DETAILED ACTION
Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Claim Rejections - 35 USC § 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.
Claims 1-5, 7-8, 11-17, and 20 rejected under 35 U.S.C. 103 as being unpatentable over ‘Molecularly Tailored Lithium–Arene Complex Enables Chemical Prelithiation of High-Capacity Lithium-Ion Battery Anodes’ hereinafter referred to as ‘Jang’ in view of ‘Rechargeable lithiated silicon–sulfur (SLS) battery prototypes’ hereinafter referred to as ‘Elazari’
Regarding Claim 1,
Jang teaches a method for manufacturing a battery cell comprising: providing an anode electrode including silicon film arranged on an anode current collector; immersing the anode electrode in a solution comprising lithium metal, an arene, and an organic solvent for a predetermined period to form a pre-lithiation coating on the silicon film (Jang, “Herein, we show that a molecularly engineered Li–arene complex with a sufficiently low redox potential drives active Li accommodation in Si-based anodes to provide an ideal Li content in a full cell”, see Abstract)(Jang, “The LAC solution was prepared by dissolving lithium metal slice in as-prepared 0.5M arene in DME for 1 hour at 30°C under a vigorous stirring in an Ar-filled glove box”, Supplemental S2); and heating the anode electrode to remove the organic solvent and the arene after the predetermined period (Jang, “Dry air stability test was proceeded in a dry room with a dew point of -86.6 ℃. SiOx anodes were first prelithiated for 90 minutes at
30 ℃. After being exposed in dry air for 5, 15, 30 and 60 minutes, the prelithiated anodes were inserted into an Ar-filled glove box”, see S2).
Jang does not teach a nonplanar silicon film.
Elazari teaches a nonplanar silicon film (Elazari, “Our results show that pre-lithiated columnar structured a-Si can serve as promising anode in a Li-ion sulfur system.”, see Conclusion).
Elazari teaches that columnar non silicon films can work well as an anode Elazari, “Our results show that pre-lithiated columnar structured a-Si can serve as promising anode in a Li-ion sulfur system.”, see Conclusion).
Jang and Elazari are analogous as they are both of the same field of silicon anodes.
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the anode as taught in Jang to be the silicon columnar anode as taught in Elazari in order to improve the performance of the cell.
Regarding Claim 2,
Modified Jang teaches the method of claim 1, wherein the arene is selected from a group consisting of naphthalene, bi phenyl, terphenyl, biphenylene, di phenyl methane, anthracene polyphenyl aliphatic hydrocarbon, polycyclic aromatic hydrocarbon, and/or a combination thereof (Jang, “ Lithiation/delithiation of prelithiated Si/SiOx using Li–arene (e.g., 4,4′-dimethylbiphenyl) complex beforehand with volume expansion and active lithium loss prior to cell assembly.”, see Scheme 1).
Regarding Claim 3,
Modified Jang teaches the method of claim 1, wherein the arene is selected from a group consisting of 4,4'-dimethylbiphenyl, 2-methylbiphenyl, 3',4,4'-tetramethylbiphenyl, 3'-dimethylbiphenyl, methyl naphthalene, 2-methylnaphthalene, 9,9-dimethyl-9H-fluorene, and/or combinations thereof (Jang, “ Lithiation/delithiation of prelithiated Si/SiOx using Li–arene (e.g., 4,4′-dimethylbiphenyl) complex beforehand with volume expansion and active lithium loss prior to cell assembly.”, see Scheme 1).
Regarding Claim 4,
Modified Jang teaches the method of claim 1, wherein the lithium metal is selected from a group consisting of a lithium powder, a lithium foil, a lithium sheet, a lithium block, and/or combinations thereof (Jang, “The LAC solution was prepared by dissolving lithium metal slice in as-prepared 0.5M arene in DME for 1 hour at 30°C under a vigorous stirring in an Ar-filled glove box”, Supplemental S2).
Regarding Claim 5,
Modified Jang teaches the method of claim 1, wherein a molar ratio of the lithium metal and the arene in the solution is 4 Jang, “The molar ratio of Li:arenes was fixed to 4:1 to supply an enough amount of Li for the formation of LACs”, see S2)
Modified Jang does not teach wherein a molar ratio of the lithium metal and the arene in the solution is in a range from 0.2 to 2.0.
Jang teaches that the molar ratio between lithium metal and arene and that the range was given to allow for enough lithium to form the LACs (Jang, “The molar ratio of Li:arenes was fixed to 4:1 to supply an enough amount of Li for the formation of LACs”, see S2)
It would have been obvious to one of ordinary skill in the art to have optimized the range from 4.0 to 2.0 in order to find the ideal about of lithium for the formation of LAC without there being an excess (see MPEP 2144.05 (II)(A)).
Regarding Claim 7,
Jang teaches the method of claim 1, wherein the organic solvent is selected from a group consisting of 1,2-dimethoxyethane (DME), diglyme (DEGDME), and tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-meTHF), tetrahydropyran (THP), and/or combinations thereof (Jang, “The LAC solution was prepared by dissolving lithium metal slice in as-prepared 0.5M arene in DME for 1 hour at 30°C under a vigorous stirring in an Ar-filled glove box”, Supplemental S2).
Regarding Claim 8,
Jang teaches the method of claim 1, further comprising arranging A of the anode electrode, C cathode electrodes, and S separators in a battery stack where A, C, and S are integers one (Jang, “For full cells, cathodes were fabricated by casting slurry composed of Li(Ni1/3Co1/3Mn1/3)O2 (NCM111) or Li(Ni0.5Co0.2Mn0.3)O2 (NCM523) (Wellcos Corporation, Korea), Super P, and polyvinylidene fluoride (PvdF) binder at a mass ratio of 84:8:8 in N-methyl-2 pyrrolidone (NMP) solvent on a carbon coated Al foil. The diameters of cathode and anode were 11.3 mm and 12 mm, respectively. The full cells were designed to have an N/P ratio (the practical capacity ratio of the negative electrode to the positive electrode) of 1.2. The method of coin cell assembly was same as those in the half-cell above except for using an additional Whatman GFD separator”, see S1).
Jang does not teach that the stack is greater than one.
It would have been an obvious matter of duplication to create a battery stack with cathodes, anode, and separator greater than one in order to increase the total capacity of the cell (see MPEP 2144.04 (VI)(B))
Regarding Claim 11,
Modified Jang teaches the method of claim 1, wherein the nonplanar silicon film comprises a plurality of columns (Elazari, “Our results show that pre-lithiated columnar structured a-Si can serve as promising anode in a Li-ion sulfur system.”, see Conclusion).
Regarding Claim 12,
Modified Jang teaches the method of claim 11, wherein the plurality of columns have a major axis in a range from 0.5 μm to 80 μm and a minor axis in a range from 0.5 μm to 80 μm (see annotated figure from Elazari below).
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Regarding Claim 13,
Modified Jang teaches the method of claim 1, wherein the nonplanar silicon film is deposited onto the anode current collector using at least one of physical vapor deposition and magnetron sputter deposition (Elzari, “Silicon thin film electrodes were prepared by DC magnetron sputtering (Angstrom Sciences Inc., USA) of n-type silicon (99.999%, Kurt J. Lesker, USA), at a pressure of about 5 × 10− 3 Torr of argon (99.9995%)”, see 2. Experimental).
Regarding Claim 14,
Modified Jang teaches the method of claim 1, wherein the nonplanar silicon film comprises one of pure silicon, silicon dioxide, and silicon mixed with at least one of graphite and carbon (Elzari, “Silicon thin film electrodes were prepared by DC magnetron sputtering (Angstrom Sciences Inc., USA) of n-type silicon (99.999%, Kurt J. Lesker, USA), at a pressure of about 5 × 10− 3 Torr of argon (99.9995%)”, see 2. Experimental).
Regarding Claim 15,
Modified Jang teaches the method of claim 1, wherein the anode current collector comprises roughened copper foil (Jang, “After casting the slurry on a Cu foil current collector, the electrodes were dried at 80°C for 1 h, roll-pressed”, see S1).
Regarding Claim 16,
Jang teaches a method for manufacturing a battery cell, comprising: providing an anode electrode including a silicon film (Jang, “Herein, we show that a molecularly engineered Li–arene complex with a sufficiently low redox potential drives active Li accommodation in Si-based anodes to provide an ideal Li content in a full cell”, see Abstract); selecting a lithiation level of the nonplanar silicon film based on a desired state of charge percentage (SOC%); using a lithiation curve and the desired SOC%, determining a voltage of the silicon film (Jang, “Prelithiation of SiOx anodes enabled by molecular tailoring of arenes. a) Cyclic voltammograms of naphthalene, biphenyl, and methyl-substituted biphenyls in 0.5 m LiPF6 in DME solution with comparison of differential capacity curves of the SiOx anode. b) Correlation between measured redox potential (E1/2) of BP derivatives and calculated LUMO energy. c) Correlation between redox potential and initial CE. d) Voltage profiles of initial discharge–charge cycle of pristine (black) and prelithiated (green) SiOx electrodes.”, see Fig. 1) (Jang, “As shown in Figure 1 d, 4,4′-DMBP, having an E1/2 of 0.19 V, successfully compensated for the irreversible Li loss during the initial discharge of the prelithiated SiOx anode, which exhibited a discharge capacity of 1483 mAh g−1 equivalent to the following charge capacity. Since the SiOx electrode is partially lithiated after prelithiation with the Li-4,4′-DMBP complex solution, discharge starts at a much lower voltage than the bare electrode.”, see Results and Discussion) ; selecting a chemical potential of a solution including lithium, an arene, and an organic solvent based on the voltage of the silicon film; and immersing the silicon film in the solution for a predetermined period to form a pre-lithiation coating (Jang, “The immersion time also exerted a profound effect on the prelithiation degree of SiOx electrodes (Figure 2 c,d). The lithiation reaction occurred within a few minutes, remarkably improving the initial CE of the SiOx electrodes. After 5 min of immersion, the initial CE increased from 57 % to 91 %, a value that is comparable to that of commercial anodes. After 30 min, when the initial CE exceeded 100 %, the prelithiation slowed down and then nearly reached equilibrium after 2 h. Given these results, we expect that precise control of prelithiation degree should be readily realised at the industrial scale by adjusting the reaction time and temperature.”, see Results and Discussion)(see Fig. 2).
Jang does not teach a nonplanar silicon film.
Elazari teaches a nonplanar silicon film (Elazari, “Our results show that pre-lithiated columnar structured a-Si can serve as promising anode in a Li-ion sulfur system.”, see Conclusion).
Elazari teaches that columnar non silicon films can work well as an anode Elazari, “Our results show that pre-lithiated columnar structured a-Si can serve as promising anode in a Li-ion sulfur system.”, see Conclusion).
Jang and Elazari are analogous as they are both of the same field of silicon anodes.
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the anode as taught in Jang to be the silicon columnar anode as taught in Elazari in order to improve the performance of the cell.
Regarding Claim 17,
Modified Jang teaches The method of claim 16, further comprising, after the predetermined period, determining the SOC% of the anode electrode (Jang, see Fig. 2(b)).
Regarding Claim 20,
Modified Jang teaches the method of claim 16, wherein the predetermined period is in a range from 2 to 180 minutes at a temperature in a range from 25°C to 80°C (Jang, “b) Initial voltage profiles of SiOx anodes after 15 min of prelithiation in solutions at different temperatures. c) Effect of immersion time on initial CE and d) corresponding initial voltage profiles of SiOx anodes at 30 ° C”, see Fig. 2).
Claims 6 and 19 are rejected under 35 U.S.C. 103 as being unpatentable over ‘Molecularly Tailored Lithium–Arene Complex Enables Chemical Prelithiation of High-Capacity Lithium-Ion Battery Anodes’ hereinafter referred to as ‘Jang’ in view of ‘Rechargeable lithiated silicon–sulfur (SLS) battery prototypes’ hereinafter referred to as ‘Elazari’, as evidenced by ‘Lithium and oxygen engineered SiO0.5 materials for high performance lithium storage materials’ hereinafter referred to as ‘Kim’
Regarding Claim 6,
Modified Jang teaches the method of claim 1, wherein areal capacity of the pre-lithiation coating is in a range from greater than or equal to 0.5 mAh/cm2 to less than 15 mAh/cm2 (Jang, “For electrode fabrication, an aqueous slurry composed of SiOx (Hansol chemical, Korea), carbon black (Super-P, Timcal, Switzerland), and binder (AST-9005, Aekyung chemical Co., Ltd. Korea) with a mass ratio of 5:3:2 was mixed using a planetary centrifugal mixer (THINKY corporation, Japan). After casting the slurry on a Cu foil current collector, the electrodes were dried at 80°C for 1 h, roll-pressed, cut into a diameter of 11.3 mm (equal to 1.003 cm2 area)… The mass loading of the active materials on each electrode was 0.6±0.05 mg cm−2, except for the case of thick electrode experiment; 1.5±0.1 mg cm-2,”, see S1)(The examiner notes that the mass loading times the capacity of SiO0.5 is the areal capacity which is 0.0015 g/cm^-2*2093 2093 mA h g = 3.1395 mAh/cm2, which is within the claimed ranged, as evidenced by ‘Lithium and oxygen engineered SiO0.5 materials for high performance lithium storage materials’ hereinafter referred to as ‘Kim’ “Prelithiated Si-enriched SiO0.5 prepared by high-energy mechanical milling of Si and SiO with lithiation followed by LiH treatment, exhibited a capacity of 2093 mA h g−1” see Abstract).
Regarding Claim 19,
Modified Jang teaches the method of claim 18, wherein areal capacity of the pre-lithiation coating is in a range from greater than or equal to 0.5 mAh/cm2 to less than 15 mAh/cm2 (Jang, “For electrode fabrication, an aqueous slurry composed of SiOx (Hansol chemical, Korea), carbon black (Super-P, Timcal, Switzerland), and binder (AST-9005, Aekyung chemical Co., Ltd. Korea) with a mass ratio of 5:3:2 was mixed using a planetary centrifugal mixer (THINKY corporation, Japan). After casting the slurry on a Cu foil current collector, the electrodes were dried at 80°C for 1 h, roll-pressed, cut into a diameter of 11.3 mm (equal to 1.003 cm2 area)… The mass loading of the active materials on each electrode was 0.6±0.05 mg cm−2, except for the case of thick electrode experiment; 1.5±0.1 mg cm-2,”, see S1)(The examiner notes that the mass loading times the capacity of SiO0.5 is the areal capacity which is 0.0015 g/cm^-2*2093 2093 mA h g = 3.1395 mAh/cm2, which is within the claimed ranged which is within the claimed ranged, as evidenced by ‘Lithium and oxygen engineered SiO0.5 materials for high performance lithium storage materials’ hereinafter referred to as ‘Kim’ “Prelithiated Si-enriched SiO0.5 prepared by high-energy mechanical milling of Si and SiO with lithiation followed by LiH treatment, exhibited a capacity of 2093 mA h g−1” see Abstract).
Claims 9 is rejected under 35 U.S.C. 103 as being unpatentable over ‘Molecularly Tailored Lithium–Arene Complex Enables Chemical Prelithiation of High-Capacity Lithium-Ion Battery Anodes’ hereinafter referred to as ‘Jang’ in view of ‘Rechargeable lithiated silicon–sulfur (SLS) battery prototypes’ hereinafter referred to as ‘Elazari in further view of (US-20220223841-A1) hereinafter referred to as ‘Anstey’
Regarding Claim 9,
Modified Jang wherein at least one of the A anode electrodes, the C cathode electrodes, and the S separators comprises solid electrolyte.
Modified Jang does not teach wherein at least one of the A anode electrodes, the C cathode electrodes, and the S separators comprises solid electrolyte.
Anstey teaches wherein at least one of the A anode electrodes, the C cathode electrodes, and the S separators comprises solid electrolyte. (Anstey, “A solid electrolyte may be used without the separator because it serves as the separator itself. It is electrically insulating, ionically conductive, and electrochemically stable”, see [0090])
Anstey teaches that the solid electrolytes are insulating and conductive and stable (Anstey, “A solid electrolyte may be used without the separator because it serves as the separator itself. It is electrically insulating, ionically conductive, and electrochemically stable”, see [0090])
Jang and Ansari are analogous as they are both of the same field of battery cells.
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the electrolyte as taught in Jang to a solid electrolyte as taught in Anstey in order to improve the stability of the cell.
Claim 10 is rejected under 35 U.S.C. 103 as being unpatentable over ‘Molecularly Tailored Lithium–Arene Complex Enables Chemical Prelithiation of High-Capacity Lithium-Ion Battery Anodes’ hereinafter referred to as ‘Jang’ in view of ‘Rechargeable lithiated silicon–sulfur (SLS) battery prototypes’ hereinafter referred to as ‘Elazari in further view of (US-20230029191-A1) hereinafter referred to as ‘Ansari’
Regarding Claim 10,
Modified Jang teaches the method of claim 8, wherein at least one of the A anode electrodes, the C cathode electrodes, and the S separators comprises gel electrolyte.
Ansari teaches at least one of the A anode electrodes, the C cathode electrodes, and the S separators comprises gel electrolyte (Ansari, “The separator 103 may be wet or soaked with a liquid or gel electrolyte. In addition, in an example embodiment, the separator 103 does not melt below about 100 to 120° C., and exhibits sufficient mechanical properties for battery applications. A battery, in operation, can experience expansion and contraction of the anode and/or the cathode. In an example embodiment, the separator 103 can expand and contract by at least about 5 to 10% without failing, and may also be flexible.”, see [0021]).
Ansari teaches that gel electrolytes are flexible and ideal for expansion of the silicon anode (Ansari, “The separator 103 may be wet or soaked with a liquid or gel electrolyte. In addition, in an example embodiment, the separator 103 does not melt below about 100 to 120° C., and exhibits sufficient mechanical properties for battery applications. A battery, in operation, can experience expansion and contraction of the anode and/or the cathode. In an example embodiment, the separator 103 can expand and contract by at least about 5 to 10% without failing, and may also be flexible.”, see [0021]).
Jang and Ansari are analogous as they are both of the same field of battery cells.
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the electrolyte as taught in Jang to a gel electrolyte as taught in Ansari in order to improve the flexibility of the cell.
Claim 18 is rejected under 35 U.S.C. 103 as being unpatentable over ‘Molecularly Tailored Lithium–Arene Complex Enables Chemical Prelithiation of High-Capacity Lithium-Ion Battery Anodes’ hereinafter referred to as ‘Jang’ in view of ‘Rechargeable lithiated silicon–sulfur (SLS) battery prototypes’ hereinafter referred to as ‘Elazari’, in view of (US-20200219669-A1) hereinafter referred to as ‘Doi’
Regarding Claim 18,
Modified Jang does not teach arranging a lithium block in the solution and rotating a paddle in the solution during lithiation of the nonplanar silicon film wherein a rotational speed of the paddle is in a range from 5 to 1000 r/min.
Doi teaches a lithium block in the solution and rotating a paddle in the solution during lithiation of the anode film wherein a rotational speed of the paddle is in a range from 5 to 1000 r/min (Doi, “Inside a glove box (dew point: −80° C.), hard carbon serving as a negative electrode active material and an electrolyte solution were mixed, lithium metal powder was further added at room temperature, and the resultant product was kneaded for 20 hours at a speed of 30 to 60 rpm”, see [0171]).
Doi teaches that the mixing with the solution allowed for the homogenous pre-lithiation of the anode with the lithium metal material which reduces gas build up (Doi, “Through this kneading treatment, the lithium ion was pre-doped to the negative electrode active material and the lithium metal powder was eliminated (pre-doping step).”, see [0171])(Doi, “As a result of the investigations by the present inventors, it has been revealed that, by further pre-doping lithium in an amount exceeding the minimum lithium pre-doping amount necessary for compensating the irreversible capacity, the amount of gas generated at the time of initial charging after the electric device is configured can be reduced.”, see [0012]).
Modified Jang and Doi are analogous as they are both of the same field of anode treatments.
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the anode as taught in Jang to be treated with lithium at the rpm as taught in Doi in order to allow for lithium to interact with the anode and, in turn, decrease gas generation.
Conclusion
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/S.P.M./Examiner, Art Unit 1752
/NICHOLAS A SMITH/Supervisory Primary Examiner, Art Unit 1752
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