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 § 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.
Claim 15 is rejected under 35 U.S.C. 112(b) as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor regards as the invention.
Claim 15 recites the limitation of “the volume ratio between anolyte: LM”. There is insufficient basis for “the volume ratio” and “LM”. For purposes of compact prosecution, the examiner interprets this limitation to recite “a volume ratio between anolyte: liquid eutectic alloys” in this Office Action. Claim 15 must be amended to withdraw this rejection.
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 is incorrect, any correction of the statutory basis 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 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 1-11, 13-14 and 16-17 are rejected under 35 U.S.C. 103 as being unpatentable over Li et al (WO 2018103517 A1) in view of Teixeira et al (US 2024/0372112 Al). These prior art references being cited to as Li and Teixeira, respectively, hereinafter in this Office Action.
Regarding claim 1, Li discloses a dendrite-free zinc-based flow battery with high areal capacity (“an alkaline zinc-iron flow battery” [0007], “The battery includes a battery module composed of one single cell or two or more single cells in series/parallel” [0008]), comprising:
an anode integrated with a first collector (“Single cells are assembled in the following order … negative electrode 6x8 cm Carbon felt, graphite current collector, negative electrode plate” [0050]);
a cathode integrated with a second collector (“Single cells are assembled in the following order … positive end plate, graphite current collector, positive electrode 6x8cm Carbon felt” [0050]);
a first storage tank comprising catholyte (“a storage tank containing cathode and anode electrolytes” [0008] with italics added for emphasis on the element corresponding to the recited limitation);
a first pump connects the cathode and the first storage tank (“a circulation pump” [0008] where “The circulation pump is used to circulate the electrolyte through the electrochemical reaction zones of the positive and negative half-cells” [0009] and “The positive and negative electrolyte storage tanks are connected by a liquid delivery pump through pipelines to the cathode and anode inlets and outlets of single cells or stacks” [0019]);
a second storage tank comprising anolyte (“a storage tank containing cathode and anode electrolytes” [0008] with italics added for emphasis on the element corresponding to the recited limitation);
a second pump connects the anode and the second storage tank (“a circulation pump” [0008] where “The circulation pump is used to circulate the electrolyte through the electrochemical reaction zones of the positive and negative half-cells” [0009] and “The positive and negative electrolyte storage tanks are connected by a liquid delivery pump through pipelines to the cathode and anode inlets and outlets of single cells or stacks” [0019]);
a separator to prevent direct contact between the anolyte and the catholyte (“ion conduction membrane is used to block the electrolyte of the positive and negative electrodes, preventing short circuits and the formation of an internal loop for ion transfer” [0009]),
wherein the catholyte flows through the battery driven by the first pump, and the anolyte flows through the battery driven by the second pump (“The positive and negative electrolyte storage tanks are connected by a liquid delivery pump through pipelines to the cathode and anode inlets and outlets of single cells or stacks.” [0019] and “When charging a single cell or stack, the electrolyte is transported by pump from the positive and negative storage tanks to the positive and negative electrodes, respectively.” [0022]),
wherein the dendrite-free zinc-based flow battery demonstrates an areal capacity of at least 600 mAh cm-2 at a current density of at least 40 mA cm-2 (“Single cells are assembled” [0050] and “a capacity of 60mA/cm2 Charge for 30 minutes undercurrent density conditions, then cut off voltage at 60mA/cm2 Under current density conditions, discharge to 0V … the battery's discharge specific capacity approaches 25Ah/L, while the discharge specific energy approaches 40Wh/L (Figure 7d)” [0062] with italics added for emphasis, which an areal capacity of at least 600 mAh/cm2 is attainable by constructing the battery to be comprised of more than one single cell as previously disclosed “The battery includes a battery module composed of one single cell or two or more single cells in series/parallel” [0008] such that the battery is at a length of at least 24 cm and which MPEP 2144.04 Section IV Part A discloses “where the only difference between the prior art and the claims was a recitation of relative dimensions of the claimed device and a device having the claimed relative dimensions would not perform differently than the prior art device, the claimed device was not patentably distinct from the prior art device”).
Li does not disclose the second storage tank comprising liquid eutectic alloys, and wherein the liquid eutectic alloys flows through the battery driven by the second pump.
However, Teixeira discloses a dendrite-free zinc-based flow battery with high areal capacity (“gallium LMAB (Liquid Metal-Air Battery) disclosed herein” [0015] and “a flow battery device suitable for use with low ambient temperature, rechargeable operation as disclosed herein. Referring to FIG. 1, a metal-air battery 100” [0016]), comprising: an anode (“a negative electrode” [0016]), a cathode (“a positive electrode” [0016]), a first storage tank comprising catholyte (“The electrolyte at the negative (negolyte) electrode 121, and positive (posolyte) electrode 111 may each be stored individually in respective tanks 122, 132” [0017]), a second storage tank comprising anolyte (“The electrolyte at the negative (negolyte) electrode 121, and positive (posolyte) electrode 111 may each be stored individually in respective tanks 122, 132” [0017] ), and a separator to prevent direct contact between the anolyte and the catholyte (“A separator 135 between the posolyte 130 and the negolyte 140” [0021]).
Teixeira teaches the second storage tank comprising liquid eutectic alloys (“The liquid metal electrode 120 also communicates with a reservoir 152. In the disclosed approach, gallium was chosen … Alternate configurations may employ other suitable ambient temperature liquid metal eutectics, such as binary or ternary eutectics of Ga with In, Sn, Zn, Cd, Bi, etc.” [0018] with italics added for emphasis), and that adding liquid eutectic alloys to the second storage tank containing the anolyte quells corrosion that is caused by a hydrogen evolution reaction ([0018]).
Therefore, it would have been obvious for a person having ordinary skill in the art to add liquid eutectic alloys to the second storage tank that comprises the anolyte of Li in view of Teixeira, and inherently by the disclosed features constituent of the battery of Li, wherein the liquid eutectic alloys flows through the battery driven by the second pump, in order to achieve an anolyte mixture that prevents corrosion in at least the anolyte side of the battery.
Regarding claim 2, modified Li discloses the dendrite-free zinc-based flow battery with all of the features set forth in claim 1, and wherein the anode comprises a carbon felt (Li “negative electrode 6x8 cm2 Carbon felt” [0050]), or a carbon felt with zinc plate or zinc foil added.
Regarding claim 3, modified Li discloses the dendrite-free zinc-based flow battery with all of the features set forth in claim 1, and wherein the anolyte comprises zinc salts and supporting electrolytes salts with a concentration of 0.5 to 3 mol L-1 (Li “the corresponding anode electrolyte is 0.5 mol/L Zn(OH)4-2” [0062]).
Regarding claim 4, modified Li discloses the dendrite-free zinc-based flow battery with all of the features set forth in claim 3, and wherein the zinc salts comprise ZnBr2, ZnCl2 (Li “the zinc salt is zinc chloride” [0016]), and ZnI2, or a combination thereof.
Regarding claim 5, modified Li discloses the dendrite-free zinc-based flow battery with all of the features set forth in claim 1, and wherein the cathode comprises carbon felt (Li “positive electrode 6x8cm Carbon felt” [0050]), or a carbon felt absorbed with the catholyte.
Regarding claim 6, modified Li discloses the dendrite-free zinc-based flow battery with all of the features set forth in claim 1, and wherein the catholyte comprises one or more Cl0/ Cl−, Br2/ Br−,I0/ I−, Fe3+/ Fe2+ (Li “The active substance in the cathode electrolyte is ferrocyanide (Fe(CN)3-)” [0015]) salts and supporting electrolytes salts with a concentration of 0.5 to 3 mol L-1 (Li “the concentration of cathode active material was increased to 1 mol/L” [0062]).
Regarding claim 7, modified Li discloses the dendrite-free zinc-based flow battery with all of the features set forth in claim 6, and wherein the supporting electrolytes salts comprise NaCl, KCl and NH4Cl, or a combination thereof (Li “A certain amount of auxiliary electrolyte (auxiliary electrolyte concentration is 0.1~6 mol/L, preferably 2~4 mol/L) can also be added to the above electrolyte solution, such as potassium chloride (KCl) or sodium sulfate (Na)2SO4, sodium chloride (NaCl),potassium sulfate (K2SO4)” [0018]).
Regarding claim 8, modified Li discloses the dendrite-free zinc-based flow battery with all of the features set forth in claim 1, and wherein the liquid eutectic alloys comprise room-temperature liquid metals based on gallium or mercury (Teixeira “The liquid metal electrode 120 also communicates with a reservoir 152. In the disclosed approach, gallium was chosen” [0018]).
Regarding claim 9, modified Li discloses the dendrite-free zinc-based flow battery with all of the features set forth in claim 8, and wherein gallium-based room-temperature liquid metals comprise EGaInSnZn alloys, and the EGaInSnZn alloys are capable of returning to EGaInSn alloys after discharge (Teixeira “ambient temperature liquid metal eutectics, such as binary or ternary eutectics of Ga with In, Sn, Zn” [0018], “The containment 102 is also configured for a reversible oxidation/reduction reaction between the electrode and the opposed electrode for recharge, also involving switching the electrodes 111 and 121 for a reverse current flow” [0019] and “The eutectics discussed above, often mixes of Ga—In—Sn” [0022]).
Regarding claim 10, modified Li discloses the dendrite-free zinc-based flow battery with all of the features set forth in claim 9, and the EGaInSnZn alloys exhibit the characteristic broad peak at around 35° (this limitation is known in the art to be a property inherent to the eutectic Ga—In—Sn—Zn alloy).
Regarding claim 11, modified Li discloses the dendrite-free zinc-based flow battery with all of the features set forth in claim 9, and herein the EGaInSnZn alloys comprises 50-80 wt% gallium, 10-30 wt% indium, 5-20 wt% tin and 1-10 wt% zinc (this limitation is known in the art to a composition inherent of the eutectic Ga—In—Sn—Zn alloy).
Regarding claim 13, modified Li discloses the dendrite-free zinc-based flow battery with all of the features set forth in claim 1 above, and wherein the first collector or the second collector comprises graphite plate (Li “graphite current collector” [0050]), carbon plastic composite plate or titanium plate.
Regarding claim 14, modified Li discloses the dendrite-free zinc-based flow battery with all of the features set forth in claim 1 above, and wherein the dendrite-free zinc-based flow battery exhibits at least 95% of coulombic efficiency, at least 84% of energy efficiency even if the areal capacity is increased up to 640 mAh cm−2 (Li “Experiments show that alkaline zinc-iron flow batteries assembled with PBI ion exchange membranes are 120mA/cm2 Under current density conditions (Figure 6a), the cell's CE remained above 99%, EE above 82%, and VE above 83%, demonstrating excellent rate performance” [0061] where Fig. 6d shows constant efficiency and capacity rates over time such that current density and time do not affect the efficiencies of the battery).
Regarding claim 16, modified Li discloses the dendrite-free zinc-based flow battery with all of the features set forth in claim 1 above, and wherein the dendrite-free zinc-based flow battery maintains a cycle life of at least 110 days even at an areal capacity of 120 mAh cm−2 (Li “120mA/cm2 Charge for 8 minutes under current density conditions, then cut off voltage at 120mA/cm2 Under current density conditions, discharge to 0V.” [0042], referring to Fig. 6(d) .
Regarding claim 17, modified Li discloses the dendrite-free zinc-based flow battery with all of the features set forth in claim 1 above, and wherein the dendrite-free zinc-based flow battery displays a stable charging/discharging performance for over 4000 hours (Li “After more than 135 hours of charge-discharge cycles, the initial discharge voltage remains around 1.9V (Figure 7b), indicating that under high concentrations of active materials, the internal ohmic polarization of the battery does not change significantly. After more than 150 cycles, the battery's CE remained above 99%, and both VE and EE remained above 91% (Figure 7c), demonstrating excellent battery performance and cycle stability.” [0062] where Fig. 7d shows that the discharge capacity essentially remains at a constant over time).
Claim 12 is rejected under 35 U.S.C. 103 as being unpatentable over Li et al (WO 2018103517 A1) in view of Teixeira et al (US 2024/0372112 Al) and Wu et al (CN 117039084 A). The latter prior art reference being cited to as Wu hereinafter in this Office Action.
Regarding claim 12, modified Li discloses the dendrite-free zinc-based flow battery with all of the features set forth in claim 1 above, and wherein the separator comprises porous membrane or an ion exchange membrane (Li “ion conduction membrane” [0009]).
Modified Li does not disclose wherein the separator comprising an ion exchange membrane has a thickness of 10 to 200 µm.
However, Wu discloses a zinc-based flow battery (“neutral zinc-iron flow batteries” [n0005]) that comprises an anode (“the negative electrode” [n0005]), a cathode (“the positive electrode” [n0005]), and a separator to prevent contact between the respective electrolytes of each the anode and the cathode (“The flow battery also includes a separator. … The separator is prepared using any of the above-mentioned composite membranes” [n0015] and “The composite membrane is used to separate the positive and negative electrolytes” [n0044]).
Wu teaches wherein the separator comprising an ion exchange membrane has a thickness of 10 to 200 µm (“the composite membrane comprising an ion exchange membrane, wherein a coating is bonded to one side of the ion exchange membrane, the coating being composed of a polymer and carbon black” [n0006], “the thickness of the ion exchange membrane is 40 μm to 200 μm” [n0007], and “the thickness of the coating is 1μm to 30μm” [n0008], which teaches a total composite membrane thickness range of 41 μm to 230 μm and is a range that overlaps with the claimed thickness range that MPEP 2144.05 Section I states “In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists.”).
Wu further teaches that the ion exchange membrane of the separator of this thickness range is designed to prevent the migration of hydrated ions, reduce cross-contamination of cathode and anode active materials, and improve the cycle stability and capacity retention of the zinc-based battery ([n0022]).
Therefore, it would have been obvious for a person having ordinary skill in the art to replace the separator of modified Li in view of Wu, wherein the separator comprising the ion exchange membrane has a thickness of 10 to 200 µm, in order to achieve a zinc-based battery with improved cycle stability and capacity retention by preventing hydrated ion migration across the separator and reduce cross-contamination of the anode and cathode active materials.
Claim 15 is rejected under 35 U.S.C. 103 as being unpatentable over Li et al (WO 2018103517 A1) in view of Teixeira et al (US 2024/0372112 Al) and Lertanantawong et al (“Chemical reactivity of Ga-based liquid metals with redox active species and its influence on electrochemical processes”; Electrochemistry Communications journal; 2018). The latter prior art reference being cited to as Lertanantawong hereinafter in this Office Action.
Regarding claim 15, modified Li discloses the dendrite-free zinc-based flow battery with all of the features set forth in claim 1 above, but does not disclose wherein the volume ratio between anolyte: LM is in a range of 5 to 20.
However, Lertanantawong discloses a tank (“a liquid drop of galinstan was immersed in the [Ru(NH3)6]3+ solution” p. 16 last paragraph of righthand column, and “a typical inner sphere or surface sensitive electron transfer process was also investigated, namely ferricyanide reduction” p. 16 first paragraph of righthand column) comprising an anolyte (“[Ru(NH3)6]3+” and “ferricyanide” p. 16 righthand column) and liquid eutectic alloys (“galinstan” p. 16).
Lertanantawong teaches wherein the volume ratio between anolyte: LM is in a range of 5 to 20 (“For the studies involving the long-term interaction of galinstan with the redox active species a galinstan drop of 450 mg was used in a total volume of 1 ml.” p. 16 second paragraph of lefthand column, which is equivalent to a corresponding anolyte:LM ratio of 7:1 and is within the claimed ratio range of 5 to 20).
Lertanantawong further teaches that this concentration of the liquid eutectic alloy in the anolyte is sufficient to reduce the anolyte due to a significant driving force for the gallium component of the liquid eutectic alloy, and is a stable way of reducing the anolyte to its one-electron reduced product (p. 16 second paragraph of righthand column).
Therefore, it would have been obvious for a person having ordinary skill in the art to add a volume ratio to the second storage tank of modified Li in view of Lertanantawong, wherein the volume ratio between anolyte: LM is in a range of 5 to 20, in order to achieve a means of controlling and improving the reduction of the anolyte, which is essential to the discharge process of the flow battery of Li (Li [0022]).
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to CHARLENE BERMUDEZ whose telephone number is (571)272-0610. The examiner can normally be reached Mondays through Thursdays generally from 12 PM to 5 PM Eastern Time.
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/CHARLENE BERMUDEZ/Examiner, Art Unit 1721
/ALLISON BOURKE/Supervisory Patent Examiner, Art Unit 1721
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