 A1 (Ma ‘731) in view of US 20130209869 A1 (Rojeski ‘869).
Regarding claim 1, Ma ‘731 teaches a secondary battery (a battery, optionally Li ion battery; [0010]; coin cell battery; [0051]) comprising:
a positive electrode (cathode; [0051]);
a negative electrode (anode; [0051]) including fiber parts (large and small graphite anode carbonaceous particles in an electrode layer, and mixed with large, CNT(B) 5 and small, CNT(A) 2, diameter carbon nanotubes, and binder 3 forming a carbon nanotube network to accommodate an unconventional packing structure; [0034] & Fig. 1C), and having voids (see the voids/spaces present in the electrode structure shown in Fig. 1C);
a separator disposed between the positive electrode and the negative electrode (cathode/separator/anode; [0051] & Fig. 4); and
an electrolytic solution (injecting electrolyte; [0051]), wherein
the fiber parts are coupled to each other to thereby form a three-dimensional mesh structure having the voids (as shown in Fig. 5, the intra-penetrating CNT(A) 505 and CNT(B) 510 form a three dimensional network of carbonaceous materials; [0034] & [0035]), the fiber parts each including carbon as a constituent element (the carbon nanotubes, corresponding to the fiber parts, may be of various kinds such as single-walled carbon nanotubes, multi-walled carbon nanotubes, vapor-phase grown carbon fibers, etc.; [0031]), and
where the negative electrode is bisected into a first part and a second part in a direction (the negative electrode may be bisected in the thickness direction of the electrode structure) in which the positive electrode and the negative electrode are opposed to each other with the separator interposed between the positive electrode and the negative electrode ([0051] & Fig. 4), at least one of an average fiber diameter of the fiber parts (the three dimensional network of carbonaceous materials comprises nanotubes with a “bi-modal” distribution, a mixture of two different uni-modal diameter distributions or distributions having only a narrow range of diameters, i.e., large diameter carbon nanotubes and small diameter carbon nanotubes; [0027] & [0045]), a proportion of a weight of the covering parts to a sum of a weight of the fiber parts and the weight of the covering parts, or a void rate varies between the first part and the second part (in the “bi-modal” distribution, the diameter of the carbon nanotubes varies because of the unconventional packing structure comprising large diameter nanotubes and small diameter nanotubes), the first part being positioned on a side close to the separator, the second part being positioned on a side far from the separator (the negative electrode may be bisected into a first part and a second part in the thickness direction having a first part closer to the separator and a second part farther away from the separator of the battery structure).
Ma ‘731 discloses exemplary anode materials such as lithium, carbon, graphite, silicon and silicon-based compounds, but Ma ‘731 does not disclose covering parts, wherein the covering parts each cover a surface of corresponding one of the fiber parts, and each include silicon as a constituent element.
Rojeski ‘869 discloses carbon nanofibers (CNFs; [0016]) with a Silicon Layer 115 deposited onto each CNF to form a gradually thinned coaxial shell ([0057]). This design enables the whole Silicon Layer 115 to be electrically connected through the CNF 110 and to remain fully active during charge-discharge cycling ([0057]). The addition of the Silicon Layer 115, corresponding to the covering part (Fig. 3A), provided significantly higher charge/discharge rate and corresponding capacity ([0057]).
Therefore, it would have been obvious to a skilled artisan, at the time of filing, to provide silicon layers, i.e., covering parts, that cover a corresponding one of the carbon nanotube/nanofiber parts, to improve capacity significantly, as suggested by Rojeski ‘869, in the negative electrode for a secondary battery, as taught by Ma ‘731.
Regarding claims 2 and 3, Ma ‘731 teaches the secondary battery according to claim 1, wherein the average fiber diameter of the fiber parts is less than the average fiber diameter of the fiber parts in the second part (a range of diameters for small carbon nanotubes is 4-15 nm and a range for large diameter nanotubes is about 30-100 nm; [0027] of Ma ‘731; further, the diameter of individual CNFs can be selected to provided desired mechanical strength; [0016] of Rojeski ‘869), wherein the average fiber diameter of the fiber parts in the first part is greater than or equal to 0.0003 times the average fiber diameter of the fiber parts in the second part and less than or equal to 0.5 times the average fiber diameter of the fiber parts in the second part (the ratio of large to small diameter nanotubes depends upon the selection of anode materials, e.g., size, electrical property, etc.; [0011] of Ma ‘731; for example, when the average diameter of the small carbon nanotubes is 5 nm and the average diameter of the large carbon nanotubes is 30 nm, the average diameter of 5 is greater than 3 (0.1 times 30)).
Based on the broadest reasonable interpretation of claim 1, the limitations of claims 2 and 3 only further narrow the scope of claim 1 when the “a void rate varies between the first part and the second part” is selected as the at least one of from the group thereof.
Ma ‘731 disclose in one embodiment of the carbon nanotube network with a “bi-modal” nanotube distribution, small diameter nanotubes are first dispersed into a liquid suspension and large diameter nanotubes are added thereafter at a desired ratio to small diameter nanotubes ([0045]). Accordingly, it would have been obvious to a skilled artisan, at the time of filing, to form a carbon nanotube network having an average diameter in the first part that is less than the average fiber diameter in the second part, to provide desired mechanical strength at a desired ratio in the secondary battery, as taught by Ma ‘731 in view of Rojeski ‘869.
Regarding claim 17, Ma ‘731 teaches the secondary battery according to claim 1, wherein the secondary battery comprises a lithium-ion secondary battery (a battery, optionally Li ion battery; [0010] of Ma ‘731).
Regarding claim 18, Ma ‘731 teaches a negative electrode for a secondary battery (anode for a coin cell battery; [0051]), the negative electrode comprising
fiber parts (large and small graphite anode carbonaceous particles in an electrode layer, and mixed with large, CNT(B) 5 and small, CNT(A) 2, diameter carbon nanotubes, and binder 3 forming a carbon nanotube network to accommodate an unconventional packing structure; [0034] & Fig. 1C),
the negative electrode having voids (see the voids/spaces present in the electrode structure shown in Fig. 1C), wherein
the fiber parts are coupled to each other to thereby form a three-dimensional mesh structure having the voids (as shown in Fig. 5, the intra-penetrating CNT(A) 505 and CNT(B) 510 form a three dimensional network of carbonaceous materials; [0034] & [0035]), the fiber parts each including carbon as a constituent element (the carbon nanotubes, corresponding to the fiber parts, may be of various kinds such as single-walled carbon nanotubes, multi-walled carbon nanotubes, vapor-phase grown carbon fibers, etc.; [0031]), and
where the negative electrode is bisected into a first part and a second part in a thickness direction (the negative electrode may be bisected in the thickness direction of the electrode structure), at least one of an average fiber diameter of the fiber parts (the three dimensional network of carbonaceous materials comprises nanotubes with a “bi-modal” distribution, a mixture of two different uni-modal diameter distributions or distributions having only a narrow range of diameters, i.e., large diameter carbon nanotubes and small diameter carbon nanotubes; [0027] & [0045]), a proportion of a weight of the covering parts to a sum of a weight of the fiber parts and the weight of the covering parts, or a void rate varies between the first part and the second part (in the “bi-modal” distribution, the diameter of the carbon nanotubes varies because of the unconventional packing structure comprising large diameter nanotubes and small diameter nanotubes).
Ma ‘731 discloses exemplary anode materials such as lithium, carbon, graphite, silicon and silicon-based compounds, but Ma ‘731 does not disclose covering parts, wherein the covering parts each cover a surface of corresponding one of the fiber parts, and each include silicon as a constituent element.
Rojeski ‘869 discloses carbon nanofibers (CNFs; [0016]) with a Silicon Layer 115 deposited onto each CNF to form a gradually thinned coaxial shell ([0057]). This design enables the whole Silicon Layer 115 to be electrically connected through the CNF 110 and to remain fully active during charge-discharge cycling ([0057]). The addition of the Silicon Layer 115, corresponding to the covering part (Fig. 3A), provided significantly higher charge/discharge rate and corresponding capacity ([0057]).
Therefore, it would have been obvious to a skilled artisan, at the time of filing, to provide silicon layers, i.e., covering parts, that cover a corresponding one of the carbon nanotube/nanofiber parts, to improve capacity significantly, as suggested by Rojeski ‘869, in the negative electrode, as taught by Ma ‘731.
Claims 4, 5, 9, 14, 15, and 16 are rejected under 35 U.S.C. 103 as being unpatentable over US 20140332731 A1 (Ma ‘731) in view of US 20130209869 A1 (Rojeski ‘869), and further in view of CN 105185961 A (Ding ‘981).
Regarding claims 4 and 5, Ma ‘731 teaches the secondary battery according to claim 1, but does not disclose wherein the proportion of the weight of the covering parts to the sum of the weight of the fiber parts and the weight of the covering parts in the first part is greater than the proportion in the second part, wherein the proportion in the first part is greater than or equal to 1.04 times the proportion in the second part and less than or equal to 4.65 times the proportion in the second part.
Based on the broadest reasonable interpretation of claim 1, the limitations of claims 4 and 5 only further narrow the scope of claim 1 when the “a proportion of a weight of the covering parts to a sum of a weight of the fiber parts and the weight of the covering parts” is selected as the at least one of from the group thereof.
Ding ‘961 discloses a silicon-carbon composite anode material having a core-shell structure ([0014]). The mass percentage of silicon content in a core-shell structure is 0.1% to 90%, for example, 50%, 60%, 70-85%, which can make the negative electrode material of the core-shell structure have a high capacity ([0104]).
Therefore, it would have been obvious to a skilled artisan, at the time of filing, to provide that the weight of the covering parts, i.e., the silicon, in the first part is greater than the proportion in the second part to achieve a high capacity, within the claimed range, as suggested by Ding ‘961, in the secondary battery, as taught by Ding ‘981.
Regarding claim 9, Ma ‘731 teaches the secondary battery according to claim 1, but does not disclose wherein a content of silicon in each of the covering parts is greater than or equal to 80 weight percent.
Ding ‘961 discloses a silicon-carbon composite anode material having a core-shell structure ([0014]). The mass percentage of silicon content in a core-shell structure is 0.1% to 90%, for example, 50%, 60%, 70-85%, which can make the negative electrode material of the core-shell structure have a high capacity ([0104]).
Therefore, it would have been obvious to a skilled artisan, at the time of filing, to provide that the weight of the covering parts, i.e., the silicon, in the first part is greater than the proportion in the second part to achieve a high capacity, within the claimed range, as suggested by Ding ‘961, in the secondary battery, as taught by Ding ‘981.
Regarding claim 14, 15, and 16, Ma ‘731 teaches the secondary battery according to claim 1, but does not disclose wherein the negative electrode further includes additional fiber parts having an average fiber diameter less than the average fiber diameter of the fiber parts, and
at least some of the additional fiber parts are each coupled to a surface of corresponding one of the covering parts, the additional fiber parts including carbon as a constituent element,
wherein the average fiber diameter of the additional fiber parts varies between the first part and the second part,
wherein the average fiber diameter of the additional fiber parts in the first part is less than the average fiber diameter of the additional fiber parts in the second part.
Ding ‘961 discloses adding a fourth carbon material to the silicon-carbon composite anode material with a core-shell structure, where the fourth carbon material is the carbon material C and/or the carbon material D, and the carbon material D is carbon nanotubes and/or carbon fibers ([0101] - [0102]). The addition of carbon material D improves the contact between material particles, thereby enhancing rate performance ([0102]). The diameter the carbon nanotubes is 1-500 nm, and the diameter of the carbon fibers is 1-1000 nm ([0099]).
Therefore, it would have been obvious to a skilled artisan, at the time of filing, to provide additional fiber parts, i.e., another carbon material made up of carbon nanotubes and/or carbon nanofibers having varying diameters, in the secondary battery, as taught by Ma ‘731, to enhance rate performance, as suggested by Ding ‘961.
Rojeski ‘869 discloses that the diameter of individual CNFs can be selected to provided desired mechanical strength ([0016]). By providing an additional carbon material of carbon nanotubes and/or carbon nanofibers, having an appropriately selected diameter to achieve improved mechanical strength, as suggested by Rojeski ‘869, and to enhance rate performance, as suggested by Ding ‘961, it would have been obvious to a skilled artisan, at the time of filing, to provide that the average diameter of the additional carbon materials has varies between the first part and the second part of the negative electrode, wherein the average fiber diameter of the additional carbon materials in the first part is less than the average fiber diameter of the additional fiber parts in the second part for the secondary battery, as taught by Ma ‘731.
Claims 6 and 7 are rejected under 35 U.S.C. 103 as being unpatentable over US 20140332731 A1 (Ma ‘731) in view of US 20130209869 A1 (Rojeski ‘869), and further in view of EP 1873846 A1 (Hiroshi ‘846).
Regarding claims 6 and 7, Ma ‘731 teaches the secondary battery according to claim 1, but does not disclose wherein the void rate in the second part is greater than the void rate in the first part, wherein the void rate in the second part is greater than or equal to 1.1 times the void rate in the first part and less than or equal to 4.5 times the void rate in the first part.
Based on the broadest reasonable interpretation of claim 1, the limitations of claims 6 and 7 only further narrow the scope of claim 1 when the “a void rate varies between the first part and the second part” is selected as the at least one of from the group thereof.
Hiroshi ‘846 discloses that when the void rate of the negative electrode coat layer becomes smaller than 30%, the thickness of the negative electrode is greatly varied to go out of the standard ([0056]). When the void rate of the negative electrode coat layer becomes greater than 70%, it can cause a failure in obtaining a desired capacity ([0056]). Consequently, the void rate of the coat layer of the negative electrode is preferably set in a range from 30% or more to 70% or less ([0057]). Thus, in order to form a coat layer having an appropriate void rate onto the negative electrode, it is important to provide appropriate voids near the outer surface of the particle ([0058]).
Therefore, it would have been obvious to a skilled artisan, at the time of filing, to provide that the void rate in the outer second part is greater than the void rate in the inner first part to achieve a desired capacity, within the claimed range, as suggested by Hiroshi ‘846, in the secondary battery, as taught by Ma ‘731.
Claim 8 is rejected under 35 U.S.C. 103 as being unpatentable over US 20140332731 A1 (Ma ‘731) in view of US 20130209869 A1 (Rojeski ‘869), and further in view of CN 105185961 A (Ding ‘981) and EP 1873846 A1 (Hiroshi ‘846).
Based on the broadest reasonable interpretation of claim 1, the limitations of claim 8 only further narrow the scope of claim 1 when a corresponding one of the “average fiber diameter”, “proportion”, or “void rate” limitations of claim 1 varying between the first part and the second part is selected as the at least one of from the group thereof.
Regarding claim 8, Ma ‘731 teaches the secondary battery according to claim 1, wherein the average fiber diameter of the negative electrode is greater than or equal to 10 nanometers and less than or equal to 12000 nanometers (a ratio of large to small diameter nanotubes depends upon the selection of anode materials, e.g., size, electrical property, etc.; [0011] of Ma ‘731; a range of diameters for small carbon nanotubes is 4-15 nm and a range for large diameter nanotubes is about 30-100 nm; [0027] of Ma ‘731; further, the diameter of individual CNFs can be selected to provided desired mechanical strength; [0016] of Rojeski ‘869; for example, when the average diameter of the small carbon nanotubes is 5 nm and the large carbon nanotubes are 35 nm, the average diameter of the whole when the amount of small and large diameter carbon nanotubes is equal would be about 20 nm).
Ma ‘731 does not disclose that the proportion of the weight of the covering parts to a sum of the weight of the fiber parts and the weight of the covering parts of the negative electrode is greater than or equal to 40 weight percent and less than or equal to 80 weight percent.
Ding ‘961 discloses a silicon-carbon composite anode material having a core-shell structure ([0014]). The mass percentage of silicon content in a core-shell structure is 0.1% to 90%, for example, 50%, 60%, 70-85%, which can make the negative electrode material of the core-shell structure have a high capacity ([0104]).
Therefore, it would have been obvious to a skilled artisan, at the time of filing, to provide that the weight of the covering parts, i.e., the silicon, is between 70% and 85%, to achieve a high capacity, which falls within the claimed range, as suggested by Ding ‘961, in the secondary battery, as taught by Ding ‘981.
Ma ‘731 does not disclose wherein the void rate in the whole is greater than or equal to 40 volume percent and less than or equal to 70 volume percent.
Hiroshi ‘846 discloses that when the void rate of the negative electrode coat layer becomes smaller than 30%, the thickness of the negative electrode is greatly varied to go out of the standard ([0056]). When the void rate of the negative electrode coat layer becomes greater than 70%, it can cause a failure in obtaining a desired capacity ([0056]). Consequently, the void rate of the coat layer of the negative electrode is preferably set in a range from 30% or more to 70% or less ([0057]). Thus, in order to form a coat layer having an appropriate void rate onto the negative electrode, it is important to provide appropriate voids near the outer surface of the particle ([0058]).
Therefore, it would have been obvious to a skilled artisan, at the time of filing, to provide that the void rate is between 30% and 70%, to achieve a desired capacity, which overlaps with the claimed range, as suggested by Hiroshi ‘846, in the secondary battery, as taught by Ma ‘731.
Further, as set forth in MPEP 2144.05, in the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art”, a prima facie case of obviousness exists (In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990)).
Claims 10 and 11 are rejected under 35 U.S.C. 103 as being unpatentable over US 20140332731 A1 (Ma ‘731) in view of US 20130209869 A1 (Rojeski ‘869), and further in view of US 20210066711 A1 (Lu ‘711).
Regarding claims 10 and 11, Ma ‘731 teaches the secondary battery according to claim 1, but does not disclose that wherein the negative electrode further includes surface parts each provided on a surface of corresponding one of the covering parts, and the surface parts each include an ion conductive material, wherein the ion conductive material includes lithium phosphorous oxynitride, lithium phosphate, or both.
Lu ‘711 discloses that the performance of the anode material can be adjusted by doping or coating with, for example, Li3PO4 (lithium phosphate – see paragraph [0314] of the present specification).
Therefore, it would have been obvious to a skilled artisan, at the time of filing, to provide ion conductive surface parts, i.e., a coating of lithium phosphate on the surface of the covering parts of the anode material to adjust the performance of the anode, as suggested by Lu ‘711, for the secondary battery, as taught by Ma ‘731.
Claims 12 and 13 are rejected under 35 U.S.C. 103 as being unpatentable over US 20140332731 A1 (Ma ‘731) in view of US 20130209869 A1 (Rojeski ‘869) and US 20210066711 A1 (Lu ‘711), and further in view of US 20160315353 A1 (Matsushita ‘353).
Regarding claims 12 and 13, Ma ‘731 teaches the secondary battery according to claim 10, but does not disclose that the surface parts have an average thickness that varies between the first part and the second part, wherein the average thickness in the second part is greater than the thickness in the first part.
Matsushita ‘353 discloses an anode active material layer obtained in the manner in which Li3PO4 was made into a film on the surface of the graphite by using a barrel-sputtering method to form a coating layer with an average thickness of 10 nm ([0088]). The thickness of the coating layer may be thickness such as to allow the active material particle and the sulfide solid electrolyte material to be restrained from reacting with each other, preferably within a range of 0.1 nm to 100 nm ([0038]). The reason thereof is when the coating layer is too thick, there is a possibility that the active material particle and the sulfide solid electrolyte material react with each other, whereas when the coating layer is too thick, there is possibility of ion conductivity and electrode conduction deterioration ([0038]).
Accordingly, it would have been obvious to a skilled artisan, at the time of filing, to provide that the surface parts of Li3PO4 have an average thickness that varies between the first part and the second part of the negative electrode when the coating is formed using a sputtering method, wherein the average thickness in the second part may be greater than the thickness in the first part, to maintain desired ion conductivity and electron conduction, as suggested by Matsushita ‘353, in the secondary battery, as taught by Ma ‘731.
Conclusion
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/TAYLOR HARRISON KRONE/Examiner, Art Unit 1725
/JONATHAN CREPEAU/Primary Examiner, Art Unit 1725
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