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 .
Claim Rejections - 35 USC § 102
The following is a quotation of the appropriate paragraphs of 35 U.S.C. 102 that form the basis for the rejections under this section made in this Office action:
A person shall be entitled to a patent unless – (a)(1) the claimed invention was patented, described in a printed publication, or in public use, on sale, or otherwise available to the public before the effective filing date of the claimed invention.
Claims 1 and 7 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Yue (CN101887966A).
Regarding claim 1, Yue teaches a composite hard carbon anode material for a lithium-ion battery (claim 1) and a method of preparing such an anode material (claim 6). For the limitation “a negative electrode,” Yue teaches a negative electrode material and describes forming it by coating on a copper foil current collector and pairing it with a lithium counter electrode (specification, pg. 7 lines 4-8), which structurally satisfies the structural and functional definition of a negative electrode. For the negative electrode active material layer limitation, Yue discloses a negative electrode active material layer (composite hard carbon anode material; claim 1), wherein the negative electrode active material layer comprises negative electrode active material particles (block-shaped fine particles; specification, pg. 2 lines 23-27).
For the limitation “each negative electrode active material particle comprises a porous portion and a nonporous portion,” Yue discloses the composite hard carbon anode material is a block-shaped fine particle with a porous structure that has a porosity of 9-19% (specification, pg. 2 lines 23-27); since the particle has a porosity of 9–19%, the remaining 81–91% of the particle inherently consists of the solid, dense hard carbon matrix (i.e. the nonporous portion). Yue further discloses that the hard carbon matrix is pyrolyzed from a precursor containing a dopant, where the dopant may be a non-metallic element such as silicon, sulfur, and/or boron (specification, pg. 2 lines 12-19). Therefore, since the dopant is mixed into the precursor to form the bulk hard carbon matrix, it is inherently present within the nonporous portion.
Regarding claim 7, Yue teaches all features of claim 1 as described above, and further teaches the negative electrode wherein condition (f) is satisfied such that the negative electrode active material particles comprise hard carbon (hard carbon negative electrode material particles; specification, pg. 2 lines 23-27).
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 3-5 are rejected under 35 U.S.C. 103 as being unpatentable over Yue (CN101887966A) as applied to claim 1 above.
Regarding claim 3, Yue teaches all features of claim 1 as described above, including a composite hard carbon anode material comprised of block-shaped fine particles with a porous structure. Yue further teaches wherein the porous portion has a pore diameter with a value ranging from 0.2 nm to 100 nm (specification, pg. 2 lines 23-27), which overlaps with the claimed range of 0.1 μm to 3 μm (i.e., 100 nm to 300 nm).
When the prior art discloses a general range that overlaps or routinely encompasses the claimed range, a prima facie case of obviousness is established (see MPEP §2144.05). Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to have selected from the overlapping portion of the ranges taught by Yue, because overlapping ranges have been held to establish prima facie obviousness.
Regarding claim 4, Yue teaches all features of claim 1 as described above, and further teaches the negative electrode wherein the negative electrode active material particles have a specific surface area of 1.9 m2/g - 75.3 m2/g (composite hard carbon anode material particles; specification, pg. 2 line 26), which overlaps with the claimed range of 1 m2/g to 10 m2/g.
When the prior art discloses a general range that overlaps or routinely encompasses the claimed range, a prima facie case of obviousness is established (see MPEP §2144.05). Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to have selected from the overlapping portion of the ranges taught by Yue, because overlapping ranges have been held to establish prima facie obviousness.
Regarding claim 5, Yue teaches all features of claim 1 as described above, and further teaches the negative electrode wherein the negative electrode has a porosity of 9 to 19% (composite hard carbon anode material porosity; specification, pg. 2 lines 23-24), which overlaps with the claimed range of 15% to 40%.
When the prior art discloses a general range that overlaps or routinely encompasses the claimed range, a prima facie case of obviousness is established (see MPEP §2144.05). Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to have selected from the overlapping portion of the ranges taught by Yue, because overlapping ranges have been held to establish prima facie obviousness.
Claims 8 and 20 are rejected under 35 U.S.C. 103 as being unpatentable over Yue (CN101887966A) and further in view of Bo (US20200099100A1).
Regarding claims 8 and 20, Yue teaches an electronic apparatus (for instant claim 20 only) comprising an electrochemical apparatus (for instant claims 8 and 20) comprising a negative electrode comprising a negative electrode active material layer, wherein the negative electrode active material layer comprises particles with a porous and non-porous portion such that the non-porous portion comprises heteroatoms.
Specifically, Yue teaches a composite hard carbon anode material for an electrochemical apparatus (lithium-ion battery; claim 1) and a method of preparing such an anode material (claim 6). Regarding the electronic apparatus limitation for instant claim 20 and the electrochemical apparatus limitation for instant claim 8, it is noted that the lithium-ion battery of Yue structurally satisfies the electrochemical apparatus limitation for both claims 8 and 20, and its disclosed use in a powered device satisfies the electronic apparatus limitation for claim 20 (Yue, portable electronic equipment contains the battery; specification, pg. 1 lines 21-24).
The rejection hereon applies to both instant claims 8 and 20, wherein the limitations for the electrochemical apparatus are otherwise identical. For the limitation “a negative electrode,” Yue teaches a negative electrode material and describes forming it by coating on a copper foil current collector and pairing it with a lithium counter electrode (specification, pg. 7 lines 4-8), which structurally satisfies the structural and functional definition of a negative electrode.
For the negative electrode active material layer limitation, Yue discloses a negative electrode active material layer (composite hard carbon anode material; claim 1), wherein the negative electrode active material layer comprises negative electrode active material particles (block-shaped fine particles; specification, pg. 2 lines 23-27). For the limitation “each negative electrode active material particle comprises a porous portion and a nonporous portion,” Yue discloses the composite hard carbon anode material is a block-shaped fine particle with a porous structure that has a porosity of 9-19% (specification, pg. 2 lines 23-27); since the particle has a porosity of 9–19%, the remaining 81–91% of the particle inherently consists of the solid, dense hard carbon matrix (i.e. the nonporous portion). Yue further discloses that the hard carbon matrix is pyrolyzed from a precursor containing a dopant, where the dopant may be a non-metallic element such as silicon, sulfur, and/or boron (specification, pg. 2 lines 12-19). Therefore, since the dopant is mixed into the precursor to form the bulk hard carbon matrix, it is inherently present within the nonporous portion.
Yue further teaches the electrochemical apparatus (i.e., the lithium-ion battery) further comprises an electrolyte (electrolytic solution; specification, pg. 7 lines 4-10). However, Yue does not expressly teach wherein the electrolyte comprises at least one of fluoroether, fluoroethylene, or ether nitrile.
Bo discloses an electrolyte for a lithium-ion battery (claim 13) wherein the electrolyte may comprise a fluoroether (claim 8; [0015]), a fluoroethylene (fluoroethylene carbonate (FEC); [0037]), and/or a dinitrile compound such as ethylene glycol bis(propionitrile) ether (claim 7). Bo further teaches that such electrolytes comprising varying combinations of the disclosed fluorosulfonyl silane acetate, di- and trinitrile compounds, cyclic ethers, and fluoroethers may help improve the cycle performance, rate performance and floating charge performance of a lithium ion battery (see Table 5; pgs. 14-15, [0134]-[0136]).
Since Yue teaches an electronic apparatus (for instant claim 20) comprising an electrochemical apparatus (for instant claims 8 and 20) comprising an electrolyte, and Bo discloses a lithium-ion battery electrolyte comprising a combination of a fluoroether, fluoroethylene, and/or an ether nitrile, and that such known and suitable electrolyte additives may help improve the cycle performance, rate performance and floating charge performance of a lithium ion battery, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to modify the electrolyte of Yue (hereby referred to as “modified Yue”) to comprise one or more of a fluoroether, fluoroethylene, and/or an ether nitrile, as taught by Bo, in order to achieve the known benefits of improved battery performance.
Claims 2 and 11 are rejected under 35 U.S.C. 103 as being unpatentable over Yue (CN101887966A) as applied to claims 1 and 8 above, and further in view of Cheng (US20180083281A1).
Regarding claims 2 and 11, Yue teaches all features of claims 1 and modified Yue teaches all features of claim 8 as described above, including a composite hard carbon anode material comprised of block-shaped fine particles with a porous portion and a nonporous porous portion, wherein the nonporous portion may comprise heteroatoms such as boron and/or sulfur. Yue does not explicitly define the atomic percentages of heteroatoms in the nonporous portion of the negative electrode active material particles.
Cheng discloses an anode material for a lithium-ion battery comprising a porous carbon material, wherein the carbon material is doped with heteroatoms such as boron (claim 4), and that a negative electrode active material with such a configuration may improve the capacity and rate capability ([0005], [0038]). Regarding the limitation “wherein the nonporous portion has an interface, and the interface is a region formed from a bordering position between the nonporous portion and the porous portion to 0.5 μm from the bordering position, wherein through analysis using a scanning electron microscope–energy spectrometer, such that condition (a) is satisfied wherein within a test area of 0.2 μm × 0.2 μm in the interface, based on a total elemental atomic percentage of the heteroatoms, C, and O, an atomic percentage of the heteroatoms is a%, wherein 1 ≤ a ≤ 6,” the a% of the heteroatoms in this interface region is interpreted in light of the specification (Applicant, [0023]) as:
a
%
h
e
t
e
r
o
a
t
o
m
s
i
n
t
h
i
s
i
n
t
e
r
f
a
c
e
r
e
g
i
o
n
=
#
o
f
h
e
t
e
r
o
a
t
o
m
s
∑
(
h
e
t
e
r
o
a
t
o
m
s
+
C
a
t
o
m
s
+
O
a
t
o
m
s
)
*
100
in any given representative cross-section of this region. Table 1 of Cheng ([0047]) discloses a "Comparative Example 2" and "Example 1" comprising boron- and nitrogen-doped carbon configurations.
PNG
media_image1.png
467
651
media_image1.png
Greyscale
Table 1 of Cheng
While Cheng expresses these elemental values in terms of weight percentages (wt%), mathematical conversion into atomic percentages (at%) yields values that fall within the claimed range of 1 ≤ a ≤ 6:
For Comparative Example 2, converting the wt% values to at% based on the atomic masses yields 82.24 at% C, 1.22 at% O, and a combined total of 2.57 at% heteroatoms (B + N). Calculating the atomic percentage of heteroatoms based on the total elements of heteroatoms, C, and O results in 2.99 at% of heteroatoms (B + N).
For Example 1, converting the wt% values to at% based on the atomic masses yields 88.75 at% C, 2.54 at% O, and a combined total of 2.79 at% heteroatoms (B + N). Calculating the atomic percentage of heteroatoms based on the total elements of heteroatoms, C, and O results in 2.97 at% of heteroatoms (B + N).
The at% of heteroatoms was calculated by converting the wt% values of Cheng to at% based on the atomic masses of C, N, H, O, and B and then using the formula:
Comparative Example 2
at% =
h
e
t
e
r
o
a
t
o
m
s
(
B
+
N
)
h
e
t
e
r
o
a
t
o
m
s
B
+
N
+
C
+
O
* 100 =
1.87
B
+
0.696
N
=
2.57
(
B
+
N
)
2.57
B
+
N
+
82.24
C
+
1.22
O
=
86.0
= 2.99 at%
Example 1
at% =
h
e
t
e
r
o
a
t
o
m
s
(
B
+
N
)
h
e
t
e
r
o
a
t
o
m
s
B
+
N
+
C
+
O
* 100 =
2.197
B
+
0.597
N
=
2.79
(
B
+
N
)
2.79
B
a
n
d
N
+
88.75
C
+
2.54
O
=
94.08
= 2.97 at%
Thus, both values in the examples fall directly within the claimed range of 1 ≤ a ≤ 6 based on a total elemental atomic percentage of the heteroatoms, C, and O.
Since Yue teaches a composite hard carbon anode material with particles that include a nonporous portion comprising heteroatoms such as boron, and Cheng discloses working examples of boron- and nitrogen-doped carbon configurations for a battery with an at% of heteroatoms that fall within the claimed range, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to modify the negative electrode active material particles of Yue to utilize the at% of heteroatoms in the nonporous portion, as taught by Cheng, in order to achieve improved capacity and rate capability of the battery (Cheng; [0005], [0038]).
In addition, when the prior art discloses a general range that overlaps or routinely encompasses the claimed range, a prima facie case of obviousness is established (see MPEP §2144.05). Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to have selected from the overlapping portion of the ranges taught by Cheng, because overlapping ranges have been held to establish prima facie obviousness.
Claims 6 and 16 are rejected under 35 U.S.C. 103 as being unpatentable over Yue (CN101887966A) as applied to claims 1 and 8 above, and further in view of Mitra (US20180375093A1).
Regarding claims 6 and 16, Yue teaches all features of claim 1 and modified Yue teaches all features of claim 8 as described above, including a negative electrode comprising a negative electrode active material layer with negative electrode active material particles. Yue further teaches the negative electrode active material particles comprise hard carbon (hard carbon negative electrode material particles; specification, pg. 2 lines 23-27). However, Yue is silent to the ID/IG ratio of the negative electrode active material particles under a Raman spectroscopy test.
Mitra discloses a method of producing a non-amorphous hard carbon (claim 1), wherein the non-amorphous hard carbon is used for constructing electrodes for Li-ion batteries (claim 9). Mitra further teaches that carbon-based negative electrode active materials (such as graphite and hard carbon) are conventionally characterized using Raman spectroscopy to measure structural disorder. Specifically, Mitra discloses that the Raman spectrum exhibits two main modes: a Disordered "D-band" peak at ~1355 cm⁻¹ (corresponding to lattice defects and disorder) and a Graphitic "G-band" peak at ~1579 cm⁻¹ (corresponding to in-plane C-C vibrations). Mitra further teaches that the intensity ratio of these bands (ID/IG) serves as a direct, quantifiable measure of the disorder or non-graphitic nature of the material, where a higher ratio indicates a more disordered, hard-carbon-like structure and a lower ratio indicates a more crystalline, graphite-like structure ([0008]). Mitra further teaches that pure graphite exhibits an ID/IG ratio of 0.113, while hard carbon exhibits an ID/IG ratio of 1.62 (see Table 1; [0008]). Thus, Mitra teaches that the ratio indicates the degree of structural disorder, where a higher ratio corresponds to more hard-carbon-like properties and a lower ratio corresponds to more graphite-like properties. In addition, the claimed range of 0.8 to 1.4 for the ID/IG ratio falls entirely within the broader prior art range of 0.113 to 1.62 established by Mitra.
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to modify the negative electrode active material particles of Yue by utilizing carbon materials having varying degrees of graphitization and disorder, as taught by Mitra, and by measuring and optimizing their structural disorder using the Raman spectroscopy testing techniques to verify the ID/IG ratio as taught by Mitra; in addition, a POSITA would be motivated to tune the structure of the carbon particles between a graphite-like state (ID/IG = 0.113) and a hard-carbon-like state (ID/IG = 1.62) in order to optimize the balance between the electrical conductivity of graphite and the lithium-ion storage capacity/structural stability of hard carbon ([0004], [0041]).
Further, when the prior art discloses a general range that overlaps or routinely encompasses the claimed range, a prima facie case of obviousness is established (see MPEP §2144.05). Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to have selected from the overlapping portion of the ID/IG ratio ranges taught by Mitra (ID/IG = 0.113 to 1.62), because overlapping ranges have been held to establish prima facie obviousness.
Claims 9 and 19 are rejected under 35 U.S.C. 103 as being unpatentable over Yue (CN101887966A) as applied to claim 8 above, and further in view of Kang (WO2020078307A1; US20210249650A1 used for purposes of translation).
Regarding claim 9, modified Yue teaches all features of claim 8 as described above, including a negative electrode comprising a negative electrode active material layer. Yue further discloses a negative electrode current collector; in particular, Yue teaches a 10 μm-thick copper foil upon which the negative electrode slurry is uniformly coated (specification, pg. 7 lines 4-8). In this case, the 10 μm-thick copper foil acts as the underlying conductive substrate supporting the negative electrode film, which satisfies the negative electrode current collector limitation. However, Yue is silent to the adhesion force between the negative electrode current collector and the negative electrode active material layer.
Kang discloses a secondary battery comprising a negative electrode sheet, wherein the negative electrode sheet comprises a negative current collector and a negative electrode film that includes a negative active substance (claim 11). Kang teaches measuring the force required to completely peel the negative electrode film from the negative current collector, which is defined as the "cohesive force" between them ([0057]). This structural interaction is identical to the claimed "adhesion force." Kang further discloses the cohesive force between the negative electrode film and the negative current collector is 1 N/m to 20 N/m (claim 17), which overlaps with the claimed range of 3 N/m to 50 N/m. Kang further teaches that balancing the cohesive force (i.e. adhesion force) between the negative electrode film and the negative current collector along with density and surface area enhances battery dynamics and cycle performance while maintaining energy density ([0007]).
Since Yue teaches an electrochemical apparatus comprising a negative electrode current collector and a negative electrode active material layer that satisfy the limitations of claim 8, and Kang discloses the cohesive force between a negative electrode film and a negative current collector is 1 N/m to 20 N/m (claim 17), which overlaps with the claimed range of 3 N/m to 50 N/m, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to use an adhesion force between the negative electrode current collector and the negative electrode active material layer in the battery of Yue within a range of 1 N/m to 20 N/m (claim 17), as taught by Kang, in order to achieve suitable adhesion and enhanced battery dynamics and cycle performance while maintaining energy density ([0007]).
In addition, when the prior art discloses a general range that overlaps or routinely encompasses the claimed range, a prima facie case of obviousness is established (see MPEP §2144.05). Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to have selected from the overlapping portion of the ranges taught by Kang, because overlapping ranges have been held to establish prima facie obviousness.
Regarding claim 19, modified Yue teaches all features of claim 8 as described above, including an electrochemical apparatus comprising a negative electrode active material layer. However, Yue does not expressly teach a compacted density of the negative electrode active material layer is 0.95 g/cm3 to 1.40 g/cm3.
Kang discloses a secondary battery comprising a negative electrode sheet, wherein the negative electrode sheet comprises a negative current collector and a negative electrode film that includes a negative active substance (claim 11). Kang further discloses the compaction density of the negative electrode film is 0.8 g/cm3 to 2.0 g/cm3, which entirely encompasses the claimed range of 0.95 g/cm3 to 1.40 g/cm3.
When the prior art discloses a general range that overlaps or routinely encompasses the claimed range, a prima facie case of obviousness is established (see MPEP §2144.05). Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to have selected from the overlapping portion of the ranges taught by Kang, because overlapping ranges have been held to establish prima facie obviousness.
Claim 10 is rejected under 35 U.S.C. 103 as being unpatentable over Yue (CN101887966A) as applied to claim 8 above, and further in view of Zhang (CN104300176A).
Regarding claim 10, modified Yue teaches all features of claim 8 as described above, including an electrochemical apparatus comprising an electrolyte. Yue further teaches the electrolyte comprises a lithium salt (1 mol/L LiPF6; specification, pg. 7 line 9). However, Yue does not expressly teach wherein the lithium salt comprises:
lithium bis(fluorosulfonyl)imide and lithium hexafluorophosphate,
a concentration of the lithium salt is 1 mol/L to 2 mol/L,
and a mass ratio of lithium bis(fluorosulfonyl)imide to lithium hexafluorophosphate is 0.06 to 5.
Regarding the lithium salt composition, Zhang discloses a lithium-ion battery electrolyte composition comprising a carbonate main solvent, lithium hexafluorophosphate (LiPF6) as the main salt of the electrolyte, and lithium bis(fluorosulfonyl)imide (LiFSI) as the auxiliary salt of the electrolyte (claim 1). Zhang additionally teaches that in addition to in addition to LiPF6, adding a small amount of another lithium salt (i.e. an auxiliary salt such as LiFSI) to the electrolyte is beneficial to further improve the performance of the battery (specification, pg. 2 lines 4-11), and further notes that when LiPF6 is used as the main salt and LiFSI is used as the auxiliary salt, the low-temperature capacity retention rate is effectively increased and the capacity retention rate after high-temperature storage is reduced (specification, pg. 2 lines 24-30).
Since Yue teaches an electrochemical apparatus comprising an electrolyte that includes a lithium salt, and Zhang discloses a lithium-ion battery electrolyte wherein the lithium salt is a mixture of lithium hexafluorophosphate (LiPF6) as the main salt and lithium bis(fluorosulfonyl)imide (LiFSI) as the auxiliary salt, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to modify the lithium salt of Yue to comprise lithium bis(fluorosulfonyl)imide (LiFSI) and lithium hexafluorophosphate (LiPF6), as taught by Zhang, in order to achieve improved capacity retention rates and battery performance.
Regarding the lithium salt concentration, Zhang discloses an electrolyte wherein the concentration of the LiPF6 main salt is 0.6 to 1.2 M, and the concentration of the LiFSI auxiliary salt is 0.1 to 0.5 M (claim 3). Thus, Zhang teaches a total concentration of the lithium salt falling within the broad range of 0.7 mol/L to 1.7 mol/L (derived from 0.6–1.2 M of LiPF6 plus 0.1–0.5 M of LiFSI; Example 1 also uses LiPF6 and LIFSI with a total salt concentration of ~1.1 mol/L, specification, pg. 5 lines 18-22), which overlaps with the claimed range of 1 mol/L to 2 mol/L.
Regarding the mass ratio of lithium bis(fluorosulfonyl)imide (LiFSI) to lithium hexafluorophosphate (LiPF6), Zhang discloses the use of 12.2 g anhydrous LiPF6 with 3.74g LiFSI in the electrolyte of Example 1 (specification, pg. 5 lines 18-22). Thus, Zhang discloses an electrolyte wherein a mass ratio of LiFSI to LiPF6 is (
3.74
g
L
i
F
S
I
12.2
g
L
i
P
F
6
= 0.306), which falls directly within the claimed range of 0.06 to 5.
When the prior art discloses a general range that overlaps or routinely encompasses the claimed range, a prima facie case of obviousness is established (see MPEP §2144.05). Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to have selected from:
the overlapping portion of the range of the lithium salt concentration, and
the overlapping portion of the range of the mass ratio of LiFSI to LiPF6,
as taught by Zhang, because overlapping ranges have been held to establish prima facie obviousness.
Claim 12 is rejected under 35 U.S.C. 103 as being unpatentable over Yue (CN101887966A) as applied to claim 8 above, and further in view of Li (Li et. al., Mechanism of Na-Ion Storage in Hard Carbon Anodes Revealed by Heteroatom Doping. Advanced Energy Materials. 2017, 7, 1602894).
Regarding claim 12, modified Yue teaches all features of claim 8 as described above, including negative electrode active material particles that comprise a nonporous portion that includes heteroatoms. Yue does not expressly teach wherein an atomic percentage of the heteroatoms ≤ 0.1 at%.
Li teaches that the characteristics of hard carbon structures for Na batteries can be modified systematically by heteroatom doping and that these structural changes greatly affect the ion storage properties (abstract), and explicitly teaches using boron (B), phosphorus (P), and sulfur (S) doping to tune the interlayer spacing and defect concentration of hard carbons (pg. 2, col. 2, lines 2-8). Li further discloses a preparation method for conventional hard carbons via pyrolysis to yield B-doped, S-doped, and P-doped hard carbons, wherein a specific doping level of 0.1 wt% is used for S in the hard carbon matrix (pg. 3, col. 1, section 2.1, para. 1, lines 1-9). Li also highlights that heteroatom doping (such as B-doping) may induce in-plane defects that bind inserted ions much more strongly, thereby enlarging storage capacity (pg. 5, col. 2, lines 1-10; pg. 8, col. 2, para. 2), and that boron doping sufficiently retains the graphenic nature of the of the doped carbon layers (pg. 5, col. 1, para. 2, lines 1-14).
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to modify the nonporous portion of the negative electrode active material particles of Yue by incorporating the heteroatom doping teachings and specific concentration levels of heteroatoms, as taught by Li. A PHOSITA would have been motivated to implement Li's doping parameters because Li teaches that systematic heteroatom doping (specifically using boron, sulfur, or phosphorus) directly tunes interlayer spacing, alters defect concentrations, and significantly increases ion-storage capacity. Furthermore, regarding the claimed limitation of an atomic percentage of heteroatoms of less than or equal to 0.1%, Li explicitly discloses a doping level of 0.1 wt% for the heteroatom sulfur; in addition, it is well-established that a weight percentage of 0.1% for sulfur in a carbon/oxygen matrix would convert to a highly similar, overlapping, or adjacent atomic percentage range.
However, it should be noted that the atomic percentage of heteroatoms is a result effective variable. A PHOSITA seeking to optimize the defect concentrations and ion storage properties (as taught by Li) would routinely vary the heteroatom concentrations, including testing amounts slightly below 0.1%, in order to find the optimum balance of structural integrity and capacity, particularly in terms of defects introduced by the heteroatoms. Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed the invention to create the battery using an atomic percentage of heteroatoms that is less than 0.1% in the nonporous portion of the negative electrode active material particles, since it has been held that discovering an optimum value of a result effective variable involves only routine skill in the art. In re Boesch, 617 F.2d 272, 205 USPQ 215 (CCPA 1980).
Claims 13-15, and 18 are rejected under 35 U.S.C. 103 as being unpatentable over Yue (CN101887966A) as applied to claim 8 above.
Regarding claim 13, modified Yue teaches all features of claim 8 as described above, including a negative electrode comprising negative electrode active material particles, wherein each particle comprises a porous and nonporous portion. Yue further teaches the negative electrode active material particles comprise hard carbon (composite hard carbon anode material; claim 1) and the particles are block-shaped fine particles with a porous structure (specification, pg. 2 lines 23-27). Yue explicitly discloses that the hard carbon anode material has a porosity of 9% to 19% (i.e. 0.09 to 0.19).
The "porous portion" represents the pore area, while the "nonporous portion" represents the remaining carbon matrix area. Based on standard stereological principles and the geometric properties of porous particles, a volumetric porosity (P) maps to an area fraction in any given representative cross-section. The area of the porous portion is proportional to P, and the area of the nonporous portion is proportional to (1 – P). Calculating the ratio of the porous-to-nonporous area from Yue’s disclosed porosity range yields:
at the lower limit (9% porosity): 0.09/(1-0.09) ≈ 0.0989
at the upper limit (19% porosity): 0.19/(1-0.19) ≈ 0.2346
Accordingly, Yue implicitly and inherently discloses a porous-to-nonporous area ratio ranging from approximately 0.099 to 0.235. This range falls entirely within the claimed range of 0.05 to 0.30.
When the prior art discloses a general range that overlaps or routinely encompasses the claimed range, a prima facie case of obviousness is established (see MPEP §2144.05). Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to have selected from the overlapping portion of the ranges taught by Yue, because overlapping ranges have been held to establish prima facie obviousness.
Regarding claim 14, modified Yue teaches all features of claim 8 as described above, including a composite hard carbon anode material comprised of block-shaped fine particles with a porous structure. Yue further teaches wherein the porous portion has a pore diameter with a value ranging from 0.2 nm to 100 nm (specification, pg. 2 lines 23-27), which overlaps with the claimed range of 0.1 μm to 3 μm (i.e., 100 nm to 300 nm).
When the prior art discloses a general range that overlaps or routinely encompasses the claimed range, a prima facie case of obviousness is established (see MPEP §2144.05). Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to have selected from the overlapping portion of the ranges taught by Yue, because overlapping ranges have been held to establish prima facie obviousness.
Regarding claim 15, modified Yue teaches all features of claim 8 as described above, and further teaches the negative electrode wherein the negative electrode has a porosity of 9 to 19% (composite hard carbon anode material porosity; specification, pg. 2 lines 23-24), which overlaps with the claimed range of 15% to 40%.
When the prior art discloses a general range that overlaps or routinely encompasses the claimed range, a prima facie case of obviousness is established (see MPEP §2144.05). Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to have selected from the overlapping portion of the ranges taught by Yue, because overlapping ranges have been held to establish prima facie obviousness.
Regarding claim 18, modified Yue teaches all features of claim 8 as described above, and further teaches the electrochemical apparatus wherein the negative electrode active material particles comprise hard carbon (hard carbon negative electrode material particles; specification, pg. 2 lines 23-27).
Claim 17 is rejected under 35 U.S.C. 103 as being unpatentable over Yue (CN101887966A) as applied to claim 8 above, and further in view of Lee (US20200266422A1).
Regarding claim 17, modified Yue teaches all features of claim 8 as described above, including a negative electrode comprising negative electrode active material particles, wherein each particle comprises a porous and nonporous portion. Yue further discloses the negative electrode active material particles comprise hard carbon (composite hard carbon anode material with hard carbon negative electrode material particles; specification, pg. 2 lines 23-27), such that the disclosed composite hard carbon anode material is a block-shaped fine particle with a porous structure and a particle size range of 0.5 μm - 90 μm (specification, pg. 2 lines 23-27).
However, Yue does not expressly teach the electrochemical apparatus wherein the negative electrode active material particles have Dv10 < 6 μm, Dv50 < 15 μm and Dv90 < 30 μm.
Lee discloses a lithium secondary battery comprising a negative electrode active material layer with a negative electrode active material that includes a mix of graphite particles and low crystalline carbon-based particles (claim 1), wherein the low crystalline carbon-based particles are hard carbon particles (claim 8) and are capable of adsorbing and releasing Li ions (claim 5). Lee further discloses a Dv10 of 2 μm or less (claim 10), a Dv50 of 4 μm or less (claim 9), and a Dv90 of 8 μm or less (claim 11); thus, the Dv10, Dv50, and Dv90 ranges of Lee overlap with the claimed ranges. Lee additionally teaches that when the Dv10, Dv50, and Dv90 values are within the disclosed ranges, excellent output characteristics and high-temperature storage efficiency of the lithium secondary battery can be achieved (Dv50, [0080]-[0082]; Dv10 [0107]; Dv90 [0102]).
Since modified Yue teaches hard carbon negative electrode material particles for a negative electrode active material with all features of claim 8, and Lee teaches negative electrode active material comprising hard carbon particles with Dv10, Dv50, and Dv90 values that overlap with the claimed ranges, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to modify the negative electrode active material particles of Yue to have a Dv10 of 2 μm or less, a Dv50 of 4 μm or less, and a Dv90 of 8 μm or less, as taught by Lee, in order to achieve excellent output characteristics and high-temperature storage efficiency of the lithium secondary battery.
In addition, when the prior art discloses a general range that overlaps or routinely encompasses the claimed range, a prima facie case of obviousness is established (see MPEP §2144.05). Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to have selected from the overlapping portion of the ranges taught by Yue, because overlapping ranges have been held to establish prima facie obviousness.
Conclusion
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/A.R.O./Examiner, Art Unit 1789
/JENNIFER A BOYD/Supervisory Patent Examiner, Art Unit 1786
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