# US 12,183,876 B2 · High-voltage ion-mediated flow/flow-assist manganese dioxide-zinc battery > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,183,876 B2 - Document ID: US12183876B2 - Status: Granted - Kind: B2 - Application number: 17/251,690 - Filed: 2019-06-13 - Published: 2021-09-09 - Granted: 2024-12-31 - Earliest claimed: 2018-06-14 - Assignees: Research Foundation of the City University of New York - Applicants: Research Foundation of the City University of New York - Inventors: Gautam G. Yadav; Jinchao Huang; Damon Turney; Michael Nyce; Alexander Couzis; Valerio Deangelis; Sanjoy Banerjee; Xia Wei - Web page: https://patentgrep.com/patent/US12183876B2 ## CPC - H01M 8/0234: Carbonaceous material - H01M 10/054: Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium - H01M 4/0404: {by coating on electrode collectors} - H01M 4/663: {containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres} - H01M 4/74: Meshes or woven material; Expanded metal - H01M 8/04186: of liquid-charged or electrolyte-charged reactants - H01M 8/188: {by recharging of redox couples containing fluids; Redox flow type batteries} - H01M 10/0563: Liquid materials, e.g. for Li-SOCl2 cells - Y02E 60/10: Energy storage using batteries - Y02E 60/50: Fuel cells - Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product - H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY - Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION - Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS ## Abstract A battery includes a cathode compartment, a catholyte solution disposed within the cathode compartment, an anode compartment, an anolyte solution disposed within the anode compartment, a separator disposed between the cathode compartment and the anode compartment, and a flow system configured to provide fluid circulation in the cathode compartment and the anode compartment. The catholyte solution and the anolyte solution have different compositions. ## Claims ### Claim 1 A method of operating a battery, the method comprising: circulating a catholyte solution within a cathode compartment of a battery, wherein the battery comprises a cathode current collector within the cathode compartment having manganese dioxide plated thereon, wherein the catholyte solution comprises manganese ions; circulating an anolyte solution within an anode compartment of the battery, wherein the battery comprises an anode current collector within the anode compartment having zinc plated thereon, wherein the anolyte solution comprises zinc ions, and wherein the catholyte solution and the anolyte solution have different compositions, and wherein the pH of the catholyte solution is less than the pH of the anolyte solution; preventing direct mixing between the anolyte and the catholyte during the circulating by using a separator disposed between the cathode compartment and the anode compartment; and generating an electrical current from the battery while circulating the catholyte solution and circulating the anolyte solution. ### Claim 2 (depends on 1) The method as recited in claim 1, wherein the catholyte solution has a temperature between 0° C. and 200° C. ### Claim 3 (depends on 1) The method as recited in claim 1, wherein the anolyte solution has a temperature between 0° C. and 200° C. ### Claim 4 (depends on 1) The method as recited in claim 1, further comprising: dissolving the manganese dioxide from the cathode current collector within the cathode compartment during the generating of the electrical current; and dissolving the zinc from the anode current collector within the anode compartment during the generating of the electrical current. ### Claim 5 (depends on 4) The method as recited in claim 4, wherein the manganese dioxide is α, β, γ, λ, ε, δ, electrolytic manganese dioxide, pyrolusite, birnessite, ramsdellite, hollandite, romanechite, todorokite, lithiophorite, chalcophanite, sodium or potassium rich birnessite, cryptomelane, buserite, manganese oxide, a spinel form of manganese dioxide. ### Claim 6 (depends on 5) The method as recited in claim 5, wherein the spinel form of manganese dioxide is hausmannite (Mn3O4), LiMn2O4, CuMn2O4, ZnMn2O4, or combinations thereof. ### Claim 7 (depends on 1) The method as recited in claim 1, further comprising; ceasing the generating of the electrical current; applying a voltage between the cathode current collector within the cathode compartment and the anode current collector within the anode compartment; electroplating the zinc onto the anode current collector in response to applying the voltage; and electroplating the manganese dioxide onto the cathode current collector in response to applying the voltage. ### Claim 8 (depends on 1) The method as recited in claim 1, wherein generating the electrical current comprises generating an electrical current at a voltage between 0 and 3.5V. ### Claim 9 (depends on 1) The method as recited in claim 1, wherein the generating the electrical current uses between 0-100% of the theoretical capacity of the manganese dioxide. ### Claim 10 (depends on 1) The method as recited in claim 1, wherein the generating the electrical current uses between 0-100% of the theoretical capacity of Zn. ### Claim 11 (depends on 1) The method as recited in claim 1, further comprising: recharging the battery a plurality of times after generating the electrical current. ### Claim 12 (depends on 1) The method as recited in claim 1, wherein the anode current collector, the cathode current collector, or both comprise at least one material comprising: carbon, lead, copper, nickel, bismuth, titanium, magnesium, aluminum, silver, or combinations thereof. ### Claim 13 (depends on 12) The method as recited in claim 12, wherein at least one of the cathode current collector or the anode current collector comprises carbon, and wherein the carbon is graphite, carbon fiber, carbon black, acetylene black, single walled carbon nanotubes, multi-walled carbon nanotubes, graphene, graphyne, graphene oxide, nitrogen-doped carbon, or combinations thereof. ### Claim 14 (depends on 12) The method as recited in claim 12, wherein the anode current collector, the cathode current collector, or both are in the form of a mesh, foil, foam, fibrous, a porous block architecture, an aerogel, or a combination thereof. ### Claim 15 (depends on 1) The method as recited in claim 1, wherein the catholyte solution in the cathode compartment contains a mixed solution comprising at least one of manganese sulfate, manganese chloride, manganese nitrate, manganese perchlorate, manganese acetate, manganese bis(trifluoromethanesulfonate), manganese triflate, manganese carbonate, manganese oxalate, manganese fluorosilicate, manganese ferrocyanide, manganese bromide, nitric acid, sulfuric acid, hydrochloric acid, sodium sulfate, potassium sulfate, sodium hydroxide, potassium hydroxide, potassium permanganate, titanium sulfate, titanium chloride, lithium nitrate, lithium chloride, lithium bromide, lithium bicarbonate, lithium acetate, lithium sulfate, lithium permanganate, lithium nitrate, lithium nitrite, lithium hydroxide, lithium perchlorate, lithium oxalate, lithium fluoride, lithium carbonate, lithium bromate, or any combination thereof. ### Claim 16 (depends on 1) The method as recited in claim 1, wherein the anolyte solution in the anode compartment is a mixed solution comprising at least one of zinc sulfate, zinc triflate, zinc chloride, zinc acetate, zinc carbonate, zinc chlorate, zinc fluoride, zinc formate, zinc nitrate, zinc oxalate, zinc sulfite, zinc tartrate, zinc cyanide, zinc oxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium chloride, sodium chloride, potassium fluoride, lithium nitrate, lithium chloride, lithium bromide, lithium bicarbonate, lithium acetate, lithium sulfate, lithium permanganate, lithium nitrate, lithium nitrite, lithium perchlorate, lithium oxalate, lithium fluoride, lithium carbonate, lithium bromate or combinations thereof. ### Claim 17 (depends on 1) The method as recited in claim 1, wherein the separator is lithium super ionic conductor (LISICON), sodium super ionic conductions (NASICON), Nafion, a bipolar membrane, water electrolysis membrane, a composite of polyvinyl alcohol and graphene oxide, Celgard, cellophane or combinations thereof. ### Claim 18 (depends on 1) The method as recited in claim 1, further comprising: circulating the anolyte solution between the anode compartment and an anolyte vessel, wherein the anolyte vessel is external to the anode compartment. ### Claim 19 (depends on 1) The method as recited in claim 1, further comprising: circulating the catholyte solution between the cathode compartment and a catholyte vessel, wherein the catholyte vessel is external to the cathode compartment. ### Claim 20 (depends on 1) The method as recited in claim 1, wherein the catholyte solution has a pH between 0 and 7. ### Claim 21 (depends on 1) The method as recited in claim 1, wherein the anolyte solution has a pH between 0 and 15.13. ### Claim 22 (depends on 1) The method as recited in claim 1, wherein the anolyte solution is basic, and wherein the catholyte solution is acidic.