ELECTRODE MATERIALS FOR RECHARGEABLE ZINC CELLS AND BATTERIES PRODUCED THEREFROM

• US 20170207492A1
• Filed: 03/17/2017
• Published: 07/20/2017
• Est. Priority Date: 06/08/2015
• Status: Active Grant

• Current Assignee: University of Waikato
• Original Assignee: Brian D. Adams, Dipan Kundu
• Inventors: ADAMS, Brian D., KUNDU, Dipan
• Granted Patent: US 9,780,412 B2
• Time in Patent Office: Days
• CPC Class Codes: H01M 10/36 Accumulators not provided for in groups H01M10/05-H01M10/34
• CPC Class Codes: H01M 2004/021 Physical characteristics, e.g. porosity, surface area
• CPC Class Codes: H01M 2300/0002 Aqueous electrolytes
• CPC Class Codes: H01M 4/38 of elements or alloys
• CPC Class Codes: H01M 4/485 of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy H01M4/505, H01M4/525 take precedence
• CPC Class Codes: H01M 4/622 being polymers
• CPC Class Codes: H01M 4/623 fluorinated polymers
• CPC Class Codes: H01M 4/625 Carbon or graphite
• CPC Class Codes: H01M 4/661 Metal or alloys, e.g. alloy coatings H01M4/669 take precedence
• CPC Class Codes: H01M 4/663 containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

The present disclosure discloses a rechargeable Zn battery based on layered/tunnelled structure vanadium/molybdenum oxides, with/without the presence of neutral/cationic/anionic species and/or water molecules inserted into the interlayers/tunnels, of nano/microparticle morphology as robust materials for high rate and long term reversible Zn²⁺ ion intercalation storage at the positive electrode, that are coupled with a metallic Zn negative electrode, and an aqueous electrolyte. The positive electrode may include electronically conducting additives and one or more binders along with the Zn²⁺ intercalation material: the negative electrode is Zn metal in any form; the aqueous electrolyte is of pH 1 to 9 and contains a soluble zinc salt in a concentration range from 0.01 to 10 molar.

Claims

1. A zinc ion battery, comprising:

a positive electrode compartment having enclosed therein an intercalation layered positive electrode material described by the formula M_xV₂O₅.nH₂O when the positive electrode is in the charged state, wherein x is in a range from 0.05 to less than 1, n is in a range from 0 to 2, wherein M is any one or combination of a d-block metal ion, f-block metal ion and alkaline earth ion, the metal M ion being in a +2 to +4 valence state, and wherein said V₂O₅ is a layered crystal structure having the metal ions M pillared between the layers, and waters of hydration coordinated to the metal ions M;

a negative electrode compartment having enclosed therein a negative electrode for storing zinc;

a separator electrically insulating and permeable to zinc ions separating the positive and negative compartments; and

an electrolyte comprising water and having a salt of zinc dissolved therein.

3. The zinc ion battery according to claim 1 wherein some of the waters of hydration are hydrogen bonded to the layers.

4. The zinc ion battery according to claim 1 wherein the negative electrode comprises zinc, and wherein the zinc ion battery is a zinc metal battery.

5. The zinc ion battery according to claim 1 wherein the electrolyte has a pH in a range from about 1 to about 8.

9. The zinc ion battery according to claim 1 wherein the intercalation layered positive electrode material has a particulate morphology being particles having a mean size in a range from about 5 nm to about 50 μ

m.

12. The zinc ion battery according to claim 9 wherein the particles are embedded in an electrically conducting matrix.

13. The zinc ion battery according to claim 12 wherein the electrically conducting matrix comprises any one or combination of carbon and conducting polymer, and including a binder.

14. The zinc ion battery according to claim 13 wherein the binder is any one or combination of styrene butadiene rubber (SBR), sodium carboxymethylcellulose (CMC), polyvinyl acetate (PVAc), polyacrylic acid (PAA), polyethylene glycol (PEG), polybutyl acrylate (PBA), polyurethane, acrylonitrile, polypyrrole, polyaniline, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), perfluorosulfonic acid (PFSA), and poly(3,4-ethylenedioxythiophene) (PEDOT).

15. The zinc ion battery according to claim 1 wherein the negative electrode comprises zinc metal or a zinc alloy in any form.

18. The zinc ion battery according to claim 1 wherein the negative electrode comprises a current collector, and a surface of the current collector facing into the negative electrode compartment having a layer of zinc bound thereto.

21. The zinc ion battery according to claim 18 wherein the current collector is comprised on any one or combination of carbon, boron, lead, vanadium, chromium, manganese, iron, cobalt, nickel, cadmium, tungsten, bismuth, tin, indium, antimony, copper, titanium, and zinc metal.

22. The zinc ion battery according to claim 1 wherein the negative electrode comprises a material that can store elemental zinc by any one or combination of intercalation, conversion, and capacitive storage.

23. The zinc ion battery according to claim 1 wherein the electrolyte further comprises water dissolved zinc present in a range from about 0.01 to about 10 molar (M), preferentially in the range from about 0.1 to about 4 M.

25. The zinc ion battery according to claim 23 wherein the salt of zinc comprises any one or combination of zinc sulfate, zinc acetate, zinc citrate, zinc iodide, zinc chloride, zinc perchlorate, zinc nitrate, zinc phosphate, zinc triflate, zinc bis(trifluoromethanesulfonyl)imide, zinc tetrafluoroborate, and zinc bromide.

2. (canceled)

6-8. -8. (canceled)

10-11. -11. (canceled)

16-17. -17. (canceled)

19-20. -20. (canceled)

24. (canceled)

26. A zinc ion battery, comprising:

a positive electrode compartment having enclosed therein and intercalated layered positive electrode material described by the formula M_xV₃O₇.nH₂O when the positive electrode is in the charged state, wherein x is in a range from 0.05 to less than 1, n is greater than 0 and less than 2, wherein M is any one or combination of a d-block metal ion, f-block metal ion and alkaline earth ion, the metal M ion being in a +2 to +4 valence state, and wherein said V₃O₇ is a layered crystal structure having the metal ions M pillared between the layers, and waters of hydration coordinated to the metal ions M and/or hydrogen bonded to the layers;

a negative electrode compartment having enclosed therein a negative electrode for storing zinc;

a separator electrically insulating and permeable to zinc ions separating the positive and negative compartments; and

an electrolyte comprising water and having a salt of zinc dissolved therein.

28. The zinc ion battery according to claim 26 wherein the negative electrode comprises zinc, and wherein the zinc ion battery is a zinc metal battery.

29. The zinc ion battery according to claim 26 wherein the electrolyte has a pH in a range from about 1 to about 8.

32. The zinc ion battery according to claim 26 wherein the intercalation layered positive electrode material has a particulate morphology being particles having a mean size in a range from about 5 nm to about 50 μ

m.

35. The zinc ion battery according to claim 32 wherein the particles are embedded in an electrically conducting matrix.

36. The zinc ion battery according to claim 35 wherein the electrically conducting matrix comprises any one or combination of carbon and conducting polymer, and including a binder.

37. The zinc ion battery according to claim 36 wherein the binder is any one or combination of styrene butadiene rubber (SBR), sodium carboxymethylcellulose (CMC), polyvinyl acetate (PVAc), polyacrylic acid (PAA), polyethylene glycol (PEG), polybutyl acrylate (PBA), polyurethane, acrylonitrile, polypyrrole, polyaniline, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), perfluorosulfonic acid (PFSA), and poly(3,4-ethylenedioxythiophene) (PEDOT).

38. The zinc ion battery according to claim 26 wherein the negative electrode comprises zinc metal or a zinc alloy in any form.

41. The zinc ion battery according to claim 26 wherein the negative electrode comprises a current collector, and a surface of the current collector facing into the negative electrode compartment having a layer of zinc bound thereto.

44. The zinc ion battery according to claim 41, wherein the current collector is comprised of any one or combination of carbon, boron, lead, vanadium, chromium, manganese, iron, cobalt, nickel, cadmium, tungsten, bismuth, tin, indium, antimony, copper, titanium, and zinc metal.

45. The zinc ion battery according to claim 26 wherein the negative electrode comprises a material that can store elemental zinc by any one or combination of intercalation, conversion, and capacitive storage.

46. The zinc ion battery according to claim 26 wherein the electrolyte further comprises water dissolved zinc present in a range from about 0.01 to about 10 Molar (M), preferentially in the range from about 0.1 to about 4 M.

48. The zinc ion battery according to claim 26 wherein the salt of zinc comprises any one or combination of zinc sulfate, zinc acetate, zinc citrate, zinc iodide, zinc chloride, zinc perchlorate, zinc nitrate, zinc phosphate, zinc triflate, zinc bis(trifluoromethanesulfonyl)imide, zinc tetrafluoroborate, and zinc bromide.

27. (canceled)

30-31. -31. (canceled)

33-34. -34. (canceled)

39-40. -40. (canceled)

42-43. -43. (canceled)

47. (canceled)

49-73. -73. (canceled)