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 30 June 2023 has been received and considered by the Examiner.
Specification
The chelating resin referred to as LonacSR-5 in [0013] is likely meant to refer to Ionac® SR-5 an ion-exchange resin. No resin with the name Lonac SR-5 could be located by the Examiner.
The use of the terms Amberlite, Ionac, Purolite, Chelex, CH-90Na, XFS4195, D851, and D402-II, which are trade names or marks used in commerce, has been noted in this application. The terms should be accompanied by the generic terminology; furthermore the term should be capitalized wherever it appears or, where appropriate, include a proper symbol indicating use in commerce such as ™, SM , or ® following the term.
Although the use of trade names and marks used in commerce (i.e., trademarks, service marks, certification marks, and collective marks) are permissible in patent applications, the proprietary nature of the marks should be respected and every effort made to prevent their use in any manner which might adversely affect their validity as commercial marks.
Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claim 4 is rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
Claim 4 contains the trademark/trade names of Amberlite, Lonac (or Ionac), Purolite, Chelex, CH-90Na, XFS4195, D851, and D402-II. Where a trademark or trade name is used in a claim as a limitation to identify or describe a particular material or product, the claim does not comply with the requirements of 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph. See Ex parte Simpson, 218 USPQ 1020 (Bd. App. 1982). The claim scope is uncertain since the trademark or trade name cannot be used properly to identify any particular material or product. A trademark or trade name is used to identify a source of goods, and not the goods themselves. Thus, a trademark or trade name does not identify or describe the goods associated with the trademark or trade name. In the present case, the trademark/trade name is used to identify/describe specific brands of chelating resins and, accordingly, the identification/description is indefinite.
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 1-3 and 6-8 are rejected under 35 U.S.C. 103 as being unpatentable over Dougherty (US 12,412,940 B1; effective filing date of 27 January 2021) in view of Chai et al. (CN 110527836 A), Zheng et al. (RSC Adv. 2016, 6, 43613–43625), and Hao et al. (Mater. Res. Bull., 2012, 47, 4048-4053; NPL document #1 on the IDS filed 30 June 2023). The provided English machine translation of Chai (CN 110527836 A) is referenced in the analysis below.
Regarding claim 1, Dougherty teaches recycling method for a mixed waste material of lithium ion batteries (recovery of lithium and various non-lithium components from lithium ion battery waste materials; abstract) including waste material from lithium nickel manganese cobalt oxide and lithium iron phosphate materials (col. 4, lines 26-30), comprising the following steps:
S1: adding the mixed waste material of lithium nickel manganese cobalt oxide and lithium iron phosphate to an acid solution for acid-leaching (the comminuted and dried material will then be transferred to a leaching tank where it is intimately mixed with a leach solution… the leach solution will be an aqueous acid; col. 4, lines 61-64), and conducting solid-liquid separation to obtain an acid-leaching liquor (the slurry from the leaching tank is filtered to remove particulates and so form a leachate; col. 5, lines 54-55) ;
S2: using a resin to adsorb nickel, cobalt, and manganese in the acid-leaching liquor (the leachate then passes to a separation system, preferably an ion-exchange system where the divalent metal ions are captured on the resin… ion exchange resins … may bind at least two or three different metal ions (e.g., two or three of cobalt, nickel, manganese; col. 5, lines 60-66), and washing a resulting saturated resin with an elution solvent (Elution of the bound ions may then be performed in a sequential manner using suitable elution solvents; col. 6, lines 5-7), and a post-adsorption solution (the pass through fraction; col. 6, line 23);
S3: heating the post-adsorption solution, and adding a lithium-precipitating reagent to obtain a lithium salt precipitate and a post-precipitation solution (lithium could be precipitated via carbonation, either by CO2 or Na2CO3, which would result in precipitation of Li2CO3….this may be performed at elevated temperatures; col. 6, lines 27-30).
Dougherty further teaches that the solvent used to elute the metal ions from the resin may be sulfuric acid (col. 6, lines 48-50) and that metals may be eluted together to obtain a mixed solution (it might also be more advantageous to strip the nickel and copper together; col. 6, lines 61-62).
Dougherty does not explicitly teach obtaining a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate. Nor does Dougherty teach concentrating the post-precipitation solution, adding a carbon source, or stirring to obtain a dispersed material, and subjecting the dispersed material to electrospinning to obtain a sheet material and drying and roasting the sheet material to obtain a ferric phosphate/carbon material.
However, Chai also teaches a method of recovering metals from waste lithium ion batteries (title) that comprises use of an ion-exchange resin to bind nickel, cobalt, and manganese while letting lithium pass through (to simultaneously adsorb valuable metals such as nickel, cobalt and manganese…so that lithium ions in the solution are not adsorbed … but remain completely in the solution after adsorption; [0025]). Chai further teaches that the cobalt, nickel, and manganese may be eluted together with sulfuric acid to form a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate (washed with sulfuric acid to obtain a mixed solution of nickel-cobalt-manganese sulfate; [0010]), and that such a solution can be used as a raw material for the synthesis of ternary precursors ([0027]).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to use the elution method of Chai in the recycling method of Dougherty. One of ordinary skill in the art would have been motivated to do so because Chai teaches that their method achieves high total recovery rates for nickel, cobalt and manganese, and is simple and easy to scale up ([0022]), and that recovered cobalt-manganese-nickel solution can be used as a raw material for ternary precursors.
Zheng also works in the field of recovery of metal materials from spent lithium ion batteries (abstract) and uses leaching with sulfuric acid and subsequent precipitation of lithium carbonate to recover lithium from the spent batteries. Zheng further teaches that FePO4 can also be recovered from the spent lithium ion batteries and subsequently mixed with a carbon source for reuse in battery materials (Fig. 22). Zheng additionally teaches that the final filtrate in the recovery scheme can be concentrated as part of the recovery process for the precipitated materials (p. 43614, col. 1, ¶ 5). In Zheng’s scheme this final solution being concentrated is a lithium-containing solution, but it would have been obvious to one of ordinary skill in the art to concentrate any post-precipitation solution in order to enhance the recovery of materials contained therein.
While Zheng teaches the recovery of the FePO4 prior to the precipitation of the lithium carbonate, it is noted that the courts have held that the selection of any order of performing process steps is prima facie obvious in the absence of new or unexpected results. In re Burhans, 154 F.2d 690, 69 USPQ 330 (CCPA 1946). MPEP 2144.04(IV)(C).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention also recover FePO4 in the method of modified Dougherty, whether before or after the precipitation of lithium carbonate, by concentrating the post-precipitation solution, as taught by Zheng. It would have also been obvious to mix the recovered FePO4 product with a carbon source for the production of new battery materials, as also taught by Zheng. One of ordinary skill in the art would have been motivated to do so because Zheng teaches that the recovery of spent lithium ion batteries, including iron phosphate materials, and the regeneration of battery materials is necessary to prevent environmental pollution and resource depletion (Introduction).
Furthermore, Hao is also in the field of lithium ion battery cathode materials, and Hao teaches that ferric phosphate can be converted into an cathode material with enhanced electrochemical performance (abstract) and which avoids the sensitivity issues associated with forming LiFePO4 (LiFePO4 can also easily deteriorate by the improper use and storage, all of these bring many difficulties to the modification research and practical application; Introduction, ¶ 1). Hao further teaches that formation of the ferric phosphate/carbon composite material can be carried by a process comprising mixing ferric phosphate (FPO) and a carbon source (PAN), stirring to obtain a dispersed mixture, and then subjecting the dispersed mixture to electrospinning to obtain a sheet material (thin film product) , and drying and roasting the sheet material to obtain a ferric phosphate/carbon material (annealed at 800 °C [which will also dry the material] …finally obtained P-FPO/C composite material; Section 2.1, ¶ 3).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to use the FePO4 obtained by concentrating the post-precipitation solution of modified Dougherty and to add a carbon source, stir to obtain a dispersed mixture; to subject this dispersed mixture to electrospinning to obtain a sheet material; and to dry and roast the sheet material to obtain a ferric phosphate/carbon material, as taught by Hao. One of ordinary skill in the art would have been motivated to do so because Hao teaches the ferric phosphate/carbon composite material so obtained has enhanced electrochemical performance and decreased deterioration.
Regarding claim 2, modified Dougherty teaches the method of claim 1 where in S1 the acid solution is sulfuric acid (col. 2, line 35).
Regarding claim 3, modified Dougherty teaches the method of claim 1 where in S1 a mass ratio of the acid solution (liquid) to the mixed waste material (solid) can be 5:1 ( suitable solid-to-liquid ratios include … 1:5; col. 5, lines 47-48), which lies in the instantly claimed range.
Regarding claim 6, modified Dougherty teaches the method of claim 1, where Dougherty teaches in S3 the lithium-precipitating reagent is sodium carbonate (col. 6, line 28) and the heating is conducted at elevated temperatures of up to 90°C-95 °C (col. 6, lines 30-31), which lies in the instantly claimed range of 40 °C to 120 °C.
Regarding claim 7, modified Dougherty teaches the method of claim 1, but neither Dougherty nor Zheng teach the concentration of iron in a post-precipitation solution.
However, Hao teaches that for the electrospinning of ferric phosphate (FePO4 or FPO) and PAN in an NMP solution, the concentration of FPO should be 3 g FPO per 30 mL of NMP solution, which corresponds to an iron concentration of 37 g/L.
Therefore, it would have been obvious to one of ordinary skill in the art to concentrate the iron containing mixture in the method of modified Dougherty to an iron concentration above 37 g/L, including into the claimed range of 40 g/L to 150 g/L. One of ordinary skill in the art would have been motivated to use such concentration so that when they are mixed with solvents according to the method of Hao, leading to dilution, they will have iron concentrations in the range taught by Hao.
It is 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 (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).
It is further noted that ,generally, differences in concentration will not support the patentability of subject matter encompassed by the prior art unless there is evidence indicating such concentration or temperature is critical. "[W]here the general conditions of a claim are disclosed in the prior art, it is not inventive to discover the optimum or workable ranges by routine experimentation." See MPEP 2144.05 and In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955).
Therefore, the claimed ranges merely represent an obvious variant and/or routine optimization of the values of the cited prior art.
Regarding claim 8, modified Dougherty teaches the method of claim 1 where Hao teaches in S4 the carbon source is polyacrylonitrile (PAN; abstract and Section 3.2).
Claim 4 is rejected under 35 U.S.C. 103 as being unpatentable over Dougherty (US 12412940 B1; effective filing date of 27 January 2021) in view of Chai et al. (CN 110527836 A), Zheng et al. (RSC Adv. 2016, 6, 43613–43625), and Hao et al. (Mater. Res. Bull., 2012, 47, 4048-4053; NPL document #1 on the IDS filed 30 June 2023), as applied to claim 1 above, and further in view of Li et al. (CN 102807296 A). The provided English machine translations of Chai (CN 110527836 A) and Li (CN 102807296 A) are used in the analysis below.
Regarding claim 4, modified Dougherty teaches the method of claim 1, but Dougherty does not teach any of the specific resins recited in the instant claim.
However, Chai teaches that the resin for absorbing nickel, cobalt, and manganese could be a chelating resin such as D401 or D402 ([0017]). Chai also does not teach any of the specific resins recited in the instant claim.
However, Li teaches that D401, D402 and D402-II are all similar macroporous chelating resins of equivalent grades, with good selectivity and exchange capacity for multivalent ions ([0024]).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to use D402-II resin in place of the D402 resin taught by Chai in the method of modified Dougherty. One of ordinary skill in the art would have been motivated to do so because Li teaches that D402 and D402-II are analogous resins that serve the same purpose of removing multivalent ions, which is the same function of the resins used by Chai and Dougherty. The change in resins is therefore the simple substitution of one known resin for another with the predictable result of separating nickel, cobalt, and manganese from lithium. MPEP 2143(I)(B).
Claim 5 is rejected under 35 U.S.C. 103 as being unpatentable over Dougherty (US 12412940 B1; effective filing date of 27 January 2021) in view of Chai et al. (CN 110527836 A), Zheng et al. (RSC Adv. 2016, 6, 43613–43625), and Hao et al. (Mater. Res. Bull., 2012, 47, 4048-4053; NPL document #1 on the IDS filed 30 June 2023), as applied to claim 1 above, and further in view of Kochhar et al. (US 2020/0078796 A1). The provided English machine translation of Chai (CN 110527836 A) is used in the analysis below.
Regarding claim 5, modified Dougherty teaches the method of claim 1, where Chai teaches using the obtained mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate as a ternary material precursor. Neither Chai nor Dougherty specifically teach subjecting the solution to precipitation to obtain a ternary precursor.
However, Kochhar also teaches a process for recovering materials from batteries comprising steps of acid leaching and isolating a mixed nickel, cobalt, manganese product (Fig 1A, elements f and m). Kochhar further teaches subjecting the nickel, manganese, cobalt product to precipitation to obtain a precipitated product such as Ni/Mn/Co hydroxide ([0122]), which is ternary precursor.
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to subject the mixed solution of nickel sulfate, cobalt sulfate, and manganese sulfate obtained by the method of modified Dougherty to a precipitation, as taught by Kochhar. One of ordinary skill in the art would have been motivated to do so in order to isolate a solid product that can be used a ternary precursor, as taught by Chai and Kochhar.
Claims 9 and 10 are rejected under 35 U.S.C. 103 as being unpatentable over Dougherty (US 12412940 B1; effective filing date of 27 January 2021) in view of Chai et al. (CN 110527836 A), Zheng et al. (RSC Adv. 2016, 6, 43613–43625), and Hao et al. (Mater. Res. Bull., 2012, 47, 4048-4053; NPL document #1 on the IDS filed 30 June 2023), as applied to claim 1 above, and further in view Toprakci et al. (J. Power Sources 2011, 196(18), 7692-769).
Regarding claim 9, modified Dougherty teaches the method of claim 1, where Hao teaches the carbon source being added to a solution of N-methylpyrrolidone (NMP) at 80 °C. Neither Hao nor Dougherty teaches the carbon source being first dissolved in dimethylformamide to obtain a solution, then pouring the solution into a concentrated post-precipitation solution.
However, Toprakci teaches a similar method of preparing iron phosphate/carbon composite materials for lithium ion batteries by electrospinning (title and abstract). Toprakci further teaches the carbon source (PAN) first being dissolved in dimethylformamide to obtain a solution, and then mixing that solution with a solution containing the iron precursors before electrospinning (LiFePO4 precursor materials and PAN were dissolved in N,N-dimethylformamide separately and they were mixed before electrospinning; abstract).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to first dissolve the PAN used in the method of modified Dougherty in dimethylformamide to obtain a solution, then pouring the solution into the concentrated post-precipitation solution that contains the iron phosphate precursors, as taught by Toprakci. One of ordinary skill in the art would have been motivated to do so because they would be replacing one polar, aprotic organic solvent (NMP) with another (DMF), as well as changing the order of addition for another that had also been shown as effective in the electrospinning of PAN and iron phosphate materials, as taught by Toprakci. MPEP 2143(I)(B).
It is also noted that the courts have held that changes in sequence of adding ingredients are prima facie obvious absent new or unexpected results. Ex parte Rubin, 128 USPQ 440 (Bd. App. 1959). See also In re Burhans, 154 F.2d 690, 69 USPQ 330 (CCPA 1946); In re Gibson, 39 F.2d 975, 5 USPQ 230 (CCPA 1930). MPEP 2144.04(IV)(C).
Regarding claim 10, modified Dougherty teaches the method of claim 1, where Hao teaches immersed in deionized water for removing the organic solvent (NMP) component, then annealing at 800 °C for 2 h using a ramp rate of 10 °C/min (Section 2.1 and Fig. 1), which will complete the drying and roasting process.
It is noted that the process taught by Hao will include 5 min in the temperature range of 40°C to 90°C, over which time residual washing water would evaporate, thereby meeting the claim limitation requiring drying to be conducted at 40° to 90 °C.
Neither Dougherty nor Hao teach the roasting being conducted at 250 °C to 600 °C.
However, Toprakci teaches a similar method of preparing iron phosphate/carbon composite materials for lithium ion batteries by electrospinning and heat treatment of an iron phosphate/carbon composite (title and abstract). Toprakci further teaches that the roasting (heat treatment/carbonization) may be conducted at 600°C (Fig. 2, and p. 7697, ¶ 2).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to conduct the roasting in the method of modified Dougherty at 600 °C, as taught by Toprakci. One of ordinary skill in the art would have been motivated to do so because Toprakci teaches that this lower, more easily accessible temperature of 600 °C is also effective at carbonization of PAN.
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to Nicholas A Piro whose telephone number is (571)272-6344. The examiner can normally be reached Mon-Fri, 8:00 am-5:00 pm.
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/NICHOLAS A. PIRO/Assistant Examiner, Art Unit 1738
/PAUL A WARTALOWICZ/Primary Examiner, Art Unit 1735