PRECURSOR MATERIAL AND PREPARATION METHOD THEREFOR, POSITIVE ELECTRODE MATERIAL, POSITIVE ELECTRODE SHEET, SECONDARY BATTERY, AND POWER CONSUMING APPARATUS
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 .
Response to Amendment
In response to communication filed on 5/11/2026:
Claims 1 and 21 have been amended; claim 23 has been canceled. Claim 24 has been added. No new matter has been entered.
Previous rejections under 35 USC 103 have been modified due to amendment.
Response to Arguments
The Applicant discloses: “Kim '963 discloses ‘a positive electrode active material precursor including nickel, cobalt, and manganese, wherein it has a crystalline size satisfying Equation 1 and Equation 2 below [:] 2.5≤C100/C001≤5 [Equation 1] 1≤C101/C001≤3.0 [Equation 2] Kim’963 ¶ [0066]’. However, Kim '963 does not disclose or suggest C100/C001>6.0.
For at least the reasons discussed above, Kim '963 does not disclose or suggest that "a ratio of grain sizes of (100) plane to (001) plane of the precursor material is greater than or equal to 6.0," as recited in amended claim 1.”
The Examiner respectfully traverses. The Applicant has amended C100/C001>4.4 to C100/C001>6.0 and cites Table 2 of specification for support of said amendment. The only example that supports this range is example 23 which has C100/C001=7.8. This is not enough data to support a case for criticality. MPEP 716.02(d) II: Demonstrating Criticality of a Claimed Range To establish unexpected results over a claimed range, applicants should compare a sufficient number of tests both inside and outside the claimed range to show the criticality of the claimed range. In re Hill, 284 F.2d 955, 128 USPQ 197 (CCPA 1960).
Further, Kim ‘963 discloses C100/C001≤5. MPEP 2144.05 I Similarly, a prima facie case of obviousness exists where the claimed ranges or amounts do not overlap with the prior art but are merely close. Titanium Metals Corp. of America v. Banner, 778 F.2d 775, 783, 227 USPQ 773, 779. See also Warner-Jenkinson Co., Inc. v. Hilton Davis Chemical Co., 520 U.S. 17, 41 USPQ2d 1865 (1997) (under the doctrine of equivalents, a purification process using a pH of 5.0 could infringe a patented purification process requiring a pH of 6.0-9.0); In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955) (Claimed process which was performed at a temperature between 40°C and 80°C and an acid concentration between 25% and 70% was held to be prima facie obvious over a reference process which differed from the claims only in that the reference process was performed at a temperature of 100°C and an acid concentration of 10%); In re Scherl, 156 F.2d 72, 74-75, 70 USPQ 204, 205-206 (CCPA 1946) (prior art showed an angle in a groove of up to 90° and an applicant claimed an angle of no less than 120°); In re Becket, 88 F.2d 684 (CCPA 1937) ("Where the component elements of alloys are the same, and where they approach so closely the same range of quantities as is here the case, it seems that there ought to be some noticeable difference in the qualities of the respective alloys."); In re Dreyfus, 73 F.2d 931, 934, 24 USPQ 52, 55 (CCPA 1934)(the prior art, which taught about 0.7:1 of alkali to water, renders unpatentable a claim that increased the proportion to at least 1:1 because there was no showing that the claimed proportions were critical); In re Lilienfeld, 67 F.2d 920, 924, 20 USPQ 53, 57 (CCPA 1933)(the prior art teaching an alkali cellulose containing minimal amounts of water, found by the Examiner to be in the 5-8% range, the claims sought to be patented were to an alkali cellulose with varying higher ranges of water (e.g., "not substantially less than 13%," "not substantially below 17%," and "between about 13[%] and 20%"); K-Swiss Inc. v. Glide N Lock GmbH, 567 Fed. App'x 906 (Fed. Cir. 2014)(reversing the Board's decision, in an appeal of an inter partes reexamination proceeding, that certain claims were not prima facie obvious due to non-overlapping ranges).
Claim Rejections - 35 USC § 103
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention(s) absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and effective filing dates of each claim that was not commonly owned as of the effective filing date of the later invention in order for the examiner to consider the applicability of 35 U.S.C. 102(b)(2)(C) for any potential 35 U.S.C. 102(a)(2) prior art against the later invention.
Claims 1-4, 7-9, 19, and 20 are rejected under 35 U.S.C. 103 as unpatentable over Ding et al. (CN 115 140 783 A) and Beierling et al. (US 2022/0194814 A1) and further in view of Kim (WO 2021/187963 A1 using US 2022/0407063 as an English language translation.).
Regarding claims 1-3, 19, and 20, Ding et al. teach a precursor material, having a chemical formula of NixCoyMnzMa(OH)2, wherein element M comprises at least one of Zr, Y, Al, Ti, W, Sr, Ta, Mo, Sb, Nb, Na, K, Ca, Ce, and La, 0.55≤x<1.0, 0≤y<0.45, 0≤z<0.45, 0<a≤0.45, a+x+y+z＝1 (Claim 1 discloses a ternary cathode material precursor characterized by the chemical formula NixCoyMnzM1-x-y-z(OH)2 wherein M=Zr, Y, Al, Ti, W, Nb, and Ca. Further, 0.6≤ x≤1.0, 0＜y≤0.4, 0＜z≤0.4, 0≤1-x-y-z≤0.4.).
However, Ding et al. do not teach the number of (101) crystal plane layers of the precursor material is 20-70 or 25-55.
Paragraph 0076 of the as-filed specification discloses the number of layers of the (101) plane of the precursor material can be calculated by methods and equipment known in the art, for example, by fitting the X-ray diffraction (XRD) pattern. A grain size D101 of the (101) plane is calculated: D101=kλ/(B101*cosθ101), where B101 is the half-peak width of the diffraction peak of the (101) plane of the precursor material, k is a coefficient (generally 0.89-0.90), θ101 is the diffraction angle at the diffraction peak of the (101) plane of the precursor material in the XRD pattern; the interlayer spacing d101 of the (101) plane is calculated: d101=nλ/(2*sinθ101), where θ101 is the diffraction angle at the diffraction peak of the (101) plane of the precursor material, and λ is the wavelength of the copper target. Then the corresponding value is calculated. After summarizing the above parameters, the number of layers of the (101) plane is obtained: N101=D101/d101.
Applying this method of calculation to the XRD data presented in Ding, one of ordinary skill in the art can find D101 and d101. Figs. 1-4 of Ding show XRD patterns of the precursors claimed. The (101) peak appears at a 2θ=40° and therefore θ101 can be set to 20° when calculating D101 and d101. Further, paragraph 0009 of Ding discloses that the XRD diffraction peak half maximum width FWHM (101) of the (101) crystal plane is 0.350°-0.550° which corresponds to B101 when calculating D101 and d101.
Calculating D101 and d101
k=0.90, n=1, λ is omitted
if B101=0.35° then D101= kλ/(B101*cosθ101) = 0.90/{(0.35°*π/180) *cos(20°*π/180)}=192
if B101=0.55° then D101= kλ/(B101*cosθ101) = 0.90/{(0.55°*π/180)*cos(20°*π/180)}=121.2
d101=nλ/(2*sinθ101) =1/{2*sin(40°*π/180)} =1.47
Further, Ding discloses that B101≤0.650° (Paragraph 0008)
Therefore, when B101=0.65° then D101= kλ/(B101*cosθ101) = 0.90/{(0.65°*π/180) *cos(20°*π/180)} =81.
Calculating N101
When B101 is 0.350°-0.550°, N101=D101/d101=(121.2-192)/1.47=68-102 layers which overlaps claim 1.
When B101 is 0.650°, N101=D101/d101=81/1.47=55 layers which overlaps claim 3.
Therefore, using the XRD pattern and FWHM values disclosed in Ding, one of ordinary skill in the art would be able to determine the number of layers in the (101) plane by the same method as claimed in the present application.
However, they do not teach wherein a pore volume of the precursor material is greater than or equal to 0.02 cm3/g and less than or equal to 0.032 cm3/g or wherein a specific surface area of the precursor material is 4 m2/g-20m2/g, and optionally 8 m2/g- 13m2/g.
Beierling et al. teach a mixed hydroxide of TM wherein TM comprises Ni and at least one of Co and Mn and, optionally, Al, Mg, Zr or Ti (Abstract). Further, the precursor can comprise the formula NiaM1bMncOx(OH)y(CO3)t wherein M1=Co and at least one metal selected from Ti, Zr, or Al, a is in the range from 0.15 to 0.95, preferably 0.5 to 0.9, b is in the range from zero to 0.35, preferably 0.03 to 0.2, c is in the range from zero to 0.8, preferably 0.05 to 0.65, 0≤x<1, 1<y≤2.2, and 0≤t≤0.3 (Paragraphs 0090-0095). Further, the pore volume can be 0.033 to 0.1 ml/g (Paragraph 0114) and a BET surface area of 12.48 m2/g (Paragraph 0160).
While Beierling et al. disclose the pore volume is at least 0.033 ml/g which is outside the claimed range of 0.02-0.032 cm3/g this difference of 0.001 cm3/g is only a 0.1% difference which is extremely close in value. MPEP 2144.05 I: Similarly, a prima facie case of obviousness exists where the claimed ranges or amounts do not overlap with the prior art but are merely close. Titanium Metals Corp. of America v. Banner, 778 F.2d 775, 783, 227 USPQ 773, 779 (Fed. Cir. 1985)
Therefore, it would have been obvious to one of ordinary skill in the art to modify Ding with Beierling in order to improve cycling stability.
However, neither Ding nor Beierling et al. teach a ratio of grain sizes of (100) plane to (001) plane of the precursor material is greater than or equal to 6.
Kim et al. teach a positive electrode active material precursor for a lithium secondary battery (Abstract). Further, the precursor comprises nickel (Paragraph 0030), cobalt (Paragraph 0031), and manganese (Paragraph 0032) and can additionally comprise a transition metal such as Zr, Ti, W, Ta, Mo, and Nb (Paragraph 0033). Finally, the positive electrode active material precursor according to the present invention may be prepared by the above-described preparation method of the present invention, and is a positive electrode active material precursor including nickel, cobalt, and manganese, wherein it has a crystalline size satisfying Equation 1: 2.5≤C100/C001≤5 wherein C100 is a crystalline size in a (100) plane and C001 is a crystalline size in a (001) plane (Paragraphs 0066-0067). MPEP 2144.05 I Similarly, a prima facie case of obviousness exists where the claimed ranges or amounts do not overlap with the prior art but are merely close. Titanium Metals Corp. of America v. Banner, 778 F.2d 775, 783, 227 USPQ 773, 779. See also Warner-Jenkinson Co., Inc. v. Hilton Davis Chemical Co., 520 U.S. 17, 41 USPQ2d 1865 (1997) (under the doctrine of equivalents, a purification process using a pH of 5.0 could infringe a patented purification process requiring a pH of 6.0-9.0); In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955) (Claimed process which was performed at a temperature between 40°C and 80°C and an acid concentration between 25% and 70% was held to be prima facie obvious over a reference process which differed from the claims only in that the reference process was performed at a temperature of 100°C and an acid concentration of 10%); In re Scherl, 156 F.2d 72, 74-75, 70 USPQ 204, 205-206 (CCPA 1946) (prior art showed an angle in a groove of up to 90° and an applicant claimed an angle of no less than 120°); In re Becket, 88 F.2d 684 (CCPA 1937) ("Where the component elements of alloys are the same, and where they approach so closely the same range of quantities as is here the case, it seems that there ought to be some noticeable difference in the qualities of the respective alloys."); In re Dreyfus, 73 F.2d 931, 934, 24 USPQ 52, 55 (CCPA 1934)(the prior art, which taught about 0.7:1 of alkali to water, renders unpatentable a claim that increased the proportion to at least 1:1 because there was no showing that the claimed proportions were critical); In re Lilienfeld, 67 F.2d 920, 924, 20 USPQ 53, 57 (CCPA 1933)(the prior art teaching an alkali cellulose containing minimal amounts of water, found by the Examiner to be in the 5-8% range, the claims sought to be patented were to an alkali cellulose with varying higher ranges of water (e.g., "not substantially less than 13%," "not substantially below 17%," and "between about 13[%] and 20%"); K-Swiss Inc. v. Glide N Lock GmbH, 567 Fed. App'x 906 (Fed. Cir. 2014)(reversing the Board's decision, in an appeal of an inter partes reexamination proceeding, that certain claims were not prima facie obvious due to non-overlapping ranges).
Therefore, it would have been obvious to one of ordinary skill in the art to modify Ding and Beierling with Kim in order to suppress growth of a (001) crystal plane to enhance electrochemical properties.
Regarding claim 4, Ding, Beierling, and Kim et al. teach the precursor material according to claim 1. However, they do not teach wherein a deformation fault probability fD of the precursor material is less than or equal to 7.0%, and optionally less than or equal to 4.0%.
Paragraph 0084 of the as-filed specification discloses fD can be calculated by methods and equipment known in the art, for example, by fitting the X-ray diffraction (XRD) pattern. After fitting the XRD pattern of the precursor, the deformation fault probability fD is calculated:
fD=8.89645×B101×π/180-1.85325×B102×π/180-43.9925/D001
where B101 is the half-height width of the diffraction peak of the (101) plane of the precursor material, B102 is the half-height width of the diffraction peak of the (102) plane of the precursor material, and D001 is the grain size of the diffraction peak of the (001) plane of the precursor material. Then the corresponding value is calculated.
Ding et al. disclose values for B101 and B102. Further, the peak for a (001) plane is shown in Figures 1-4. Being that Ding et al. disclose the exact precursor composition as claimed and also the exact methods and equipment known in the art (by fitting the XRD pattern displayed), it would be obvious to one of ordinary skill in the art to determine the fD within the claimed range. Wherein the claimed and prior art products are identical or substantially identical, the burden of proof is on application to establish that the prior art products do not necessarily or inherently possess the characteristics of the instantly claimed products.
I. PRODUCT AND APPARATUS CLAIMS — WHEN THE STRUCTURE RECITED IN THE REFERENCE IS SUBSTANTIALLY IDENTICAL TO THAT OF THE CLAIMS, CLAIMED PROPERTIES OR FUNCTIONS ARE PRESUMED TO BE INHERENT Where the claimed and prior art products are identical or substantially identical in structure or composition, or are produced by identical or substantially identical processes, a prima facie case of either anticipation or obviousness has been established. In re Best, 562 F.2d 1252, 1255, 195 USPQ 430, 433 (CCPA 1977). "When the PTO shows a sound basis for believing that the products of the applicant and the prior art are the same, the applicant has the burden of showing that they are not." In re Spada, 911 F.2d 705, 709, 15 USPQ2d 1655, 1658 (Fed. Cir. 1990). Therefore, the prima facie case can be rebutted by evidence showing that the prior art products do not necessarily possess the characteristics of the claimed product. In re Best, 562 F.2d at 1255, 195 USPQ at 433. See also Titanium Metals Corp. v. Banner, 778 F.2d 775, 227 USPQ 773 (Fed. Cir. 1985) II. COMPOSITION CLAIMS — IF THE COMPOSITION IS PHYSICALLY THE SAME, IT MUST HAVE THE SAME PROPERTIES "Products of identical chemical composition cannot have mutually exclusive properties." In re Spada, 911 F.2d 705, 709, 15 USPQ2d 1655, 1658 (Fed. Cir. 1990). A chemical composition and its properties are inseparable. Therefore, if the prior art teaches the identical chemical structure, the properties applicant discloses and/or claims are necessarily present.
Regarding claim 7, Ding, Beierling, and Kim et al teach the precursor material according to claim 1. Further, Ding et al. teach wherein a Dv50 of the precursor material is 3 µm to 15 µm (Paragraph 0032 discloses 7-13 µm.).
Regarding claim 9, Ding, Beierling, and Kim et al teach the precursor material according to claim 1. Further, Ding et al. teach wherein an intensity ratio of diffraction peaks of the (001) plane and (101) plane of the precursor material is 0.60-1.25, and optionally 0.9-1.18 (Figs. 1-4 show the (001) and (100) plane having intensities that show ratios between the claimed values.).
Claim 22 is rejected under 35 U.S.C. 103 as unpatentable over Ding et al. (CN 115 140 783 A), Beierling et al. (US 2022/0194814 A1), and Kim (WO 2021/187963 A1 using US 2022/0407063 as an English language translation.) as applied to claim 1 above, and further in view of Park et al. (KR 2021-0006869 A1)
Regarding claim 22, the combination of Ding, Beierling, and Kim et al. teach the precursor material according to claim 1. However, they do not teach wherein the element M comprises at least one of Sb, Na, K, or La.
Park et al. disclose a positive electrode active material for a secondary battery which comprises a precursor made of Ni, Co, and Mn (Abstract). Further, the precursor can comprise formula NixCoyMnzMpOH2 wherein 0.6<x<1.0, 0<y<0.4, 0<z<0.3, 0≤p<0.05, x+y+z+p=1 and M=La (Claim 4).
Therefore, it would have been obvious to one of ordinary skill in the art to modify Ding, Beierling, and Kim with Park in order to improve reactivity of the precursor.
Claim 24 is rejected under 35 U.S.C. 103 as unpatentable over Ding et al. (CN 115 140 783 A), Beierling et al. (US 2022/0194814 A1), and Kim (WO 2021/187963 A1 using US 2022/0407063 as an English language translation.) and further in view of Wang et al. (WO 2021/175233 A1 using US 2022/03371911 A1 as an English language translation.).
Regarding claim 24, Ding et al. teach a precursor material, having a chemical formula of NixCoyMnzMa(OH)2, wherein 0.55≤x<1.0, 0≤y<0.45, 0≤z<0.45, 0<a≤0.45, a+x+y+z＝1 (Claim 1 discloses a ternary cathode material precursor characterized by the chemical formula NixCoyMnzM1-x-y-z(OH)2. Further, 0.6≤ x≤1.0, 0＜y≤0.4, 0＜z≤0.4, 0≤1-x-y-z≤0.4.).
However, Ding et al. do not teach the number of (101) crystal plane layers of the precursor material is 20-70 or 25-55.
Paragraph 0076 of the as-filed specification discloses the number of layers of the (101) plane of the precursor material can be calculated by methods and equipment known in the art, for example, by fitting the X-ray diffraction (XRD) pattern. A grain size D101 of the (101) plane is calculated: D101=kλ/(B101*cosθ101), where B101 is the half-peak width of the diffraction peak of the (101) plane of the precursor material, k is a coefficient (generally 0.89-0.90), θ101 is the diffraction angle at the diffraction peak of the (101) plane of the precursor material in the XRD pattern; the interlayer spacing d101 of the (101) plane is calculated: d101=nλ/(2*sinθ101), where θ101 is the diffraction angle at the diffraction peak of the (101) plane of the precursor material, and λ is the wavelength of the copper target. Then the corresponding value is calculated. After summarizing the above parameters, the number of layers of the (101) plane is obtained: N101=D101/d101.
Applying this method of calculation to the XRD data presented in Ding, one of ordinary skill in the art can find D101 and d101. Figs. 1-4 of Ding show XRD patterns of the precursors claimed. The (101) peak appears at a 2θ=40° and therefore θ101 can be set to 20° when calculating D101 and d101. Further, paragraph 0009 of Ding discloses that the XRD diffraction peak half maximum width FWHM (101) of the (101) crystal plane is 0.350°-0.550° which corresponds to B101 when calculating D101 and d101.
Calculating D101 and d101
k=0.90, n=1, λ is omitted
if B101=0.35° then D101= kλ/(B101*cosθ101) = 0.90/{(0.35°*π/180) *cos(20°*π/180)}=192
if B101=0.55° then D101= kλ/(B101*cosθ101) = 0.90/{(0.55°*π/180)*cos(20°*π/180)}=121.2
d101=nλ/(2*sinθ101) =1/{2*sin(40°*π/180)} =1.47
Further, Ding discloses that B101≤0.650° (Paragraph 0008)
Therefore, when B101=0.65° then D101= kλ/(B101*cosθ101) = 0.90/{(0.65°*π/180) *cos(20°*π/180)} =81.
Calculating N101
When B101 is 0.350°-0.550°, N101=D101/d101=(121.2-192)/1.47=68-102 layers which overlaps claim 1.
When B101 is 0.650°, N101=D101/d101=81/1.47=55 layers which overlaps claim 3.
Therefore, using the XRD pattern and FWHM values disclosed in Ding, one of ordinary skill in the art would be able to determine the number of layers in the (101) plane by the same method as claimed in the present application.
However, they do not teach wherein a pore volume of the precursor material is greater than or equal to 0.02 cm3/g and less than or equal to 0.032 cm3/g or wherein a specific surface area of the precursor material is 4 m2/g-20m2/g, and optionally 8 m2/g- 13m2/g.
Beierling et al. teach a mixed hydroxide of TM wherein TM comprises Ni and at least one of Co and Mn and, optionally, Al, Mg, Zr or Ti (Abstract). Further, the precursor can comprise the formula NiaM1bMncOx(OH)y(CO3)t wherein M1=Co and at least one metal selected from Ti, Zr, or Al, a is in the range from 0.15 to 0.95, preferably 0.5 to 0.9, b is in the range from zero to 0.35, preferably 0.03 to 0.2, c is in the range from zero to 0.8, preferably 0.05 to 0.65, 0≤x<1, 1<y≤2.2, and 0≤t≤0.3 (Paragraphs 0090-0095). Further, the pore volume can be 0.033 to 0.1 ml/g (Paragraph 0114) and a BET surface area of 12.48 m2/g (Paragraph 0160).
While Beierling et al. disclose the pore volume is at least 0.033 ml/g which is outside the claimed range of 0.02-0.032 cm3/g this difference of 0.001 cm3/g is only a 0.1% difference which is extremely close in value. MPEP 2144.05 I: Similarly, a prima facie case of obviousness exists where the claimed ranges or amounts do not overlap with the prior art but are merely close. Titanium Metals Corp. of America v. Banner, 778 F.2d 775, 783, 227 USPQ 773, 779 (Fed. Cir. 1985)
Therefore, it would have been obvious to one of ordinary skill in the art to modify Ding with Beierling in order to improve cycling stability.
However, neither Ding nor Beierling et al. teach a ratio of grain sizes of (100) plane to (001) plane of the precursor material is greater than or equal to 6.
Kim et al. teach a positive electrode active material precursor for a lithium secondary battery (Abstract). Further, the precursor comprises nickel (Paragraph 0030), cobalt (Paragraph 0031), and manganese (Paragraph 0032) and can additionally comprise a transition metal such as Zr, Ti, W, Ta, Mo, and Nb (Paragraph 0033). Finally, the positive electrode active material precursor according to the present invention may be prepared by the above-described preparation method of the present invention, and is a positive electrode active material precursor including nickel, cobalt, and manganese, wherein it has a crystalline size satisfying Equation 1: 2.5≤C100/C001≤5 wherein C100 is a crystalline size in a (100) plane and C001 is a crystalline size in a (001) plane (Paragraphs 0066-0067). MPEP 2144.05 I Similarly, a prima facie case of obviousness exists where the claimed ranges or amounts do not overlap with the prior art but are merely close. Titanium Metals Corp. of America v. Banner, 778 F.2d 775, 783, 227 USPQ 773, 779. See also Warner-Jenkinson Co., Inc. v. Hilton Davis Chemical Co., 520 U.S. 17, 41 USPQ2d 1865 (1997) (under the doctrine of equivalents, a purification process using a pH of 5.0 could infringe a patented purification process requiring a pH of 6.0-9.0); In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955) (Claimed process which was performed at a temperature between 40°C and 80°C and an acid concentration between 25% and 70% was held to be prima facie obvious over a reference process which differed from the claims only in that the reference process was performed at a temperature of 100°C and an acid concentration of 10%); In re Scherl, 156 F.2d 72, 74-75, 70 USPQ 204, 205-206 (CCPA 1946) (prior art showed an angle in a groove of up to 90° and an applicant claimed an angle of no less than 120°); In re Becket, 88 F.2d 684 (CCPA 1937) ("Where the component elements of alloys are the same, and where they approach so closely the same range of quantities as is here the case, it seems that there ought to be some noticeable difference in the qualities of the respective alloys."); In re Dreyfus, 73 F.2d 931, 934, 24 USPQ 52, 55 (CCPA 1934)(the prior art, which taught about 0.7:1 of alkali to water, renders unpatentable a claim that increased the proportion to at least 1:1 because there was no showing that the claimed proportions were critical); In re Lilienfeld, 67 F.2d 920, 924, 20 USPQ 53, 57 (CCPA 1933)(the prior art teaching an alkali cellulose containing minimal amounts of water, found by the Examiner to be in the 5-8% range, the claims sought to be patented were to an alkali cellulose with varying higher ranges of water (e.g., "not substantially less than 13%," "not substantially below 17%," and "between about 13[%] and 20%"); K-Swiss Inc. v. Glide N Lock GmbH, 567 Fed. App'x 906 (Fed. Cir. 2014)(reversing the Board's decision, in an appeal of an inter partes reexamination proceeding, that certain claims were not prima facie obvious due to non-overlapping ranges).
Therefore, it would have been obvious to one of ordinary skill in the art to modify Ding and Beierling with Kim in order to suppress growth of a (001) crystal plane to enhance electrochemical properties.
However, neither Ding, Beierling, nor Kim et al. teach wherein element M comprises at least one of Sb, Na, or K.
Wang et al. teach a lithium-manganese precursor material is at least one substance selected from the substances represented by the chemical formula MnaCobNicM1−a−b−c(OH)2 wherein 0.5≤a≤1, 0≤b≤0.5, 0≤c≤0.5, M is at least one element selected from the group consisting of Na or K (Paragraphs 0043-0044).
Therefore, it would have been obvious to one of ordinary skill in the art to modify the combination of Ding, Beierling, and Kim with Wang in order to improve capacity and cycle stability.
Claims 1, 3, 8, 9, 19, and 20 are 35 U.S.C. 103 as unpatentable over Kim et al. (US 2011/0305954 A1), Beierling et al. (US 2022/0194814 A1), and further in view of Kim (WO 2021/187963 A1 using US 2022/0407063 as an English language translation, referred to as “Kim ‘063” for clarity.).
Regarding claims 1, 3, 8, 19, and 20, Kim et al. teach a precursor material, having a chemical formula of NixCoyMnzMa(OH)2, wherein element M comprises at least one of Zr, Y, Al, Ti, W, Sr, Ta, Mo, Sb, Nb, Na, K, Ca, Ce, and La, 0.55≤x<1.0, 0≤y<0.45, 0≤z<0.45, 0<a≤0.45, a+x+y+z＝1 (Abstract; paragraph 0048 disclose a positive active material precursor characterized by the chemical formula NixCoyMnzMk(OH)2 wherein M is a metal such as Al, Ti, or Zr. Further, 0.45≤x≤0.65, 0.15≤y≤0.25, 0.15≤z≤0.35, 0≤k≤0.1.).
However, Kim et al. do not teach the number of (101) crystal plane layers of the precursor material is 20-70 or 25-55.
Paragraph 0076 of the as-filed specification discloses the number of layers of the (101) plane of the precursor material can be calculated by methods and equipment known in the art, for example, by fitting the X-ray diffraction (XRD) pattern. A grain size D101 of the (101) plane is calculated: D101=kλ/(B101*cosθ101), where B101 is the half-peak width of the diffraction peak of the (101) plane of the precursor material, k is a coefficient (generally 0.89-0.90), θ101 is the diffraction angle at the diffraction peak of the (101) plane of the precursor material in the XRD pattern; the interlayer spacing d101 of the (101) plane is calculated: d101=nλ/(2*sinθ101), where θ101 is the diffraction angle at the diffraction peak of the (101) plane of the precursor material, and λ is the wavelength of the copper target. Then the corresponding value is calculated. After summarizing the above parameters, the number of layers of the (101) plane is obtained: N101=D101/d101.
Applying this method of calculation to the XRD data presented in Kim, one of ordinary skill in the art can find D101 and d101. Figure 2 and Table 1 show XRD patterns of the precursors claimed. The (101) peak appears at a 2θ=39.452° and therefore θ101 can be set to 19.726° when calculating D101 and d101. Further, Table 1 of Ding discloses that the XRD diffraction peak half maximum width FWHM (101) of the (101) crystal plane is 1.2348° which corresponds to B101 when calculating D101 and d101.
Calculating D101 and d101
k=0.90, n=1, λ is omitted
D101= kλ/(B101*cosθ101) = 0.90/{(1.2348°*π/180) *cos(19.726°*π/180)}=45
d101=nλ/(2*sinθ101) =1/{2*sin(19.726°*π/180)}=1.48
Calculating N101
N101=D101/d101=45/1.48=30 layers which overlaps claims 1 and 3.
Therefore, using the XRD pattern and FWHM values disclosed in Kim, one of ordinary skill in the art would be able to determine the number of layers in the (101) plane by the same method as claimed in the present application.
However, they do not teach wherein a pore volume of the precursor material is greater than or equal to 0.02 cm3/g and less than or equal to 0.032 cm3/g or wherein a specific surface area of the precursor material is 4 m2/g-20m2/g, and optionally 8 m2/g- 13m2/g.
Beierling et al. teach a mixed hydroxide of TM wherein TM comprises Ni and at least one of Co and Mn and, optionally, Al, Mg, Zr or Ti (Abstract). Further, the precursor can comprise the formula NiaM1bMncOx(OH)y(CO3)t wherein M1=Co and at least one metal selected from Ti, Zr, or Al, a is in the range from 0.15 to 0.95, preferably 0.5 to 0.9, b is in the range from zero to 0.35, preferably 0.03 to 0.2, c is in the range from zero to 0.8, preferably 0.05 to 0.65, 0≤x<1, 1<y≤2.2, and 0≤t≤0.3 (Paragraphs 0090-0095). Further, the pore volume can be 0.033 to 0.1 ml/g (Paragraph 0114) and a BET surface area of 12.48 m2/g (Paragraph 0160).
While Beierling et al. disclose the pore volume is at least 0.033 ml/g which is outside the claimed range of 0.02-0.032 cm3/g this difference of 0.001 cm3/g is only a 0.1% difference which is extremely close in value. MPEP 2144.05 I: Similarly, a prima facie case of obviousness exists where the claimed ranges or amounts do not overlap with the prior art but are merely close. Titanium Metals Corp. of America v. Banner, 778 F.2d 775, 783, 227 USPQ 773, 779 (Fed. Cir. 1985)
Therefore, it would have been obvious to one of ordinary skill in the art to modify Kim with Beierling in order to improve cycling stability.
However, neither Kim nor Beierling et al. teach a ratio of grain sizes of (100) plane to (001) plane of the precursor material is greater than or equal to 6.
Kim ‘063 et al. teach a positive electrode active material precursor for a lithium secondary battery (Abstract). Further, the precursor comprises nickel (Paragraph 0030), cobalt (Paragraph 0031), and manganese (Paragraph 0032) and can additionally comprise a transition metal such as Zr, Ti, W, Ta, Mo, and Nb (Paragraph 0033). Finally, the positive electrode active material precursor according to the present invention may be prepared by the above-described preparation method of the present invention, and is a positive electrode active material precursor including nickel, cobalt, and manganese, wherein it has a crystalline size satisfying Equation 1: 2.5≤C100/C001≤5 wherein C100 is a crystalline size in a (100) plane and C001 is a crystalline size in a (001) plane (Paragraphs 0066-0067). MPEP 2144.05 I Similarly, a prima facie case of obviousness exists where the claimed ranges or amounts do not overlap with the prior art but are merely close. Titanium Metals Corp. of America v. Banner, 778 F.2d 775, 783, 227 USPQ 773, 779. See also Warner-Jenkinson Co., Inc. v. Hilton Davis Chemical Co., 520 U.S. 17, 41 USPQ2d 1865 (1997) (under the doctrine of equivalents, a purification process using a pH of 5.0 could infringe a patented purification process requiring a pH of 6.0-9.0); In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955) (Claimed process which was performed at a temperature between 40°C and 80°C and an acid concentration between 25% and 70% was held to be prima facie obvious over a reference process which differed from the claims only in that the reference process was performed at a temperature of 100°C and an acid concentration of 10%); In re Scherl, 156 F.2d 72, 74-75, 70 USPQ 204, 205-206 (CCPA 1946) (prior art showed an angle in a groove of up to 90° and an applicant claimed an angle of no less than 120°); In re Becket, 88 F.2d 684 (CCPA 1937) ("Where the component elements of alloys are the same, and where they approach so closely the same range of quantities as is here the case, it seems that there ought to be some noticeable difference in the qualities of the respective alloys."); In re Dreyfus, 73 F.2d 931, 934, 24 USPQ 52, 55 (CCPA 1934)(the prior art, which taught about 0.7:1 of alkali to water, renders unpatentable a claim that increased the proportion to at least 1:1 because there was no showing that the claimed proportions were critical); In re Lilienfeld, 67 F.2d 920, 924, 20 USPQ 53, 57 (CCPA 1933)(the prior art teaching an alkali cellulose containing minimal amounts of water, found by the Examiner to be in the 5-8% range, the claims sought to be patented were to an alkali cellulose with varying higher ranges of water (e.g., "not substantially less than 13%," "not substantially below 17%," and "between about 13[%] and 20%"); K-Swiss Inc. v. Glide N Lock GmbH, 567 Fed. App'x 906 (Fed. Cir. 2014)(reversing the Board's decision, in an appeal of an inter partes reexamination proceeding, that certain claims were not prima facie obvious due to non-overlapping ranges).
Therefore, it would have been obvious to one of ordinary skill in the art to modify Kim and Beierling with Kim ‘063 in order to suppress growth of a (001) crystal plane to enhance electrochemical properties.
Regarding claim 9, Kim, Beierling, and Kim’063 et al. teach the precursor material according to claim 1. Further, Kim et al. disclose wherein an intensity ratio of diffraction peaks of the (001) plane and (101) plane of the precursor material is 0.60-1.25, and optionally 0.9-1.18 (Table 1, example 1 discloses a ratio of 1.).
Claim 22 is 35 U.S.C. 103 as unpatentable over Kim et al. (US 2011/0305954 A1) and Beierling et al. (US 2022/0194814 A1), and Kim (WO 2021/187963 A1 using US 2022/0407063 as an English language translation, referred to as “Kim ‘063” for clarity.) as applied to claim 1 above and further in view of Park et al. (KR 2021-0006869 A1)
Regarding claim 22, the combination of Kim, Beierling, and Kim ‘063 et al. teach the precursor material according to claim 1. However, they do not teach wherein the element M comprises at least one of Sb, Na, K, or La.
Park et al. disclose a positive electrode active material for a secondary battery which comprises a precursor made of Ni, Co, and Mn (Abstract). Further, the precursor can comprise formula NixCoyMnzMpOH2 wherein 0.6<x<1.0, 0<y<0.4, 0<z<0.3, 0≤p<0.05, x+y+z+p=1 and M=La (Claim 4).
Therefore, it would have been obvious to one of ordinary skill in the art to modify Kim, Beierling, and Kim ‘063 with Park in order to improve reactivity of the precursor.
Claim 24 is 35 U.S.C. 103 as unpatentable over Kim et al. (US 2011/0305954 A1), Beierling et al. (US 2022/0194814 A1), Kim (WO 2021/187963 A1 using US 2022/0407063 as an English language translation, referred to as “Kim ‘063” for clarity.) and further in view of Wang et al. (WO 2021/175233 using US 2022/0371911 A1 as an English language translation.).
Regarding claim 24, Kim et al. teach a precursor material, having a chemical formula of NixCoyMnzMa(OH)2, wherein element M comprises at least one of Zr, Y, Al, Ti, W, Sr, Ta, Mo, Sb, Nb, Na, K, Ca, Ce, and La, 0.55≤x<1.0, 0≤y<0.45, 0≤z<0.45, 0<a≤0.45, a+x+y+z＝1 (Abstract; paragraph 0048 disclose a positive active material precursor characterized by the chemical formula NixCoyMnzMk(OH)2 wherein M is a metal such as Al, Ti, or Zr. Further, 0.45≤x≤0.65, 0.15≤y≤0.25, 0.15≤z≤0.35, 0≤k≤0.1.).
However, Kim et al. do not teach the number of (101) crystal plane layers of the precursor material is 20-70 or 25-55.
Paragraph 0076 of the as-filed specification discloses the number of layers of the (101) plane of the precursor material can be calculated by methods and equipment known in the art, for example, by fitting the X-ray diffraction (XRD) pattern. A grain size D101 of the (101) plane is calculated: D101=kλ/(B101*cosθ101), where B101 is the half-peak width of the diffraction peak of the (101) plane of the precursor material, k is a coefficient (generally 0.89-0.90), θ101 is the diffraction angle at the diffraction peak of the (101) plane of the precursor material in the XRD pattern; the interlayer spacing d101 of the (101) plane is calculated: d101=nλ/(2*sinθ101), where θ101 is the diffraction angle at the diffraction peak of the (101) plane of the precursor material, and λ is the wavelength of the copper target. Then the corresponding value is calculated. After summarizing the above parameters, the number of layers of the (101) plane is obtained: N101=D101/d101.
Applying this method of calculation to the XRD data presented in Kim, one of ordinary skill in the art can find D101 and d101. Figure 2 and Table 1 show XRD patterns of the precursors claimed. The (101) peak appears at a 2θ=39.452° and therefore θ101 can be set to 19.726° when calculating D101 and d101. Further, Table 1 of Ding discloses that the XRD diffraction peak half maximum width FWHM (101) of the (101) crystal plane is 1.2348° which corresponds to B101 when calculating D101 and d101.
Calculating D101 and d101
k=0.90, n=1, λ is omitted
D101= kλ/(B101*cosθ101) = 0.90/{(1.2348°*π/180) *cos(19.726°*π/180)}=45
d101=nλ/(2*sinθ101) =1/{2*sin(19.726°*π/180)}=1.48
Calculating N101
N101=D101/d101=45/1.48=30 layers which overlaps claims 1 and 3.
Therefore, using the XRD pattern and FWHM values disclosed in Kim, one of ordinary skill in the art would be able to determine the number of layers in the (101) plane by the same method as claimed in the present application.
However, they do not teach wherein a pore volume of the precursor material is greater than or equal to 0.02 cm3/g and less than or equal to 0.032 cm3/g or wherein a specific surface area of the precursor material is 4 m2/g-20m2/g, and optionally 8 m2/g- 13m2/g.
Beierling et al. teach a mixed hydroxide of TM wherein TM comprises Ni and at least one of Co and Mn and, optionally, Al, Mg, Zr or Ti (Abstract). Further, the precursor can comprise the formula NiaM1bMncOx(OH)y(CO3)t wherein M1=Co and at least one metal selected from Ti, Zr, or Al, a is in the range from 0.15 to 0.95, preferably 0.5 to 0.9, b is in the range from zero to 0.35, preferably 0.03 to 0.2, c is in the range from zero to 0.8, preferably 0.05 to 0.65, 0≤x<1, 1<y≤2.2, and 0≤t≤0.3 (Paragraphs 0090-0095). Further, the pore volume can be 0.033 to 0.1 ml/g (Paragraph 0114) and a BET surface area of 12.48 m2/g (Paragraph 0160).
While Beierling et al. disclose the pore volume is at least 0.033 ml/g which is outside the claimed range of 0.02-0.032 cm3/g this difference of 0.001 cm3/g is only a 0.1% difference which is extremely close in value. MPEP 2144.05 I: Similarly, a prima facie case of obviousness exists where the claimed ranges or amounts do not overlap with the prior art but are merely close. Titanium Metals Corp. of America v. Banner, 778 F.2d 775, 783, 227 USPQ 773, 779 (Fed. Cir. 1985)
Therefore, it would have been obvious to one of ordinary skill in the art to modify Kim with Beierling in order to improve cycling stability.
However, neither Kim nor Beierling et al. teach a ratio of grain sizes of (100) plane to (001) plane of the precursor material is greater than or equal to 6.
Kim ‘063 et al. teach a positive electrode active material precursor for a lithium secondary battery (Abstract). Further, the precursor comprises nickel (Paragraph 0030), cobalt (Paragraph 0031), and manganese (Paragraph 0032) and can additionally comprise a transition metal such as Zr, Ti, W, Ta, Mo, and Nb (Paragraph 0033). Finally, the positive electrode active material precursor according to the present invention may be prepared by the above-described preparation method of the present invention, and is a positive electrode active material precursor including nickel, cobalt, and manganese, wherein it has a crystalline size satisfying Equation 1: 2.5≤C100/C001≤5 wherein C100 is a crystalline size in a (100) plane and C001 is a crystalline size in a (001) plane (Paragraphs 0066-0067). MPEP 2144.05 I Similarly, a prima facie case of obviousness exists where the claimed ranges or amounts do not overlap with the prior art but are merely close. Titanium Metals Corp. of America v. Banner, 778 F.2d 775, 783, 227 USPQ 773, 779. See also Warner-Jenkinson Co., Inc. v. Hilton Davis Chemical Co., 520 U.S. 17, 41 USPQ2d 1865 (1997) (under the doctrine of equivalents, a purification process using a pH of 5.0 could infringe a patented purification process requiring a pH of 6.0-9.0); In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955) (Claimed process which was performed at a temperature between 40°C and 80°C and an acid concentration between 25% and 70% was held to be prima facie obvious over a reference process which differed from the claims only in that the reference process was performed at a temperature of 100°C and an acid concentration of 10%); In re Scherl, 156 F.2d 72, 74-75, 70 USPQ 204, 205-206 (CCPA 1946) (prior art showed an angle in a groove of up to 90° and an applicant claimed an angle of no less than 120°); In re Becket, 88 F.2d 684 (CCPA 1937) ("Where the component elements of alloys are the same, and where they approach so closely the same range of quantities as is here the case, it seems that there ought to be some noticeable difference in the qualities of the respective alloys."); In re Dreyfus, 73 F.2d 931, 934, 24 USPQ 52, 55 (CCPA 1934)(the prior art, which taught about 0.7:1 of alkali to water, renders unpatentable a claim that increased the proportion to at least 1:1 because there was no showing that the claimed proportions were critical); In re Lilienfeld, 67 F.2d 920, 924, 20 USPQ 53, 57 (CCPA 1933)(the prior art teaching an alkali cellulose containing minimal amounts of water, found by the Examiner to be in the 5-8% range, the claims sought to be patented were to an alkali cellulose with varying higher ranges of water (e.g., "not substantially less than 13%," "not substantially below 17%," and "between about 13[%] and 20%"); K-Swiss Inc. v. Glide N Lock GmbH, 567 Fed. App'x 906 (Fed. Cir. 2014)(reversing the Board's decision, in an appeal of an inter partes reexamination proceeding, that certain claims were not prima facie obvious due to non-overlapping ranges).
Therefore, it would have been obvious to one of ordinary skill in the art to modify Kim and Beierling with Kim ‘063 in order to suppress growth of a (001) crystal plane to enhance electrochemical properties.
However, neither Kim, Beierling, nor Kim ‘063 et al. teach wherein element M comprises at least one of Sb, Na, or K.
Wang et al. teach a lithium-manganese precursor material is at least one substance selected from the substances represented by the chemical formula MnaCobNicM1−a−b−c(OH)2 wherein 0.5≤a≤1, 0≤b≤0.5, 0≤c≤0.5, M is at least one element selected from the group consisting of Na or K (Paragraphs 0043-0044).
Therefore, it would have been obvious to one of ordinary skill in the art to modify the combination of Kim, Beierling, and Kim ‘063 with Wang in order to improve capacity and cycle stability.
Claims 1-4, 7-9, 19, and 20 are rejected under 35 U.S.C. 103 as unpatentable over Ding et al. (CN 115 140 783 A) and Kaneda et al. (US 2019/0248673 A1) and further in view of Kim (WO 2021/187963 A1 using US 2022/0407063 as an English language translation.).
Regarding claims 1-3, 19, and 20, Ding et al. teach a precursor material, having a chemical formula of NixCoyMnzMa(OH)2, wherein element M comprises at least one of Zr, Y, Al, Ti, W, Sr, Ta, Mo, Sb, Nb, Na, K, Ca, Ce, and La, 0.55≤x<1.0, 0≤y<0.45, 0≤z<0.45, 0<a≤0.45, a+x+y+z＝1 (Claim 1 discloses a ternary cathode material precursor characterized by the chemical formula NixCoyMnzM1-x-y-z(OH)2 wherein M=Zr, Y, Al, Ti, W, Nb, and Ca. Further, 0.6≤ x≤1.0, 0＜y≤0.4, 0＜z≤0.4, 0≤1-x-y-z≤0.4.).
However, Ding et al. do not teach the number of (101) crystal plane layers of the precursor material is 20-70 or 25-55.
Paragraph 0076 of the as-filed specification discloses the number of layers of the (101) plane of the precursor material can be calculated by methods and equipment known in the art, for example, by fitting the X-ray diffraction (XRD) pattern. A grain size D101 of the (101) plane is calculated: D101=kλ/(B101*cosθ101), where B101 is the half-peak width of the diffraction peak of the (101) plane of the precursor material, k is a coefficient (generally 0.89-0.90), θ101 is the diffraction angle at the diffraction peak of the (101) plane of the precursor material in the XRD pattern; the interlayer spacing d101 of the (101) plane is calculated: d101=nλ/(2*sinθ101), where θ101 is the diffraction angle at the diffraction peak of the (101) plane of the precursor material, and λ is the wavelength of the copper target. Then the corresponding value is calculated. After summarizing the above parameters, the number of layers of the (101) plane is obtained: N101=D101/d101.
Applying this method of calculation to the XRD data presented in Ding, one of ordinary skill in the art can find D101 and d101. Figs. 1-4 of Ding show XRD patterns of the precursors claimed. The (101) peak appears at a 2θ=40° and therefore θ101 can be set to 20° when calculating D101 and d101. Further, paragraph 0009 of Ding discloses that the XRD diffraction peak half maximum width FWHM (101) of the (101) crystal plane is 0.350°-0.550° which corresponds to B101 when calculating D101 and d101.
Calculating D101 and d101
k=0.90, n=1, λ is omitted
if B101=0.35° then D101= kλ/(B101*cosθ101) = 0.90/{(0.35°*π/180) *cos(20°*π/180)} =192
if B101=0.55° then D101= kλ/(B101*cosθ101) = 0.90/{(0.55°*π/180) *cos(20°*π/180)} =121.2
d101=nλ/(2*sinθ101) =1/{2*sin(40°*π/180)} =1.47
Further, Ding discloses that B101≤0.650° (Paragraph 0008)
Therefore, when B101=0.65° then D101= kλ/(B101*cosθ101) = 0.90/{(0.65°*π/180) *cos(20°*π/180)} =81.
Calculating N101
When B101 is 0.350°-0.550°, N101=D101/d101= (121.2-192)/1.47=68-102 layers which overlaps claim 1.
When B101 is 0.650°, N101=D101/d101=81/1.47=55 layers which overlaps claim 3.
Therefore, using the XRD pattern and FWHM values disclosed in Ding, one of ordinary skill in the art would be able to determine the number of layers in the (101) plane by the same method as claimed in the present application.
However, they do not teach wherein a pore volume of the precursor material is greater than or equal to 0.02 cm3/g and less than or equal to 0.032 cm3/g or wherein a specific surface area of the precursor material is 4 m2/g-20m2/g, and optionally 8 m2/g- 13m2/g.
Kaneda et al. teach a mixed hydroxide of TM wherein TM comprises Ni and Mn and, optionally, Co, Zr, Ti, W, Ta, Mo, and Nb (Abstract; claim 1). Further, the precursor can comprise the formula NixMnyMzOx(OH)2+α wherein M=Co and at least one metal selected from Co, Zr, Ti, W, Ta, Mo, and Nb, 0.1≤x≤0.9, 0.05≤y≤0.8, 0≤z≤0.8, x+y+z=1.0, and 0≤α≤0.4 (Abstract; claim 1). Further, the pore volume can be 0.01 to 0.04 ml/g (Claim 2; example 2) and a BET surface area of 5-15 m2/g (Claim 4).
Therefore, it would have been obvious to one of ordinary skill in the art to modify Ding with Kaneda in order to improve energy density.
However, neither Ding nor Kaneda et al. teach a ratio of grain sizes of (100) plane to (001) plane of the precursor material is greater than or equal to 6.
Kim et al. teach a positive electrode active material precursor for a lithium secondary battery (Abstract). Further, the precursor comprises nickel (Paragraph 0030), cobalt (Paragraph 0031), and manganese (Paragraph 0032) and can additionally comprise a transition metal such as Zr, Ti, W, Ta, Mo, and Nb (Paragraph 0033). Finally, the positive electrode active material precursor according to the present invention may be prepared by the above-described preparation method of the present invention, and is a positive electrode active material precursor including nickel, cobalt, and manganese, wherein it has a crystalline size satisfying Equation 1: 2.5≤C100/C001≤5 wherein C100 is a crystalline size in a (100) plane and C001 is a crystalline size in a (001) plane (Paragraphs 0066-0067). MPEP 2144.05 I Similarly, a prima facie case of obviousness exists where the claimed ranges or amounts do not overlap with the prior art but are merely close. Titanium Metals Corp. of America v. Banner, 778 F.2d 775, 783, 227 USPQ 773, 779. See also Warner-Jenkinson Co., Inc. v. Hilton Davis Chemical Co., 520 U.S. 17, 41 USPQ2d 1865 (1997) (under the doctrine of equivalents, a purification process using a pH of 5.0 could infringe a patented purification process requiring a pH of 6.0-9.0); In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955) (Claimed process which was performed at a temperature between 40°C and 80°C and an acid concentration between 25% and 70% was held to be prima facie obvious over a reference process which differed from the claims only in that the reference process was performed at a temperature of 100°C and an acid concentration of 10%); In re Scherl, 156 F.2d 72, 74-75, 70 USPQ 204, 205-206 (CCPA 1946) (prior art showed an angle in a groove of up to 90° and an applicant claimed an angle of no less than 120°); In re Becket, 88 F.2d 684 (CCPA 1937) ("Where the component elements of alloys are the same, and where they approach so closely the same range of quantities as is here the case, it seems that there ought to be some noticeable difference in the qualities of the respective alloys."); In re Dreyfus, 73 F.2d 931, 934, 24 USPQ 52, 55 (CCPA 1934)(the prior art, which taught about 0.7:1 of alkali to water, renders unpatentable a claim that increased the proportion to at least 1:1 because there was no showing that the claimed proportions were critical); In re Lilienfeld, 67 F.2d 920, 924, 20 USPQ 53, 57 (CCPA 1933)(the prior art teaching an alkali cellulose containing minimal amounts of water, found by the Examiner to be in the 5-8% range, the claims sought to be patented were to an alkali cellulose with varying higher ranges of water (e.g., "not substantially less than 13%," "not substantially below 17%," and "between about 13[%] and 20%"); K-Swiss Inc. v. Glide N Lock GmbH, 567 Fed. App'x 906 (Fed. Cir. 2014)(reversing the Board's decision, in an appeal of an inter partes reexamination proceeding, that certain claims were not prima facie obvious due to non-overlapping ranges).
Therefore, it would have been obvious to one of ordinary skill in the art to modify Ding and Kaneda with Kim in order to suppress growth of a (001) crystal plane to enhance electrochemical properties.
Regarding claim 4, Ding, Kaneda, Kim et al. teach the precursor material according to claim 1. However, they do not teach wherein a deformation fault probability fD of the precursor material is less than or equal to 7.0%, and optionally less than or equal to 4.0%.
Paragraph 0084 of the as-filed specification discloses fD can be calculated by methods and equipment known in the art, for example, by fitting the X-ray diffraction (XRD) pattern. After fitting the XRD pattern of the precursor, the deformation fault probability fD is calculated:
fD=8.89645×B101×π/180-1.85325×B102×π/180-43.9925/D001
where B101 is the half-height width of the diffraction peak of the (101) plane of the precursor material, B102 is the half-height width of the diffraction peak of the (102) plane of the precursor material, and D001 is the grain size of the diffraction peak of the (001) plane of the precursor material. Then the corresponding value is calculated.
Ding et al. disclose values for B101 and B102. Further, the peak for a (001) plane is shown in Figures 1-4. Being that Ding et al. disclose the exact precursor composition as claimed and also the exact methods and equipment known in the art (by fitting the XRD pattern displayed), it would be obvious to one of ordinary skill in the art to determine the fD within the claimed range. Wherein the claimed and prior art products are identical or substantially identical, the burden of proof is on application to establish that the prior art products do not necessarily or inherently possess the characteristics of the instantly claimed products.
I. PRODUCT AND APPARATUS CLAIMS — WHEN THE STRUCTURE RECITED IN THE REFERENCE IS SUBSTANTIALLY IDENTICAL TO THAT OF THE CLAIMS, CLAIMED PROPERTIES OR FUNCTIONS ARE PRESUMED TO BE INHERENT Where the claimed and prior art products are identical or substantially identical in structure or composition, or are produced by identical or substantially identical processes, a prima facie case of either anticipation or obviousness has been established. In re Best, 562 F.2d 1252, 1255, 195 USPQ 430, 433 (CCPA 1977). "When the PTO shows a sound basis for believing that the products of the applicant and the prior art are the same, the applicant has the burden of showing that they are not." In re Spada, 911 F.2d 705, 709, 15 USPQ2d 1655, 1658 (Fed. Cir. 1990). Therefore, the prima facie case can be rebutted by evidence showing that the prior art products do not necessarily possess the characteristics of the claimed product. In re Best, 562 F.2d at 1255, 195 USPQ at 433. See also Titanium Metals Corp. v. Banner, 778 F.2d 775, 227 USPQ 773 (Fed. Cir. 1985) II. COMPOSITION CLAIMS — IF THE COMPOSITION IS PHYSICALLY THE SAME, IT MUST HAVE THE SAME PROPERTIES "Products of identical chemical composition cannot have mutually exclusive properties." In re Spada, 911 F.2d 705, 709, 15 USPQ2d 1655, 1658 (Fed. Cir. 1990). A chemical composition and its properties are inseparable. Therefore, if the prior art teaches the identical chemical structure, the properties applicant discloses and/or claims are necessarily present.
Regarding claim 7, Ding, Kaneda, Kim et al. teach the precursor material according to claim 1. Further, Ding et al. teach wherein a Dv50 of the precursor material is 3 µm to 15 µm (Paragraph 0032 discloses 7-13 µm.).
Regarding claim 9, Ding, Kaneda, Kim et al. teach the precursor material according to claim 1. Further, Ding et al. teach wherein an intensity ratio of diffraction peaks of the (001) plane and (101) plane of the precursor material is 0.60-1.25, and optionally 0.9-1.18 (Figs. 1-4 show the (001) and (100) plane having intensities that show ratios between the claimed values.).
Claim 22 is rejected under 35 U.S.C. 103 as unpatentable over Ding et al. (CN 115 140 783 A) and Kaneda et al. (US 2019/0248673 A1), and Kim (WO 2021/187963 A1 using US 2022/0407063 as an English language translation.) as applied to claim 1 above and further in view of Park et al. (KR 2021-0006869 A1)
Regarding claim 22, the combination of Ding, Kaneda, and Kim ‘063 et al. teach the precursor material according to claim 1. However, they do not teach wherein the element M comprises at least one of Sb, Na, K, or La.
Park et al. disclose a positive electrode active material for a secondary battery which comprises a precursor made of Ni, Co, and Mn (Abstract). Further, the precursor can comprise formula NixCoyMnzMpOH2 wherein 0.6<x<1.0, 0<y<0.4, 0<z<0.3, 0≤p<0.05, x+y+z+p=1 and M=La (Claim 4).
Therefore, it would have been obvious to one of ordinary skill in the art to modify Ding, Kaneda, and Kim ‘063 with Park in order to improve reactivity of the precursor.
Claims 24 is rejected under 35 U.S.C. 103 as unpatentable over Ding et al. (CN 115 140 783 A) and Kaneda et al. (US 2019/0248673 A1) and further in view of Kim (WO 2021/187963 A1 using US 2022/0407063 as an English language translation.).
Regarding claim 24, Regarding claims 1-3, 19, and 20, Ding et al. teach a precursor material, having a chemical formula of NixCoyMnzMa(OH)2, wherein element M comprises at least one of Zr, Y, Al, Ti, W, Sr, Ta, Mo, Sb, Nb, Na, K, Ca, Ce, and La, 0.55≤x<1.0, 0≤y<0.45, 0≤z<0.45, 0<a≤0.45, a+x+y+z＝1 (Claim 1 discloses a ternary cathode material precursor characterized by the chemical formula NixCoyMnzM1-x-y-z(OH)2 wherein M=Zr, Y, Al, Ti, W, Nb, and Ca. Further, 0.6≤ x≤1.0, 0＜y≤0.4, 0＜z≤0.4, 0≤1-x-y-z≤0.4.).
However, Ding et al. do not teach the number of (101) crystal plane layers of the precursor material is 20-70 or 25-55.
Paragraph 0076 of the as-filed specification discloses the number of layers of the (101) plane of the precursor material can be calculated by methods and equipment known in the art, for example, by fitting the X-ray diffraction (XRD) pattern. A grain size D101 of the (101) plane is calculated: D101=kλ/(B101*cosθ101), where B101 is the half-peak width of the diffraction peak of the (101) plane of the precursor material, k is a coefficient (generally 0.89-0.90), θ101 is the diffraction angle at the diffraction peak of the (101) plane of the precursor material in the XRD pattern; the interlayer spacing d101 of the (101) plane is calculated: d101=nλ/(2*sinθ101), where θ101 is the diffraction angle at the diffraction peak of the (101) plane of the precursor material, and λ is the wavelength of the copper target. Then the corresponding value is calculated. After summarizing the above parameters, the number of layers of the (101) plane is obtained: N101=D101/d101.
Applying this method of calculation to the XRD data presented in Ding, one of ordinary skill in the art can find D101 and d101. Figs. 1-4 of Ding show XRD patterns of the precursors claimed. The (101) peak appears at a 2θ=40° and therefore θ101 can be set to 20° when calculating D101 and d101. Further, paragraph 0009 of Ding discloses that the XRD diffraction peak half maximum width FWHM (101) of the (101) crystal plane is 0.350°-0.550° which corresponds to B101 when calculating D101 and d101.
Calculating D101 and d101
k=0.90, n=1, λ is omitted
if B101=0.35° then D101= kλ/(B101*cosθ101) = 0.90/{(0.35°*π/180) *cos(20°*π/180)} =192
if B101=0.55° then D101= kλ/(B101*cosθ101) = 0.90/{(0.55°*π/180) *cos(20°*π/180)} =121.2
d101=nλ/(2*sinθ101) =1/{2*sin(40°*π/180)} =1.47
Further, Ding discloses that B101≤0.650° (Paragraph 0008)
Therefore, when B101=0.65° then D101= kλ/(B101*cosθ101) = 0.90/{(0.65°*π/180) *cos(20°*π/180)} =81.
Calculating N101
When B101 is 0.350°-0.550°, N101=D101/d101= (121.2-192)/1.47=68-102 layers which overlaps claim 1.
When B101 is 0.650°, N101=D101/d101=81/1.47=55 layers which overlaps claim 3.
Therefore, using the XRD pattern and FWHM values disclosed in Ding, one of ordinary skill in the art would be able to determine the number of layers in the (101) plane by the same method as claimed in the present application.
However, they do not teach wherein a pore volume of the precursor material is greater than or equal to 0.02 cm3/g and less than or equal to 0.032 cm3/g or wherein a specific surface area of the precursor material is 4 m2/g-20m2/g, and optionally 8 m2/g- 13m2/g.
Kaneda et al. teach a mixed hydroxide of TM wherein TM comprises Ni and Mn and, optionally, Co, Zr, Ti, W, Ta, Mo, and Nb (Abstract; claim 1). Further, the precursor can comprise the formula NixMnyMzOx(OH)2+α wherein M=Co and at least one metal selected from Co, Zr, Ti, W, Ta, Mo, and Nb, 0.1≤x≤0.9, 0.05≤y≤0.8, 0≤z≤0.8, x+y+z=1.0, and 0≤α≤0.4 (Abstract; claim 1). Further, the pore volume can be 0.01 to 0.04 ml/g (Claim 2; example 2) and a BET surface area of 5-15 m2/g (Claim 4).
Therefore, it would have been obvious to one of ordinary skill in the art to modify Ding with Kaneda in order to improve energy density.
However, neither Ding nor Kaneda et al. teach a ratio of grain sizes of (100) plane to (001) plane of the precursor material is greater than or equal to 6.
Kim et al. teach a positive electrode active material precursor for a lithium secondary battery (Abstract). Further, the precursor comprises nickel (Paragraph 0030), cobalt (Paragraph 0031), and manganese (Paragraph 0032) and can additionally comprise a transition metal such as Zr, Ti, W, Ta, Mo, and Nb (Paragraph 0033). Finally, the positive electrode active material precursor according to the present invention may be prepared by the above-described preparation method of the present invention, and is a positive electrode active material precursor including nickel, cobalt, and manganese, wherein it has a crystalline size satisfying Equation 1: 2.5≤C100/C001≤5 wherein C100 is a crystalline size in a (100) plane and C001 is a crystalline size in a (001) plane (Paragraphs 0066-0067). MPEP 2144.05 I Similarly, a prima facie case of obviousness exists where the claimed ranges or amounts do not overlap with the prior art but are merely close. Titanium Metals Corp. of America v. Banner, 778 F.2d 775, 783, 227 USPQ 773, 779. See also Warner-Jenkinson Co., Inc. v. Hilton Davis Chemical Co., 520 U.S. 17, 41 USPQ2d 1865 (1997) (under the doctrine of equivalents, a purification process using a pH of 5.0 could infringe a patented purification process requiring a pH of 6.0-9.0); In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955) (Claimed process which was performed at a temperature between 40°C and 80°C and an acid concentration between 25% and 70% was held to be prima facie obvious over a reference process which differed from the claims only in that the reference process was performed at a temperature of 100°C and an acid concentration of 10%); In re Scherl, 156 F.2d 72, 74-75, 70 USPQ 204, 205-206 (CCPA 1946) (prior art showed an angle in a groove of up to 90° and an applicant claimed an angle of no less than 120°); In re Becket, 88 F.2d 684 (CCPA 1937) ("Where the component elements of alloys are the same, and where they approach so closely the same range of quantities as is here the case, it seems that there ought to be some noticeable difference in the qualities of the respective alloys."); In re Dreyfus, 73 F.2d 931, 934, 24 USPQ 52, 55 (CCPA 1934)(the prior art, which taught about 0.7:1 of alkali to water, renders unpatentable a claim that increased the proportion to at least 1:1 because there was no showing that the claimed proportions were critical); In re Lilienfeld, 67 F.2d 920, 924, 20 USPQ 53, 57 (CCPA 1933)(the prior art teaching an alkali cellulose containing minimal amounts of water, found by the Examiner to be in the 5-8% range, the claims sought to be patented were to an alkali cellulose with varying higher ranges of water (e.g., "not substantially less than 13%," "not substantially below 17%," and "between about 13[%] and 20%"); K-Swiss Inc. v. Glide N Lock GmbH, 567 Fed. App'x 906 (Fed. Cir. 2014)(reversing the Board's decision, in an appeal of an inter partes reexamination proceeding, that certain claims were not prima facie obvious due to non-overlapping ranges).
Therefore, it would have been obvious to one of ordinary skill in the art to modify Ding and Kaneda with Kim in order to suppress growth of a (001) crystal plane to enhance electrochemical properties.
However, neither Ding, Kaneda, nor Kim et al. teach wherein element M comprises at least one of Sb, Na, or K.
Wang et al. teach a lithium-manganese precursor material is at least one substance selected from the substances represented by the chemical formula MnaCobNicM1−a−b−c(OH)2 wherein 0.5≤a≤1, 0≤b≤0.5, 0≤c≤0.5, M is at least one element selected from the group consisting of Na or K (Paragraphs 0043-0044).
Therefore, it would have been obvious to one of ordinary skill in the art to modify the combination of Ding, Kaneda, and Kim with Wang in order to improve capacity and cycle stability.
Claims 1, 3, 8, 9, 19, and 20 are 35 U.S.C. 103 as unpatentable over Kim et al. (US 2011/0305954 A1) and Kaneda et al. (US 2019/0248673 A1) and further in view of Kim (WO 2021/187963 A1 using US 2022/0407063 as an English language translation, referred to as Kim ‘063 for clarity.).
Regarding claims 1, 3, 8, 19, and 20, Kim et al. teach a precursor material, having a chemical formula of NixCoyMnzMa(OH)2, wherein element M comprises at least one of Zr, Y, Al, Ti, W, Sr, Ta, Mo, Sb, Nb, Na, K, Ca, Ce, and La, 0.55≤x<1.0, 0≤y<0.45, 0≤z<0.45, 0<a≤0.45, a+x+y+z＝1 (Abstract; paragraph 0048 disclose a positive active material precursor characterized by the chemical formula NixCoyMnzMk(OH)2 wherein M is a metal such as Al, Ti, or Zr. Further, 0.45≤x≤0.65, 0.15≤y≤0.25, 0.15≤z≤0.35, 0≤k≤0.1.).
However, Kim et al. do not teach the number of (101) crystal plane layers of the precursor material is 20-70 or 25-55.
Paragraph 0076 of the as-filed specification discloses the number of layers of the (101) plane of the precursor material can be calculated by methods and equipment known in the art, for example, by fitting the X-ray diffraction (XRD) pattern. A grain size D101 of the (101) plane is calculated: D101=kλ/(B101*cosθ101), where B101 is the half-peak width of the diffraction peak of the (101) plane of the precursor material, k is a coefficient (generally 0.89-0.90), θ101 is the diffraction angle at the diffraction peak of the (101) plane of the precursor material in the XRD pattern; the interlayer spacing d101 of the (101) plane is calculated: d101=nλ/(2*sinθ101), where θ101 is the diffraction angle at the diffraction peak of the (101) plane of the precursor material, and λ is the wavelength of the copper target. Then the corresponding value is calculated. After summarizing the above parameters, the number of layers of the (101) plane is obtained: N101=D101/d101.
Applying this method of calculation to the XRD data presented in Kim, one of ordinary skill in the art can find D101 and d101. Figure 2 and Table 1 show XRD patterns of the precursors claimed. The (101) peak appears at a 2θ=39.452° and therefore θ101 can be set to 19.726° when calculating D101 and d101. Further, Table 1 of Ding discloses that the XRD diffraction peak half maximum width FWHM (101) of the (101) crystal plane is 1.2348° which corresponds to B101 when calculating D101 and d101.
Calculating D101 and d101
k=0.90, n=1, λ is omitted
D101= kλ/(B101*cosθ101) = 0.90/{(1.2348°*π/180) *cos(19.726°*π/180)} =45
d101=nλ/(2*sinθ101) =1/{2*sin(19.726°*π/180)} =1.48
Calculating N101
N101=D101/d101=45/1.48=30 layers which overlaps claims 1 and 3.
Therefore, using the XRD pattern and FWHM values disclosed in Kim, one of ordinary skill in the art would be able to determine the number of layers in the (101) plane by the same method as claimed in the present application.
However, they do not teach wherein a pore volume of the precursor material is greater than or equal to 0.02 cm3/g and less than or equal to 0.032 cm3/g or wherein a specific surface area of the precursor material is 4 m2/g-20m2/g, and optionally 8 m2/g- 13m2/g.
Kaneda et al. teach a mixed hydroxide of TM wherein TM comprises Ni and Mn and, optionally, Co, Zr, Ti, W, Ta, Mo, and Nb (Abstract; claim 1). Further, the precursor can comprise the formula NixMnyMzOx(OH)2+α wherein M=Co and at least one metal selected from Co, Zr, Ti, W, Ta, Mo, and Nb, 0.1≤x≤0.9, 0.05≤y≤0.8, 0≤z≤0.8, x+y+z=1.0, and 0≤α≤0.4 (Abstract; claim 1). Further, the pore volume can be 0.01 to 0.04 ml/g (Claim 2; example 2) and a BET surface area of 5-15 m2/g (Claim 4).
Therefore, it would have been obvious to one of ordinary skill in the art to modify Ding with Kaneda in order to improve energy density.
However, neither Kim nor Kaneda et al. teach a ratio of grain sizes of (100) plane to (001) plane of the precursor material is greater than or equal to 6.
Kim ‘063 et al. teach a positive electrode active material precursor for a lithium secondary battery (Abstract). Further, the precursor comprises nickel (Paragraph 0030), cobalt (Paragraph 0031), and manganese (Paragraph 0032) and can additionally comprise a transition metal such as Zr, Ti, W, Ta, Mo, and Nb (Paragraph 0033). Finally, the positive electrode active material precursor according to the present invention may be prepared by the above-described preparation method of the present invention, and is a positive electrode active material precursor including nickel, cobalt, and manganese, wherein it has a crystalline size satisfying Equation 1: 2.5≤C100/C001≤5 wherein C100 is a crystalline size in a (100) plane and C001 is a crystalline size in a (001) plane (Paragraphs 0066-0067). MPEP 2144.05 I Similarly, a prima facie case of obviousness exists where the claimed ranges or amounts do not overlap with the prior art but are merely close. Titanium Metals Corp. of America v. Banner, 778 F.2d 775, 783, 227 USPQ 773, 779. See also Warner-Jenkinson Co., Inc. v. Hilton Davis Chemical Co., 520 U.S. 17, 41 USPQ2d 1865 (1997) (under the doctrine of equivalents, a purification process using a pH of 5.0 could infringe a patented purification process requiring a pH of 6.0-9.0); In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955) (Claimed process which was performed at a temperature between 40°C and 80°C and an acid concentration between 25% and 70% was held to be prima facie obvious over a reference process which differed from the claims only in that the reference process was performed at a temperature of 100°C and an acid concentration of 10%); In re Scherl, 156 F.2d 72, 74-75, 70 USPQ 204, 205-206 (CCPA 1946) (prior art showed an angle in a groove of up to 90° and an applicant claimed an angle of no less than 120°); In re Becket, 88 F.2d 684 (CCPA 1937) ("Where the component elements of alloys are the same, and where they approach so closely the same range of quantities as is here the case, it seems that there ought to be some noticeable difference in the qualities of the respective alloys."); In re Dreyfus, 73 F.2d 931, 934, 24 USPQ 52, 55 (CCPA 1934)(the prior art, which taught about 0.7:1 of alkali to water, renders unpatentable a claim that increased the proportion to at least 1:1 because there was no showing that the claimed proportions were critical); In re Lilienfeld, 67 F.2d 920, 924, 20 USPQ 53, 57 (CCPA 1933)(the prior art teaching an alkali cellulose containing minimal amounts of water, found by the Examiner to be in the 5-8% range, the claims sought to be patented were to an alkali cellulose with varying higher ranges of water (e.g., "not substantially less than 13%," "not substantially below 17%," and "between about 13[%] and 20%"); K-Swiss Inc. v. Glide N Lock GmbH, 567 Fed. App'x 906 (Fed. Cir. 2014)(reversing the Board's decision, in an appeal of an inter partes reexamination proceeding, that certain claims were not prima facie obvious due to non-overlapping ranges).
Therefore, it would have been obvious to one of ordinary skill in the art to modify Ding and Kaneda with Kim ‘063 in order to suppress growth of a (001) crystal plane to enhance electrochemical properties.
Claim 9, Kim and Kaneda and Kim ‘063 et al. teach the precursor material according to claim 1. Further, Kim et al. disclose wherein an intensity ratio of diffraction peaks of the (001) plane and (101) plane of the precursor material is 0.60-1.25, and optionally 0.9-1.18 (Table 1, example 1 discloses a ratio of 1.).
Claim 22 is 35 U.S.C. 103 as unpatentable over Kim et al. (US 2011/0305954 A1) and Kaneda et al. (US 2019/0248673 A1), and Kim (WO 2021/187963 A1 using US 2022/0407063 as an English language translation, referred to as Kim ‘063 for clarity.) as applied to claim 1 above, and further in view of Park et al. (KR 2021-0006869 A1)
Regarding claim 22, the combination of Kim, Kaneda, and Kim ‘063 et al. teach the precursor material according to claim 1. However, they do not teach wherein the element M comprises at least one of Sb, Na, K, or La.
Park et al. disclose a positive electrode active material for a secondary battery which comprises a precursor made of Ni, Co, and Mn (Abstract). Further, the precursor can comprise formula NixCoyMnzMpOH2 wherein 0.6<x<1.0, 0<y<0.4, 0<z<0.3, 0≤p<0.05, x+y+z+p=1 and M=La (Claim 4).
Therefore, it would have been obvious to one of ordinary skill in the art to modify Kim, Kaneda, and Kim ‘063 with Park in order to improve reactivity of the precursor.
Claim 24 is rejected under 35 U.S.C. 103 as unpatentable over Kim et al. (US 2011/0305954 A1) and Kaneda et al. (US 2019/0248673 A1) and further in view of Kim (WO 2021/187963 A1 using US 2022/0407063 as an English language translation, referred to as Kim ‘063 for clarity.).
Regarding claim 24, Kim et al. teach a precursor material, having a chemical formula of NixCoyMnzMa(OH)2, wherein element M comprises at least one of Zr, Y, Al, Ti, W, Sr, Ta, Mo, Sb, Nb, Na, K, Ca, Ce, and La, 0.55≤x<1.0, 0≤y<0.45, 0≤z<0.45, 0<a≤0.45, a+x+y+z＝1 (Abstract; paragraph 0048 disclose a positive active material precursor characterized by the chemical formula NixCoyMnzMk(OH)2 wherein M is a metal such as Al, Ti, or Zr. Further, 0.45≤x≤0.65, 0.15≤y≤0.25, 0.15≤z≤0.35, 0≤k≤0.1.).
However, Kim et al. do not teach the number of (101) crystal plane layers of the precursor material is 20-70 or 25-55.
Paragraph 0076 of the as-filed specification discloses the number of layers of the (101) plane of the precursor material can be calculated by methods and equipment known in the art, for example, by fitting the X-ray diffraction (XRD) pattern. A grain size D101 of the (101) plane is calculated: D101=kλ/(B101*cosθ101), where B101 is the half-peak width of the diffraction peak of the (101) plane of the precursor material, k is a coefficient (generally 0.89-0.90), θ101 is the diffraction angle at the diffraction peak of the (101) plane of the precursor material in the XRD pattern; the interlayer spacing d101 of the (101) plane is calculated: d101=nλ/(2*sinθ101), where θ101 is the diffraction angle at the diffraction peak of the (101) plane of the precursor material, and λ is the wavelength of the copper target. Then the corresponding value is calculated. After summarizing the above parameters, the number of layers of the (101) plane is obtained: N101=D101/d101.
Applying this method of calculation to the XRD data presented in Kim, one of ordinary skill in the art can find D101 and d101. Figure 2 and Table 1 show XRD patterns of the precursors claimed. The (101) peak appears at a 2θ=39.452° and therefore θ101 can be set to 19.726° when calculating D101 and d101. Further, Table 1 of Ding discloses that the XRD diffraction peak half maximum width FWHM (101) of the (101) crystal plane is 1.2348° which corresponds to B101 when calculating D101 and d101.
Calculating D101 and d101
k=0.90, n=1, λ is omitted
D101= kλ/(B101*cosθ101) = 0.90/{(1.2348°*π/180) *cos(19.726°*π/180)} =45
d101=nλ/(2*sinθ101) =1/{2*sin(19.726°*π/180)} =1.48
Calculating N101
N101=D101/d101=45/1.48=30 layers which overlaps claims 1 and 3.
Therefore, using the XRD pattern and FWHM values disclosed in Kim, one of ordinary skill in the art would be able to determine the number of layers in the (101) plane by the same method as claimed in the present application.
However, they do not teach wherein a pore volume of the precursor material is greater than or equal to 0.02 cm3/g and less than or equal to 0.032 cm3/g or wherein a specific surface area of the precursor material is 4 m2/g-20m2/g, and optionally 8 m2/g- 13m2/g.
Kaneda et al. teach a mixed hydroxide of TM wherein TM comprises Ni and Mn and, optionally, Co, Zr, Ti, W, Ta, Mo, and Nb (Abstract; claim 1). Further, the precursor can comprise the formula NixMnyMzOx(OH)2+α wherein M=Co and at least one metal selected from Co, Zr, Ti, W, Ta, Mo, and Nb, 0.1≤x≤0.9, 0.05≤y≤0.8, 0≤z≤0.8, x+y+z=1.0, and 0≤α≤0.4 (Abstract; claim 1). Further, the pore volume can be 0.01 to 0.04 ml/g (Claim 2; example 2) and a BET surface area of 5-15 m2/g (Claim 4).
Therefore, it would have been obvious to one of ordinary skill in the art to modify Ding with Kaneda in order to improve energy density.
However, neither Kim nor Kaneda et al. teach a ratio of grain sizes of (100) plane to (001) plane of the precursor material is greater than or equal to 6.
Kim ‘063 et al. teach a positive electrode active material precursor for a lithium secondary battery (Abstract). Further, the precursor comprises nickel (Paragraph 0030), cobalt (Paragraph 0031), and manganese (Paragraph 0032) and can additionally comprise a transition metal such as Zr, Ti, W, Ta, Mo, and Nb (Paragraph 0033). Finally, the positive electrode active material precursor according to the present invention may be prepared by the above-described preparation method of the present invention, and is a positive electrode active material precursor including nickel, cobalt, and manganese, wherein it has a crystalline size satisfying Equation 1: 2.5≤C100/C001≤5 wherein C100 is a crystalline size in a (100) plane and C001 is a crystalline size in a (001) plane (Paragraphs 0066-0067). MPEP 2144.05 I Similarly, a prima facie case of obviousness exists where the claimed ranges or amounts do not overlap with the prior art but are merely close. Titanium Metals Corp. of America v. Banner, 778 F.2d 775, 783, 227 USPQ 773, 779. See also Warner-Jenkinson Co., Inc. v. Hilton Davis Chemical Co., 520 U.S. 17, 41 USPQ2d 1865 (1997) (under the doctrine of equivalents, a purification process using a pH of 5.0 could infringe a patented purification process requiring a pH of 6.0-9.0); In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955) (Claimed process which was performed at a temperature between 40°C and 80°C and an acid concentration between 25% and 70% was held to be prima facie obvious over a reference process which differed from the claims only in that the reference process was performed at a temperature of 100°C and an acid concentration of 10%); In re Scherl, 156 F.2d 72, 74-75, 70 USPQ 204, 205-206 (CCPA 1946) (prior art showed an angle in a groove of up to 90° and an applicant claimed an angle of no less than 120°); In re Becket, 88 F.2d 684 (CCPA 1937) ("Where the component elements of alloys are the same, and where they approach so closely the same range of quantities as is here the case, it seems that there ought to be some noticeable difference in the qualities of the respective alloys."); In re Dreyfus, 73 F.2d 931, 934, 24 USPQ 52, 55 (CCPA 1934)(the prior art, which taught about 0.7:1 of alkali to water, renders unpatentable a claim that increased the proportion to at least 1:1 because there was no showing that the claimed proportions were critical); In re Lilienfeld, 67 F.2d 920, 924, 20 USPQ 53, 57 (CCPA 1933)(the prior art teaching an alkali cellulose containing minimal amounts of water, found by the Examiner to be in the 5-8% range, the claims sought to be patented were to an alkali cellulose with varying higher ranges of water (e.g., "not substantially less than 13%," "not substantially below 17%," and "between about 13[%] and 20%"); K-Swiss Inc. v. Glide N Lock GmbH, 567 Fed. App'x 906 (Fed. Cir. 2014)(reversing the Board's decision, in an appeal of an inter partes reexamination proceeding, that certain claims were not prima facie obvious due to non-overlapping ranges).
Therefore, it would have been obvious to one of ordinary skill in the art to modify Ding and Kaneda with Kim ‘063 in order to suppress growth of a (001) crystal plane to enhance electrochemical properties.
However, neither Ding, Kaneda, nor Kim ‘063 et al. teach wherein element M comprises at least one of Sb, Na, or K.
Wang et al. teach a lithium-manganese precursor material is at least one substance selected from the substances represented by the chemical formula MnaCobNicM1−a−b−c(OH)2 wherein 0.5≤a≤1, 0≤b≤0.5, 0≤c≤0.5, M is at least one element selected from the group consisting of Na or K (Paragraphs 0043-0044).
Therefore, it would have been obvious to one of ordinary skill in the art to modify the combination of Ding, Kaneda, and Kim ‘063 with Wang in order to improve capacity and cycle stability.
Claim 21 is rejected under 35 U.S.C. 103 as being unpatentable over Ding et al. (CN 115 140 783 A) and Kim et al. (US 2018/0151876 A1) and further in view of Kim (WO 2021/187963 A1 using US 2022/0407063 as an English language translation, referred to as “Kim ‘063” for clarity.).
Regarding claim 21, Ding et al. teach a precursor material, having a chemical formula of NixCoyMnzMa(OH)2, wherein element M comprises at least one of Zr, Y, Al, Ti, W, Sr, Ta, Mo, Sb, Nb, Na, K, Ca, Ce, and La, 0.55≤x<1.0, 0≤y<0.45, 0≤z<0.45, 0<a≤0.45, a+x+y+z＝1 (Claim 1 discloses a ternary cathode material precursor characterized by the chemical formula NixCoyMnzM1-x-y-z(OH)2 wherein M=Zr, Y, Al, Ti, W, Nb, and Ca. Further, 0.6≤ x≤1.0, 0＜y≤0.4, 0＜z≤0.4, 0≤1-x-y-z≤0.4.).
However, Ding et al. do not teach the number of (101) crystal plane layers of the precursor material is 20-70 or 25-55.
Paragraph 0076 of the as-filed specification discloses the number of layers of the (101) plane of the precursor material can be calculated by methods and equipment known in the art, for example, by fitting the X-ray diffraction (XRD) pattern. A grain size D101 of the (101) plane is calculated: D101=kλ/(B101*cosθ101), where B101 is the half-peak width of the diffraction peak of the (101) plane of the precursor material, k is a coefficient (generally 0.89-0.90), θ101 is the diffraction angle at the diffraction peak of the (101) plane of the precursor material in the XRD pattern; the interlayer spacing d101 of the (101) plane is calculated: d101=nλ/(2*sinθ101), where θ101 is the diffraction angle at the diffraction peak of the (101) plane of the precursor material, and λ is the wavelength of the copper target. Then the corresponding value is calculated. After summarizing the above parameters, the number of layers of the (101) plane is obtained: N101=D101/d101.
Applying this method of calculation to the XRD data presented in Ding, one of ordinary skill in the art can find D101 and d101. Figs. 1-4 of Ding show XRD patterns of the precursors claimed. The (101) peak appears at a 2θ=40° and therefore θ101 can be set to 20° when calculating D101 and d101. Further, paragraph 0009 of Ding discloses that the XRD diffraction peak half maximum width FWHM (101) of the (101) crystal plane is 0.350°-0.550° which corresponds to B101 when calculating D101 and d101.
Calculating D101 and d101
k=0.90, n=1, λ is omitted
if B101=0.35° then D101= kλ/(B101*cosθ101) = 0.90/{(0.35°*π/180) *cos(20°*π/180)} =192
if B101=0.55° then D101= kλ/(B101*cosθ101) = 0.90/{(0.55°*π/180) *cos(20°*π/180)} =121.2
d101=nλ/(2*sinθ101) =1/{2*sin(40°*π/180)} =1.47
Further, Ding discloses that B101≤0.650° (Paragraph 0008)
Therefore, when B101=0.65° then D101= kλ/(B101*cosθ101) = 0.90/{(0.65°*π/180) *cos(20°*π/180)} =81.
Calculating N101
When B101 is 0.350°-0.550°, N101=D101/d101= (121.2-192)/1.47=68-102 layers which overlaps claim 1.
When B101 is 0.650°, N101=D101/d101=81/1.47=55 layers which overlaps claim 3.
Therefore, using the XRD pattern and FWHM values disclosed in Ding, one of ordinary skill in the art would be able to determine the number of layers in the (101) plane by the same method as claimed in the present application.
However, Ding et al. do not teach wherein M comprises at least one of Sb, Na, K, Ca, or La.
Kim et al. teach Ni1-x-yCoxMnyMz(OH)2, wherein element M comprises Ca and 0<x≤0.33, 0≤y≤0.5, 0≤z≤0.05, and 0.33≤(1-x-y-z)≤3.95 (Paragraphs 0063 and 0064; 0066).
Therefore, it would have been obvious to one of ordinary skill in the art to modify Ding with Kim in order to improve capacity retention.
However, neither Ding nor Kim et al. teach a ratio of grain sizes of (100) plane to (001) plane of the precursor material is greater than or equal to 4.4
Kim ‘063 et al. teach a positive electrode active material precursor for a lithium secondary battery (Abstract). Further, the precursor comprises nickel (Paragraph 0030), cobalt (Paragraph 0031), and manganese (Paragraph 0032) and can additionally comprise a transition metal such as Zr, Ti, W, Ta, Mo, and Nb (Paragraph 0033). Finally, the positive electrode active material precursor according to the present invention may be prepared by the above-described preparation method of the present invention, and is a positive electrode active material precursor including nickel, cobalt, and manganese, wherein it has a crystalline size satisfying Equation 1: 2.5≤C100/C001≤5 wherein C100 is a crystalline size in a (100) plane and C001 is a crystalline size in a (001) plane (Paragraphs 0066-0067).
Therefore, it would have been obvious to one of ordinary skill in the art to modify Ding and Kim with Kim ‘063 in order to suppress growth of a (001) crystal plane to enhance electrochemical properties.
Claim 21 is rejected under 35 U.S.C. 103 as being unpatentable over Kim et al. (US 2011/0305954 A1) and Kim et al. (US 2018/0151876 A1) and further in view of Kim (WO 2021/187963 A1 using US 2022/0407063 as an English language translation, referred to as “Kim ‘063” for clarity.).
Regarding claim 21, Kim et al. teach a precursor material, having a chemical formula of NixCoyMnzMa(OH)2, wherein element M comprises at least one of Zr, Y, Al, Ti, W, Sr, Ta, Mo, Sb, Nb, Na, K, Ca, Ce, and La, 0.55≤x<1.0, 0≤y<0.45, 0≤z<0.45, 0<a≤0.45, a+x+y+z＝1 (Abstract; paragraph 0048 disclose a positive active material precursor characterized by the chemical formula NixCoyMnzMk(OH)2 wherein M is a metal such as Al, Ti, or Zr. Further, 0.45≤x≤0.65, 0.15≤y≤0.25, 0.15≤z≤0.35, 0≤k≤0.1.).
However, Kim et al. do not teach the number of (101) crystal plane layers of the precursor material is 20-70 or 25-55.
Paragraph 0076 of the as-filed specification discloses the number of layers of the (101) plane of the precursor material can be calculated by methods and equipment known in the art, for example, by fitting the X-ray diffraction (XRD) pattern. A grain size D101 of the (101) plane is calculated: D101=kλ/(B101*cosθ101), where B101 is the half-peak width of the diffraction peak of the (101) plane of the precursor material, k is a coefficient (generally 0.89-0.90), θ101 is the diffraction angle at the diffraction peak of the (101) plane of the precursor material in the XRD pattern; the interlayer spacing d101 of the (101) plane is calculated: d101=nλ/(2*sinθ101), where θ101 is the diffraction angle at the diffraction peak of the (101) plane of the precursor material, and λ is the wavelength of the copper target. Then the corresponding value is calculated. After summarizing the above parameters, the number of layers of the (101) plane is obtained: N101=D101/d101.
Applying this method of calculation to the XRD data presented in Kim, one of ordinary skill in the art can find D101 and d101. Figure 2 and Table 1 show XRD patterns of the precursors claimed. The (101) peak appears at a 2θ=39.452° and therefore θ101 can be set to 19.726° when calculating D101 and d101. Further, Table 1 of Ding discloses that the XRD diffraction peak half maximum width FWHM (101) of the (101) crystal plane is 1.2348° which corresponds to B101 when calculating D101 and d101.
Calculating D101 and d101
k=0.90, n=1, λ is omitted
D101= kλ/(B101*cosθ101) = 0.90/{(1.2348°*π/180) *cos(19.726°*π/180)}=45
d101=nλ/(2*sinθ101) =1/{2*sin(19.726°*π/180)}=1.48
Calculating N101
N101=D101/d101=45/1.48=30 layers which overlaps claims 1 and 3.
Therefore, using the XRD pattern and FWHM values disclosed in Kim, one of ordinary skill in the art would be able to determine the number of layers in the (101) plane by the same method as claimed in the present application.
However, Kim et al. do not teach wherein M comprises at least one of Sb, Na, K, Ca, or La.
Kim ‘876 teach Ni1-x-yCoxMnyMz(OH)2, wherein element M comprises Ca and 0<x≤0.33, 0≤y≤0.5, 0≤z≤0.05, and 0.33≤(1-x-y-z)≤3.95 (Paragraphs 0063 and 0064; 0066).
Therefore, it would have been obvious to one of ordinary skill in the art to modify Kim with Kim ‘876 in order to improve capacity retention.
However, neither Kim nor Kim’876 et al. teach a ratio of grain sizes of (100) plane to (001) plane of the precursor material is greater than or equal to 4.4
Kim ‘063 et al. teach a positive electrode active material precursor for a lithium secondary battery (Abstract). Further, the precursor comprises nickel (Paragraph 0030), cobalt (Paragraph 0031), and manganese (Paragraph 0032) and can additionally comprise a transition metal such as Zr, Ti, W, Ta, Mo, and Nb (Paragraph 0033). Finally, the positive electrode active material precursor according to the present invention may be prepared by the above-described preparation method of the present invention, and is a positive electrode active material precursor including nickel, cobalt, and manganese, wherein it has a crystalline size satisfying Equation 1: 2.5≤C100/C001≤5 wherein C100 is a crystalline size in a (100) plane and C001 is a crystalline size in a (001) plane (Paragraphs 0066-0067).
Therefore, it would have been obvious to one of ordinary skill in the art to modify Kim and Kim’876 with Kim ‘063 in order to suppress growth of a (001) crystal plane to enhance electrochemical properties.
Conclusion
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
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Daniel S. Gatewood, Ph.D.
Primary Examiner
Art Unit 1729
/DANIEL S GATEWOOD, Ph. D/Primary Examiner, Art Unit 1729 May 22nd, 2026
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