REDOX FLOW BATTERY SYSTEM

• US 20140178735A1
• Filed: 07/05/2012
• Published: 06/26/2014
• Est. Priority Date: 07/21/2011
• Status: Abandoned Application

• Current Assignee: National University of Singapore
• Original Assignee: National University of Singapore
• Inventors: Wang, Qing, Huang, Qizhao
• Application Number:
  US14/232,968
• Publication Number:
  US 20140178735A1
• Time in Patent Office: Days
• US Class Current: 429/105
• CPC Class Codes: H01M 8/188 by recharging of redox couples containing fluids; Redox flow type batteries
• CPC Class Codes: H01M 8/20 Indirect fuel cells, e.g. fuel cells with redox couple being irreversible H01M8/18 takes precedence
• CPC Class Codes: Y02E 60/50 Fuel cells

Abstract

A redox flow battery system having an electrochemical cell and an energy reservoir. The system includes a cathodic compartment, an anodic compartment, a separator that divides the two compartments, and an energy reservoir which contains an electro-active material, electro-active ions, an electrolyte, and a redox mediator. The reservoir is connected to either the cathodic compartment or the anodic compartment via an inlet-outlet pair for circulating the electrolyte from the energy reservoir to the cathodic compartment or the anodic compartment.

Claims

1. A redox flow battery system having an electrochemical cell, the system comprising:

a cathodic compartment having a cathodic electrode;

an anodic compartment having an anodic electrode;

an energy reservoir (i) containing an electro-active material that stores electro-active ions, an electrolyte that contains the electro-active ions, and a redox mediator that is present in the electrolyte, and (ii) connected to either the cathodic compartment or the anodic compartment via an outlet for delivering the electrolyte from the energy reservoir to the cathodic compartment or the anodic compartment, and also via an inlet for returning the electrolyte from the cathodic compartment or the anodic compartment to the reservoir; and

a separator that divides the cathodic compartment and the anodic compartment while allowing the electro-active ions to move therebetween.

2. The battery system of claim 1, wherein the electro-active ions are lithium ions, sodium ions, magnesium ions, aluminum ions, silver ions, copper ions, protons, fluoride ions, hydroxide ions, or a combination thereof.

3. The battery system of claim 2, wherein the energy reservoir is connected to the cathodic compartment, the electro-active material therein being a cathodic electro-active material and the redox mediator therein being a p-type redox mediator.

4. The battery system of claim 2, wherein the energy reservoir is connected to the anodic compartment, the electro-active material therein being an anodic electro-active material and the redox mediator therein being an n-type redox mediator.

5. The battery system of claim 2, wherein the electro-active ions are lithium ions.

6. The battery system of claim 5, wherein the energy reservoir is connected to the cathodic compartment, the electro-active material therein being a cathodic electro-active material and the redox mediator therein being a p-type redox mediator.

7. The battery system of claim 6, wherein

the cathodic electro-active material is a metal fluoride, a metal oxide, Li_1-x-zM_1-zPO₄, (Li_1-yZ_y)MPO₄, LiMO₂, LiM₂O₄, Li₂MSiO₄, LiMPO₄F, LiMSO₄F, Li₂MnO₃, sulfur, oxygen, or a combination thereof, in which M is Ti, V, Cr, Mn, Fe, Co, or Ni, Z is Ti, Zr, Nb, Al, or Mg, x is 0 to 1, y is 0 to 0.1, and z is −

0.5 to 0.5;

the electrolyte is a solution in which one or more lithium salts are dissolved in a polar protic solvent, an aprotic solvent, or a combination thereof;

the p-type redox mediator is a metallocene derivative, a triarylamine derivative, a phenothiazine derivative, a phenoxazine derivative, a carbazole derivative, a transition metal complex, an aromatic derivative, a nitroxide radical, a disulfide, or a combination is thereof; and

the separator is a lithium ion conducting membrane.

8. The battery system of claim 7, wherein

the cathodic electro-active material is LiFePO₄, LiMnPO₄, LiVPO₄F, LiFeSO₄F, LiNi_0.5Mn_0.5O₂, LiCo_1/3Ni_1/3Mn_1/3O₂, LiMn₂O₄, LiNi_0.5Mn_1.5O₄, or a combination thereof;

the electrolyte is a solution in which LiClO₄, LiPF₆, LiBF₄, LiSbF₆, LiCF₃SO₃, LiN(SO₂CF₃)₂, LiN(SO₂C₂F₅)₂, LiN(SO₂F)₂, LiC(SO₂CF₃)₃, Li[N(SO₂C₄F₉)(SO₂F)], LiAIO₄, LiAlCl₄, LiCl, LiI, lithium bis(oxalato)borate, or a combination thereof is dissolved in water, a carbonate, an ether, an ester, a ketone, a nitrile, or a combination thereof;

the p-type redox mediator is a metallocene derivative; and

the separator is a lithium phosphorus oxynitride glass, a lithium thiophosphate glass, a NASICON-type lithium conducting glass ceramic, a Garnet-type lithium conducting glass ceramic, a ceramic nanofiltration membrane, a lithium ion-exchange membrane, or a combination thereof.

9. The battery system of claim 5, wherein the energy reservoir is connected to the anodic compartment, the electro-active material therein being an anodic electro-active material and the redox mediator therein being an n-type redox mediator.

10. The battery system of claim 9, wherein

the anodic electro-active material is a carbonaceous material, a lithium titanate, a metal oxide, a metal, a metal alloy, a metalloid, a metalloid alloy, a conjugated dicarboxylate, or a combination thereof;

the electrolyte is a solution in which one or more lithium salts are dissolved in a io polar protic solvent, an aprotic solvent, or a combination thereof;

the n-type redox mediator is a transition metal derivative, an aryl derivative, a conjugated carboxylate derivative, a rare earth metal cation, or a combination thereof; and

the separator is a lithium ion conducting membrane, provided that when the anodic electro-active material contains a lithium metal, the electrolyte is a solution in which one or more lithium salts are dissolved in an aprotic organic solvent.

11. The battery system of claim 10, wherein

the anodic electro-active material is Li₄Ti₅O₁₂, TiO₂, Si, Al, Sn, Sb, a carbonaceous material, or a combination thereof;

the electrolyte is a solution in which LiClO₄, LiPF₆, LiBF₄, LiSbF₆, LiCF₃SO₃, LiN(SO₂CF₃)₂, LiN(SO₂C₂F₅)₂, LiN(SO₂F)₂, LiC(SO₂CF₃)₃, Li[N(SO₂C₄F₉)(SO₂F)], LiAlO₄, LiAlCl₄, LiCI, LiI, lithium bis(oxalato)borate, or a combination thereof is dissolved in water, a carbonate, an ether, an ester, a ketone, a nitrile, or a combination thereof;

the n-type redox mediator is a transition metal derivative, an aryl derivative, or a combination thereof; and

the separator is a lithium phosphorus oxynitride glass, a lithium thiophosphate glass, a NASICON-type lithium conducting glass ceramic, a Garnet-type lithium conducting glass ceramic, a ceramic nanofiltration membrane, a lithium ion-exchange membrane, or a combination thereof.

12. The battery system of claim 1, wherein the cathodic electrode, is a carbon, a metal, or a combination thereof;

and the anodic electrode is a carbon, a metal, or a combination thereof.

13. The battery system of claim 12, wherein

the energy reservoir is connected to the cathodic compartment;

the electro-active material therein is a metal fluoride, a metal oxide, Li_1-x-zM_1-zPO₄, (Li_1-yZ_y)MPO₄, LiMO₂, LiM₂O₄, Li₂MSiO₄, LiMPO₄F, LiMSO₄F, Li₂MnO₃, sulfur, oxygen, or a combination thereof;

in which M is Ti, V, Cr, Mn, Fe, Co, or Ni, Z is Ti, Zr, Nb, Al, or Mg, x is 0 to 1, y is 0 to 0.1, and z is −

0.5 to 0.5;

the electrolyte is a solution in which one or more lithium salts are dissolved in a polar protic solvent, an aprotic solvent, or a combination thereof; and

the redox mediator therein is a p-type redox mediator.

14. The battery system of claim 12, wherein

the energy reservoir is connected to the anodic compartment;

the electro-active material therein is a carbonaceous material, a lithium titanate, a metal oxide, a conjugated dicarboxylate, a metal, a metal alloy, a metalloid, a metalloid alloy, a lithium metal, or a combination thereof;

the electrolyte is a solution in which one or more lithium salts dissolved in a polar protic solvent, an aprotic solvent, or a combination thereof; and

the redox mediator therein is an n-type redox mediator, provided that when the anodic electro-active material contains a lithium metal, the electrolyte is a solution in which one or more lithium salts are dissolved in an aprotic organic solvent.

15. The battery system of claim 1, further comprising a second energy reservoir, wherein

one of the two energy reservoirs is connected to the cathodic compartment, in which the electro-active material is a cathodic electro-active material and the redox mediator is a p-type redox mediator;

and

the other energy reservoir is connected to the anodic compartment, in which the electro-active material is an anodic electro-active material and the redox mediator is an n-type redox mediator.

16. The battery system of claim 15, wherein the electro-active ions are lithium ions, sodium ions, magnesium ions, aluminum ions, silver ions, copper ions, protons, fluoride ions, hydroxide ions, or a combination thereof.

17. The battery system of claim 16, wherein the electro-active ions are lithium ions.

18. The battery system of claim 17, wherein

the cathodic electro-active material is a metal fluoride, a metal oxide, Li_1-x-zM_1-zPO₄, (Li_1-yZ_y)MPO₄, LiMO₂, LiM₂O₄, Li₂MSiO₄, LiMPO₄F, LiMSO₄F, Li₂MnO₃, sulfur, oxygen, or a combination thereof, in which M is Ti, V, Cr, Mn, Fe, Co, or Ni, Z is Ti, Zr, Nb, Al, or Mg, x is 0 to 1, y is 0 to 0.1, and z is −

0.5 to 0.5;

the anodic electro-active material is a carbonaceous material, a lithium titanate, a metal oxide, a conjugated dicarboxylate, a metal, a metal alloy, a metalloid, a metalloid alloy, or a combination thereof;

the electrolyte is a solution in which one or more lithium salts are dissolved in a polar protic solvent, an aprotic solvent, or a combination thereof;

the p-type redox mediator is a metallocene derivative, a triarylamine derivative, a phenothiazine derivative, a phenoxazine derivative, a carbazole derivative, a transition metal complex, an aromatic derivative, a nitroxide radical, a disulfide, or a combination thereof;

the n-type redox mediator is a transition metal derivative, an aryl derivative, a conjugated carboxylate derivative, a rare earth metal cation, or a combination thereof; and

the separator is a lithium ion conducting membrane, provided that when the anodic electro-active material contains a lithium metal, the electrolyte is a solution in which one or more lithium salts are dissolved in an aprotic organic solvent.

19. The battery system of claim 18, wherein

the cathodic electro-active material is LiFePO₄, LiMnPO₄, LiVPO₄F, LiFeSO₄F, LiNi_0.5Mn_0.5O₂, LiCo_1/3Ni _1/3M1/3O₂, LiMn₂O₄, LiNi_0.5Mn_1.5O₄, or a combination thereof;

the anodic electro-active material is Li₄Ti₅O₁₂, TiO₂, Si, Al, Sn, Sb, a carbonaceous material, or a combination thereof;

the electrolyte is a solution in which LiClO₄, LiPF₆, LiBF₄, LiSbF₆, LiCF₃SO₃, LiN(SO₂CF₃)₂, LiN(SO₂C₂F₅)₂, LiN(SO₂F)₂, LiC(SO₂CF₃)₃, Li[N(SO₂C₄F₉)(SO₂F)], LiAlO₄, LiAlCL₄, LiCl, LiI, lithium bis(oxalato)borate, or a combination thereof is dissolved in water, a carbonate, an ether, an ester, a ketone, a nitrile, or a combination thereof;

the p-type redox mediator is a metallocene derivative;

the n-type redox mediator is a transition metal derivative, an aryl derivative, or a combination thereof; and

the separator is a lithium phosphorus oxynitride glass, a lithium thiophosphate glass, a NASICON-type lithium conducting glass ceramic, a Garnet-type lithium conducting glass ceramic, a ceramic nanofiltration membrane, a lithium ion-exchange membrane, or a combination thereof.

20. The battery system of claim 17, wherein the cathodic electrode is a carbon, a metal, or a combination thereof;

and the anodic electrode is a carbon, a metal, or a combination thereof.

21. The battery system of claim 20, wherein

the cathodic electro-active material is a metal fluoride, a metal oxide, Li_1-x-zM_1-zPO₄, (Li_1-yZ_y)MPO₄, LiMO₂, LiM₂O₄, Li₂MSiO₄, LiMPO₄F, LiMSO₄F, Li₂MnO₃, sulfur, oxygen, or a combination thereof, in which M is Ti, V, Cr, Mn, Fe, Co, or Ni, Z is Ti, Zr, Nb, Al, or Mg, x is 0 to 1,y is 0 to 0.1, and z is −

0.5 to 0.5;

the anodic electro-active material is a carbonaceous material, a lithium titanate, a metal oxide, a conjugated dicarboxylate, a metal, a metal alloy, a metalloid, a metalloid alloy, or a combination thereof;

the electrolyte is a solution in which one or more lithium salts are dissolved in a polar protic solvent, an aprotic solvent, or a combination thereof;

the p-type redox mediator is a metallocene derivative, a triarylamine derivative, a phenothiazine derivative, a phenoxazine derivative, a carbazole derivative, a transition metal complex, an aromatic derivative, a nitroxide radical, a disulfide, or a combination thereof;

the n-type redox mediator is a transition metal derivative, an aryl derivative, a conjugated carboxylate derivative, a rare earth metal cation, or a combination thereof; and

the separator is a lithium ion conducting membrane, provided that when the anodic electro-active material contains a lithium metal, the electrolyte is a solution in which one or more lithium salts are dissolved in an aprotic o organic solvent.

22. The battery system of claim 21, wherein

the cathodic electro-active material is LiFePO₄, LiMnPO₄, LiVPO₄F, LiFeSO₄F, LiNi_0.5Mn_0.5O₂, LiCo_1/3Ni_1/3Mn_1/3O₂, LiMn₂O₄, LiNi_0.5Mn_1.5O₄, or a combination thereof;

the anodic electro-active material is Li₄Ti₅O₁₂, TiO₂, Si, Al, Sn, Sb, a carbonaceous material, or a combination thereof;

the electrolyte is a solution in which LiClO₄, LiPF₆, LiBF₄, LiSbF₆, LiCF₃SO₃, LiN(SO₂CF₃)₂, LiN(SO₂C₂F₅)₂, LiN(SO₂F)₂, LiC(SO₂CF₃)₃, Li[N(SO₂C₄F₉)(SO₂F)], LiAlO₄, LiAlCl₄, LiCI, LiI, lithium bis(oxalato)borate, or a combination thereof is dissolved in water, a carbonate, an ether, an ester, a ketone, a nitrile, or a combination thereof;

the p-type redox mediator is a metallocene derivative;

the n-type redox mediator is a transition metal derivative, an aryl derivative, or a combination thereof; and

the separator is a lithium phosphorus oxynitride glass, a lithium thiophosphate glass, a NASICON-type lithium conducting glass ceramic, a Garnet-type lithium conducting glass ceramic, a ceramic nanofiltration membrane, a lithium ion-exchange membrane, or a combination thereof.

23. The battery system of claim 1, wherein the battery system has a plurality of electrochemical cells, the cathodic electrode is connected to one or more other cells or to an external load, and the anodic electrode is connected to one or more other cells or to an external load.