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 .
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.
Information Disclosure Statements
The Information Disclosure Statement filed on 18 August 2023 has been received and considered by the Examiner.
Claim Objections
Claim 1 is objected to because of the following informalities:
Line 13 of claim 13 should be amended to read: “… and controlling the ammonia concentration in the range [[at]] 0 to 5 g/L…”
Appropriate correction is required.
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.
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 1-8 are rejected under 35 U.S.C. 103 as being unpatentable over Liu et al. (CN 111370679 A). The provided English machine translation of Liu is referenced in the analysis below.
Regarding claim 1, Liu discloses a radially-structured nickel-based precursor, wherein an overall shape of the precursor is a secondary sphere formed by aggregation of primary crystal grains; the secondary sphere has a loose and porous network core inside, and has a uniform and regular strip-shaped primary crystal grains outside, and the strip-shaped primary crystal grains grow outward perpendicularly to a surface of the core and are arranged radially and closely ([0008], [00049] and Fig. 1, copied below); and the precursor has a chemical formula of NixCoyM(1-x-y)(OH)2, where 0.6<x<1, 0<y<1, 0.6<x+y<1, and M is Al or Mn ([0049]); it is noted that the restrictions on x and x+y limit the value of y to being no greater than 0.4. Liu therefore teaches a precursor with the formula of NixCoyM(1-x-y)(OH)2, where 0.6<x<1 and 0<y<0.4, which anticipates the formula recited in the instant claim with z=0 and a doping element of Mn or Al.
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Figure 1 of Liu (CN 111370679 A).
Liu further teaches that a diameter of the core of the precursor may account for anywhere from 1% to 75% of the entire precursor particle (the ratio of the radius of the internal region to the radius of the secondary particles is 1% to 75%; [0045]), which overlaps with the instantly claimed diameter of the core of the precursors accounting for more than ½ (50%) of a diameter of an entire precursor particle.
It is noted that the courts have stated where the claimed ranges “overlap or lie inside the ranges disclosed by the prior art” a prima facie case of obviousness exists (see In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990); Titanium Metals Corp. of America v. Banner, 778 F2d 775. 227 USPQ 773 (Fed. Cir. 1985) (see MPEP 2144.05.01). Therefore, the claimed range merely represents an obvious variant and/or routine optimization of the values of the cited prior art.
The remaining limitations of claim 1 recite product by process limitations. It is noted that the courts have held that "[E]ven though product-by-process claims are limited by and defined by the process, determination of patentability is based on the product itself. The patentability of a product does not depend on its method of production. If the product in the product-by-process claim is the same as or obvious from a product of the prior art, the claim is unpatentable even though the prior product was made by a different process." In re Thorpe, 777 F.2d 695, 698, 227 USPQ 964, 966 (Fed. Cir. 1985). MPEP 2113(I).
In the instant case, the products disclosed by Liu meet the description of those in claim 1 and are prepared by a substantially identical process (vide infra). Therefore, the product of the instant claim are held unpatentable over Liu.
Further regarding the process of Liu yielding the same products as instantly claimed, Liu teaches a method of forming the precursor of the instant claim that renders the instantly claim method obvious. In particular, Liu teaches that the radially-structured nickel-based precursor is prepared by a method comprising the following steps: (1) adding a metal solution (mixed salt solution…contains nickel salt, cobalt salt, and M salt;[0055]), an alkali liquor (precipitant solution, which is preferably NaOH, an alkali; [0061]), and ammonia water (complexing agent, which can be ammonia; [0063]) to a first reactor (Add the mixed salt solution, precipitant solution and complexing agent solution to the base liquid, in a controlled crystallization reactor; [0056] and [0071]), and heating and stirring ([0067]) to allow a reaction to prepare a seed crystal (carry out the first-stage co-precipitation reaction to obtain initial particles formed by the aggregation of multiple primary particles; [0056]), during the reaction controlling the pH within a range of 10.8 to 11.8 ([0071]), which falls in the instantly claimed range of 9-12, and controlling the ammonia concentration in the range 0.3 g to 13.6 g/L (0.02-0.8 mol/L; [0071]), which overlaps with the instantly claimed range of 0 to 5 g/L, and continuously feeding the metal solution, the alkali liquor, and the ammonia water until a particle size reaches a target value of the seed crystal (mixed salt solution, precipitant solution, and complexing agent solution are added to the controlled crystallization reactor in a co-current flow at a certain flow rate…until the particle size of the internal region…is reached; [0071]), wherein the metal solution comprises a nickel salt and a cobalt salt ([0055]).
Liu further teaches continued heating and stirring of the seed crystal, the metal solution, the alkali liquor, and the ammonia water to allow a reaction, during the reaction, controlling the pH at 10.8-11.8, which falls in the instantly claimed range of 9-12, controlling an ammonia concentration in the reaction system and continuously feeding the metal solution, the alkali liquor, and the ammonia water until a particle size reaches a target value of the precursor to obtain a product (in step S30, while keeping other process conditions unchanged, the concentration of the complexing agent in the reaction solution is controlled to increase linearly at a rate of 0.005 mol/L/h--0.02 mol/L/h, preferably linearly at a rate of 0.005 mol/L/h-0.01 mol/L/h. The reaction continues for a period of time until the target particle size of the positive electrode active material precursor is reached; [0071]) ; and collecting, washing, dewatering, and drying the product to obtain the radially-structured nickel-based precursor (washing and drying it to obtain the final positive electrode active material precursor product; [0074]; obtaining the product means it was collected, while drying the product means it was dewatered).
While Liu is silent on the final concentration of ammonia reached in the second reaction, the starting concentration will be in the range of 0.3 g to 13.6 g/L [0071], which overlaps with the claimed range of 5-10 g/L for step (2).
While Liu is silent on the time of the second rection, they do teach continuing the reaction until a desired size is reached. Therefore it would have been obvious to one of ordinary skill in the art to vary by routine experimentation the reaction time, and thereby the final concentrations reached in the second step, as the final concentration will be a function of reaction time given the rate of increasing concentration. Therefore, the claimed range of ammonia concentrations in step (2) merely represents an obvious variant and/or routine optimization of the values used by Liu.
Liu also does not teach adding the seed crystal, the metal solution, the alkali liquor, and the ammonia water to a second reactor, but it is not believed that the mere use of separate vessel would yield a product significantly distinct from the product obtained by Liu.
It is noted the “Patent Office bears a lesser burden of proof in making out a case of prima facie obviousness for product-by-process claims because of their peculiar nature" than when a product is claimed in the conventional fashion. In re Fessmann, 489 F.2d 742, 744, 180 USPQ 324, 326 (CCPA 1974). Once the examiner provides a rationale tending to show that the claimed product appears to be the same or similar to that of the prior art, although produced by a different process, the burden shifts to applicant to come forward with evidence establishing an nonobvious difference between the claimed product and the prior art product. In re Marosi, 710 F.2d 799, 803, 218 USPQ 289, 292-33 (Fed. Cir. 1983). MPEP 2113(II).
Regarding claim 2, Liu teaches the radially-structured nickel-based precursor according to claim 1, where the average particle size is between 3 μm and 20 μm ([0048]), which overlaps with the instantly claimed range of 3 to 10 μm.
It is noted that the courts have stated where the claimed ranges “overlap or lie inside the ranges disclosed by the prior art” a prima facie case of obviousness exists (see In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990); Titanium Metals Corp. of America v. Banner, 778 F2d 775. 227 USPQ 773 (Fed. Cir. 1985) (see MPEP 2144.05.01). Therefore, the claimed ranges merely represent an obvious variant and/or routine optimization of the values of the cited prior art.
Regarding claim 3, Liu teaches the radially-structured nickel-based precursor according to claim 1 where M is Al ([0049]).
Regarding claim 4, Liu teaches the radially-structured nickel-based precursor according to claim 1 where the total metals in the metal solution more preferably have a molar concentration of 1.5 mol/L to 2.0 mol/L ([0060]), which lies in the instantly claimed range.
Regarding claim 5, Liu teaches the radially-structured nickel-based precursor according to claim 1 where the metal solution further comprises the doped metal salt of aluminum sulfate ([0055] and [0059]).
Regarding claims 6 and 7, Liu teaches the radially-structures nickel-based precursors according to claim 1, and the further limitations recited in in claims 6 and 7 merely limit the process by which the precursor particles are generated. Because the method required is still substantially similar to the method described by Liu, the particles are also expected to be the same or obvious variations of the structures obtained by Liu.
It is again noted that the “Patent Office bears a lesser burden of proof in making out a case of prima facie obviousness for product-by-process claims because of their peculiar nature" than when a product is claimed in the conventional fashion. In re Fessmann, 489 F.2d 742, 744, 180 USPQ 324, 326 (CCPA 1974). Once the examiner provides a rationale tending to show that the claimed product appears to be the same or similar to that of the prior art, although produced by a different process, the burden shifts to applicant to come forward with evidence establishing an nonobvious difference between the claimed product and the prior art product. In re Marosi, 710 F.2d 799, 803, 218 USPQ 289, 292-33 (Fed. Cir. 1983). MPEP 2113(II).
Regarding claim 8, Liu teaches the radially-structured nickel-based precursor according to claim 1 where in step 1 and step 2 the heating is conducted at 30 °C to 80 °C ([0067]), which overlaps with the instantly claimed range of 50-80°C. It is further noted that Liu teaches a specific embodiment where the heating is conducted at 55 °C, [0115] which lies in the instantly claimed range.
It is again noted that the courts have stated where the claimed ranges overlap or lie inside the ranges disclosed by the prior art and even when the claimed ranges and prior art ranges do not overlap but are close enough that one skilled in the art would have expected them to have similar properties, a prima facie case of obviousness exists.
Claims 1-5 and 8 are rejected under 35 U.S.C. 103 as being unpatentable over Liu et al. (CN 111370679 A) in view of Ma et al. (US 2019/0359497 A1). The provided English machine translation of Liu (CN 111370679 A) is relied upon in the analysis below.
Regarding claim 1, Liu discloses a radially-structured nickel-based precursor, wherein an overall shape of the precursor is a secondary sphere formed by aggregation of primary crystal grains; the secondary sphere has a loose and porous network core inside, and has a uniform and regular strip-shaped primary crystal grains outside, and the strip-shaped primary crystal grains grow outward perpendicularly to a surface of the core and are arranged radially and closely ([0008], [00049] and Fig. 1, copied above); and the precursor has a chemical formula of NixCoyM(1-x-y)(OH)2, where 0.6<x<1, 0<y<1, 0.6<x+y<1, and M is Al or Mn ([0049]); it is noted that the restrictions on x and x+y limit the value of y to being no greater than 0.4. Liu therefore teaches a precursor with the formula of NixCoyM(1-x-y)(OH)2, where 0.6<x<1 and 0<y<0.4, which anticipates the formula recited in the instant claim with z=0 and a doping element of Mn or Al.
Liu further teaches that a diameter of the core of the precursor may account for anywhere from 1% to 75% of the entire precursor particle (the ratio of the radius of the internal region to the radius of the secondary particles is 1% to 75%; [0045]), which overlaps with the instantly claimed more than ½ (50%) of a diameter of an entire precursor particle.
It is noted that the courts have stated where the claimed ranges “overlap or lie inside the ranges disclosed by the prior art” a prima facie case of obviousness exists (see In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990); Titanium Metals Corp. of America v. Banner, 778 F2d 775. 227 USPQ 773 (Fed. Cir. 1985) (see MPEP 2144.05.01). Therefore, the claimed range merely represents an obvious variant and/or routine optimization of the values of the cited prior art.
Furthermore, Liu also teaches that the radially-structured nickel-based precursor is prepared by a method comprising the following steps: (1) adding a metal solution (mixed salt solution…contains nickel salt, cobalt salt, and M salt;[0055])), an alkali liquor (precipitant solution, which is preferably NaOH, an alkali; [0061]), and ammonia water (complexing agent, which can be ammonia; [0063]) to a first reactor (Add the mixed salt solution, precipitant solution and complexing agent solution to the base liquid, in a controlled crystallization reactor; [0056] and [0071]), and heating and stirring ([0067]) to allow a reaction to prepare a seed crystal (carry out the first-stage co-precipitation reaction to obtain initial particles formed by the aggregation of multiple primary particles; [0056]), during the reaction controlling the pH within a range of 10.8 to 11.8 ([0071]), which falls in the instantly claimed range of 9-12, and controlling the ammonia concentration in the range 0.3 g to 13.6 g/L (0.02-0.8 mol/L; [0071]), which overlaps with the instantly claimed range of 0 to 5 g/L, and continuously feeding the metal solution, the alkali liquor, and the ammonia water until a particle size reaches a target value of the seed crystal (mixed salt solution, precipitant solution, and complexing agent solution are added to the controlled crystallization reactor in a co-current flow at a certain flow rate…until the particle size of the internal region…is reached; [0071]), wherein the metal solution comprises a nickel salt and a cobalt salt ([0055]). It is additionally noted that Liu also teaches an example where the concentration of ammonia is 2.55-4.25 g/L (0.15-0.25 mol/L; [0130]), which falls within the instantly claimed range of 0-5 g/L.
Liu further teaches continued heating and stirring of the seed crystal, the metal solution, the alkali liquor, and the ammonia water to allow a reaction, during the reaction, controlling the pH at 10.8-11.8, which falls in the instantly claimed range of 9-12, controlling an ammonia concentration in the reaction system and continuously feeding the metal solution, the alkali liquor, and the ammonia water until a particle size reaches a target value of the precursor to obtain a product (in step S30, while keeping other process conditions unchanged, the concentration of the complexing agent in the reaction solution is controlled to increase linearly at a rate of 0.005 mol/L/h--0.02 mol/L/h, preferably linearly at a rate of 0.005 mol/L/h-0.01 mol/L/h. The reaction continues for a period of time until the target particle size of the positive electrode active material precursor is reached; [0071]) ; and collecting, washing, dewatering, and drying the product to obtain the radially-structured nickel-based precursor (washing and drying it to obtain the final positive electrode active material precursor product; [0074]; obtaining the product means it was collected, while drying the product means it was dewatered).
While Liu is silent on the final concentration of ammonia reached in the second reaction, it is noted that the starting concentration will be in the range of 0.3 g to 13.6 g/L [0071], which overlaps with the claimed range of 5-10 g/L for step (2).
While Liu is silent on the time of the second rection, Ma also teaches the production of ternary precursor particles with a core shell type structure that comprise a shell around a porous core (abstract) by a similar method (Fig. 1), and Ma further teaches the second growth stage lasting 1 to 12 hours ([0029]). For even a 12 h reaction time for step (2), the final concentrations of ammonia taught by Liu would be in the range of 1.4 g/L to 17.7 g/L (0.02 mol/L + 0.005 mol/L/h*12 h to 0.8 mol/L + 0.02 mol/L/h*12 h, or 0.08 mol/L to 1.04 mol/L), which also overlaps with the instantly claimed range of 5 g/L to 10 g/L. Additionally, because Liu teaches continuing the reaction until a desired size is reached, it would have been obvious to one of ordinary skill in the art to vary by routine experimentation the reaction time, and hence the exact concentrations reached in the second step, in order to achieve the desired particle sizes.
It is again noted that the courts have stated where the claimed ranges overlap or lie inside the ranges disclosed by the prior art a prima facie case of obviousness exists. Therefore, the claimed range of ammonia concentrations in step (2) merely represents an obvious variant and/or routine optimization of the values used by Liu.
Liu does not specifically teach adding the seed crystal, the metal solution, the alkali liquor, and the ammonia water to a second reactor, as recited in claim 1.
However, Ma also teaches that the after forming the crystal seeds, they can be transferred to a second reactor for continued growth around the core ([0022]-[0023] and Fig. 1).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to transfer the seed crystals obtained in the method of Liu to a second vessel for continued growth, as taught by Ma. One of ordinary skill in the art would have been motivated to do so in order to separately control the conditions in the second reactor, and because it is common in the art to carry out different reaction steps in different vessels.
Regarding claim 2, modified Liu teaches the radially-structured nickel-based precursor according to claim 1, where the average particle size is between 3 μm and 20 μm ([0048]), which overlaps with the instantly claimed range of 3 to 10 μm.
It is noted that the courts have stated where the claimed ranges “overlap or lie inside the ranges disclosed by the prior art” a prima facie case of obviousness exists (see In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990); Titanium Metals Corp. of America v. Banner, 778 F2d 775. 227 USPQ 773 (Fed. Cir. 1985) (see MPEP 2144.05.01). Therefore, the claimed ranges merely represent an obvious variant and/or routine optimization of the values of the cited prior art.
Regarding claim 3, modified Liu teaches the radially-structured nickel-based precursor according to claim 1 where M is Al ([0049]).
Regarding claim 4, modified Liu teaches the radially-structured nickel-based precursor according to claim 1 where the total metals in the metal solution more preferably have a molar concentration of 1.5 mol/L to 2.0 mol/L ([0060]), which lies in the instantly claimed range.
Regarding claim 5, modified Liu teaches the radially-structured nickel-based precursor according to claim 1 where the metal solution further comprises the doped metal salt of aluminum sulfate ([0055] and [0059]).
Regarding claim 8, modified Liu teaches the radially-structured nickel-based precursor according to claim 1 where in step 1 and step 2 the heating is conducted at 30 °C to 80 °C ([0067]), which overlaps with the instantly claimed range of 50-80°C. It is further noted that Liu teaches a specific embodiment where the heating is conducted at 55 °C, [0115] which lies in the instantly claimed range.
It is again noted that the courts have stated where the claimed ranges overlap or lie inside the ranges disclosed by the prior art and even when the claimed ranges and prior art ranges do not overlap but are close enough that one skilled in the art would have expected them to have similar properties, a prima facie case of obviousness exists.
Claim 6 is rejected under 35 U.S.C. 103 as being unpatentable over Liu et al. (CN 111370679 A) in view of Ma et al. (US 2019/0359497 A1), as applied to claim 1 above, and further in view of Long et al. (Met. Funct. Mater. 2020, 27(3), 18-23). The provided English machine translations of Liu and Long are relied upon in the analysis below.
Regarding claim 6, modified Liu teaches the radially-structured nickel-based precursor according to claim 1, but does not teach the precursor being produced by a method wherein in step (1), when the particle reaches the target value of the seed crystal the pH is increased to make a new crystal nucleus grow.
However, Long also teaches the preparation of nickel cobalt manganese hydroxide cathode precursor materials by co-precipitation (abstract) and further teaches controlling nucleation and growth by adjusting the pH value of the solution (abstract). In particular, Long teaches that increasing the pH of the growth solution promotes nucleation and the produces more seed crystals (the pH was adjusted [from 11.6] to 12.1 to further promote the nucleation process and produce more seed crystal particles; p. 4, col. 1).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to further modify the method of Liu to in step (1), when the particle reaches the target value of the seed crystal, increase the pH to make a new crystal nucleus grow, which will keep the particle size of the seed crystal in the reactor around the target value.
One of ordinary skill in the art would have been motivated to do so because Long teaches that this step increases the number of seed crystal particles and growing seed crystals is the purpose of the step (1) carried out by Liu.
Claim 7 is rejected under 35 U.S.C. 103 as being unpatentable over Liu et al. (CN 111370679 A) in view of Ma et al. (US 2019/0359497 A1), as applied to claim 1 above, and further in view of Nakamura et al. (US 2019/0260024). The provided English machine translation of Liu (CN 111370679 A) is relied upon in the analysis below.
Regarding claim 7, modified Liu teaches the radially-structured nickel-based precursor according to claim 1, but Liu does not teach in step (2), when the particle size reaches the target value of the precursor, the seed crystal being fed while overflowing.
However, Nakamura also teaches the synthesis of radially-structured nickel based precursor materials by a co-precipitation method (abstract) and further teaches that the particles can be recovered by overflowing during a continuous crystallization (the continuous crystallization method is the crystallization method in which while continuously feeding the mixed aqueous solution described above, pH is controlled by feeding the neutralizing agent, whereby the composite hydroxide particles thus produced is recovered by overflowing; [0072]). Nakamura further teaches that such a method is suitable for mass production and is industrially advantageous ([0072]).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to produce the particles disclosed by Liu by a method where in step (2), when the particle size reaches the target value of the precursor, the seed crystal is fed while overflowing, which will maintain a solid content in the reactor relatively stable, keep the particle size of the precursor in the reactor will be kept around the target value. One of ordinary skill in the art would have been motivated to do so because such a process for collecting the precursor material is suitable for mass production and industrially advantageous, as taught by Nakamura.
Conclusion
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/NICHOLAS A. PIRO/Assistant Examiner, Art Unit 1738
/PAUL A WARTALOWICZ/Primary Examiner, Art Unit 1735