ELECTROCHEMICAL CELL WITH DIVALENT CATION ELECTROLYTE AND AT LEAST ONE INTERCALATION ELECTRODE
The present invention provides a novel electrochemical cell that comprises a cathode, an anode, and an electrolyte, where an ion species present in the electrolyte intercalates into the cathode upon discharge of the electrochemical cell.
1 . An electrochemical cell comprising:
an aqueous electrolyte comprising a divalent cation;
a cathode comprising a layered material; and
an anode comprising a metal,
wherein the divalent cation intercalates into the layered material when the cell discharges; and the divalent cation de-intercalates from the cathode material and deposits onto the anode material as a neutral metal when the cell charges.
2 . The electrochemical cell of claim 1 , wherein the divalent cation is selected from Zn 2+ , Ca 2+ , Mg 2+ , Fe 2+ , or any combination thereof.
3 . The electrochemical cell of either of claim 1 or 2 , wherein the divalent cation is Zn 2+ .
4 . The electrochemical cell of claim 3 , wherein the aqueous electrolyte further comprises SO 4 2− , CHO − , NO 3 − , CO 2 CH 3 − , Cl − , ClO 4 − , or any combination thereof.
5 . The electrochemical cell of any one of claims 1 - 4 , wherein the electrolyte has a pH that is approximately neutral.
6 . The electrochemical cell of any one of claims 1 - 5 , wherein the electrolyte has a pH of from about 6 to about 8.
7 . The electrochemical cell of any one of claims 1 - 4 , wherein the electrolyte has a pH of from about 3 to about 6.
8 . The electrochemical cell of any one of claims 1 - 7 , wherein the layered material comprises a metal oxide, a mixed metal oxide, a metal sulfide, a zinc metal phosphate, a zinc metal oxide, or any combination thereof.
9 . The electrochemical cell of claim 8 , wherein the layered material comprises manganese oxide, vanadium oxide, manganese vanadium oxide, TiS 2 , WO 2 Cl 2 , or any combination thereof.
10 . The electrochemical cell of any one of claims 1 - 9 , wherein the layered material comprises manganese oxide that undergoes a reduction in its oxidation state of 1 or more during the discharge of the electrochemical cell.
11 . The electrochemical cell of claim 10 , wherein the cathode material comprises manganese oxide having a chemical formula of Mn x O y where x is greater than or equal to 1, and y is greater than or equal to 2.
12 . The electrochemical cell of claim 9 , wherein the cathode material comprises manganese vanadium oxide having a chemical formula of Mn x V z O y , where x is greater than or equal to 1, y is greater than or equal to 2, and z is greater than or equal to 1.
13 . The electrochemical cell of claim 9 , wherein the layered material comprises manganese oxide having a chemical formula of MnO 2 , Mn 5 O 8 , Mn 3 O 7 .3H 2 O, Mn 7 O 14 .3H 2 O, Mn 4 O 9 .3H 2 O, Mn 2 O 4 , Mn 4 O 18 .H 2 O, or any combination thereof.
14 . The electrochemical cell of claim 9 , wherein the layered material comprises manganese oxide having a predominant crystal structure of α-MnO 2 , β-MnO 2 , γ-MnO 2 , δ-MnO 2 , layered, or any combination thereof.
15 . The electrochemical cell of claim 13 , wherein the layered material comprises Mn 5 O 8 that comprises a power having a mean particle diameter of about 50 μm or less.
16 . The electrochemical cell of any one of claims 1 - 15 , wherein the cathode further comprises a carbon powder.
17 . The electrochemical cell of claim 16 , wherein the cathode further comprises about 15 wt % or less of the carbon powder by weight of the cathode.
18 . The electrochemical cell of either of claim 16 or 17 , wherein the carbon powder comprises acetylene black, furnace black, channel black, graphite, activated carbon, graphene, or any combination thereof.
19 . The electrochemical cell of any one of claims 9 - 18 , wherein the cathode further comprises an additive that stabilizes the crystal lattice structure of manganese oxide.
20 . The electrochemical cell of claim 19 , wherein the additive comprises TiS 2 , TiB 2 , Bi 2 O 3 , or any combination thereof.
21 . The electrochemical cell of either of claim 19 or 20 , wherein the additive is present at a concentration of about 20 wt % or less by weight of the cathode.
22 . The electrochemical cell of any one of claims 1 - 21 , wherein the cathode is doped with Al, B, or any combination thereof.
23 . The electrochemical cell of any one of claims 1 - 22 , wherein the anode comprises a metal, and a portion of the metal transforms into a divalent cation when the cell is discharged.
24 . The electrochemical cell of claim 23 , wherein the metal comprises zinc, magnesium, or a combination thereof.
25 . The electrochemical cell of any one of claims 1 - 24 , wherein the cathode, the anode, or both further comprises a binder.
26 . The electrochemical cell of claim 25 , wherein the binder comprises polyacrylonitrile, polyvinyl alcohol, polyvinyl chloride, polyethylene oxide, polytetrafluoroethylene, polyvinylidene difluoride, polymethylmethacrylate, or any combination thereof.
27 . The electrochemical cell of either of claim 25 or 26 , wherein the binder is present at a concentration of from about 3 wt % to about 15 wt % by weight of the cathode or anode.
28 . The electrochemical cell of any one of claims 1 - 27 , wherein the anode, the cathode, or both further comprises a current collector.
29 . The electrochemical cell of claim 28 , wherein the current collector comprises one or more electrically conductive metals or an electrically conductive polymer material.
30 . The electrochemical cell of either of claim 28 or 29 , wherein the current collector comprises a woven material, a non-woven material, or a combination thereof.
31 . The electrochemical cell of claim 30 , wherein the current collector comprises a sheet of non-woven material that optionally comprises one or more perforations.
32 . An electrochemical cell comprising:
an aqueous electrolyte comprising a divalent cation that comprises Zn 2+ , Mg 2+ , or a combination thereof;
a cathode comprising a metal oxide; and
an anode comprising zinc metal, magnesium metal, or a combination thereof,
wherein the aqueous electrolyte has a nearly neutral pH, the divalent cation intercalates into the cathode when the cell discharges; and the divalent cation deposits onto the anode as a neutral metal when the cell charges.
33 . The electrochemical cell of claim 32 , wherein the divalent cation is Zn 2+ .
34 . The electrochemical cell of claim 33 , wherein the aqueous electrolyte further comprises SO 4 2− , CHO − , NO 3 − , CO 2 CH 3 − , Cl − , Br − , ClO 4 − , or any combination thereof.
35 . The electrochemical cell of claim 34 , wherein the cathode comprises manganese oxide, and the manganese oxide is not substantially soluble in the aqueous electrolyte.
36 . The electrochemical cell of claim 35 , wherein the manganese oxide has a chemical formula of Mn x O y where x is greater than or equal to 1, and y is greater than or equal to 2.
37 . The electrochemical cell of claim 34 , wherein the cathode material comprises manganese vanadium oxide having a chemical formula of Mn x V z O y , where x is greater than or equal to 1, y is greater than or equal to 2, and z is greater than or equal to 1.
38 . The electrochemical cell of claim 34 , wherein the cathode material comprises manganese oxide having a chemical formula of MnO 2 , Mn 5 O 8 , Mn 3 O 7 .3H 2 O, Mn 7 O 14 .3H 2 O, Mn 4 O 9 .3H 2 O, Mn 2 O 4 , Mn 4 O 18 .H 2 O, or any combination thereof.
39 . The electrochemical cell of claim 34 , wherein the layered material comprises manganese oxide having a predominant crystal structure of α-MnO 2 , β-MnO 2 , γ-MnO 2 , δ-MnO 2 , layered, or any combination thereof.
40 . The electrochemical cell of claim 38 , wherein the manganese oxide has a chemical formula of Mn 5 O 8 , and the manganese oxide comprises a power having a mean particle diameter of about 50 μm or less.
41 . The electrochemical cell of any one of claims 32 - 40 , wherein the cathode further comprises a carbon powder.
42 . The electrochemical cell of claim 41 , wherein the cathode further comprises about 15 wt % or less of the carbon powder by weight of the cathode.
43 . The electrochemical cell of claim 42 , wherein the carbon powder comprises acetylene black, furnace black, channel black, graphite, activated carbon, graphene, or any combination thereof.
44 . The electrochemical cell of any one of claims 35 - 43 , wherein the cathode further comprises an additive that stabilizes the crystal lattice structure of manganese oxide.
45 . The electrochemical cell of claim 44 , wherein the additive comprises TiS 2 , TiB 2 , Bi 2 O 3 , or any combination thereof.
46 . The electrochemical cell of claim 45 , wherein the additive is present at a concentration of about 20 wt % or less by weight of the cathode.
47 . The electrochemical cell of any one of claims 32 - 46 , wherein the anode comprises zinc metal.
48 . The electrochemical cell of any one of claims 32 - 47 , wherein the anode comprises zinc metal and the divalent cation is Zn 2+ .
49 . The electrochemical cell of any one of claims 32 - 48 , wherein the anode material, the cathode material, or both further comprises a binder.
50 . The electrochemical cell of claim 49 , wherein the binder comprises polyacrylonitrile, polyvinyl alcohol, polyvinyl chloride, polyethylene oxide, polytetrafluoroethylene, polyvinylidene difluoride, polymethylmethacrylate, or any combination thereof.
51 . The electrochemical cell of either of claim 49 or 50 , wherein the binder is present at a concentration of from about 3 wt % to about 15 wt % by weight of the cathode or anode.
52 . The electrochemical cell of any one of claims 32 - 51 , wherein the anode, the cathode, or both further comprises a current collector.
53 . The electrochemical cell of claim 52 , wherein the current collector comprises one or more electrically conductive metals or an electrically conductive polymer material.
54 . The electrochemical cell of either of claim 52 or 53 , wherein the current collector comprises a woven material, a non-woven material, or a combination thereof.
55 . The electrochemical cell of claim 54 , wherein the current collector comprises a sheet of non-woven material that optionally comprises perforations.
56 . The electrochemical cell of any one of claims 32 - 55 , wherein the cathode is doped with Al, B, or any combination thereof.
57 . A method of manufacturing an electrochemical cell comprising:
providing a cathode comprising a layered material;
providing an anode comprising a metal; and
providing an aqueous electrolyte comprising a divalent cation,
wherein the divalent cation intercalates into the layered material when the cell discharges; and the divalent cation de-intercalates from the cathode material and deposits onto the anode material as a neutral metal when the cell charges.
58 . The method of claim 57 , wherein the divalent cation is selected from Zn 2+ , Ca 2+ , Mg 2+ , Fe 2+ , or any combination thereof.
59 . The method of claim 58 , wherein the divalent cation is Zn 2+ .
60 . The method of claim 59 , further comprising dissolving ZnSO 4 , Zn(CHO 2 ) 2 , Zn(NO 3 ) 2 , Zn(CO 2 CH 3 ) 2 , ZnCl 2 , ZnBr 2 , Zn(ClO 4 ) 2 , or any combination thereof in water to generate the Zn 2+ divalent cation.
61 . The method of any one of claims 57 - 60 , wherein the cathode comprises a layered material comprising a metal oxide, a mixed metal oxide, a metal sulfide, a zinc metal phosphate, a zinc metal oxide, or any combination thereof.
62 . The method of claim 61 , wherein the cathode comprises manganese oxide, vanadium oxide, manganese vanadium oxide, TiS 2 , WO 2 Cl 2 , or any combination thereof.
63 . The method of either of claim 61 or 62 , wherein the cathode comprises a metal oxide that undergoes a reduction in its oxidation state of 1 or more during the discharge of the electrochemical cell.
64 . The method of claim 63 , wherein the cathode comprises manganese oxide having a chemical formula of Mn x O y and x is greater than or equal to 1, and y is greater than or equal to 2.
65 . The method of claim 64 , wherein the cathode comprises manganese oxide having a chemical formula of MnO 2 , Mn 5 O 8 , Mn 3 O 7 .3H 2 O, Mn 7 O 14 .3H 2 O, Mn 4 O 9 .3H 2 O, Mn 2 O 4 , Mn 4 O 18 .H 2 O, or any combination thereof.
66 . The method of claim 64 , wherein the cathode comprises manganese oxide having a predominant crystal structure of α-MnO 2 , β-MnO 2 , γ-MnO 2 , δ-MnO 2 , layered, or any combination thereof.
67 . The method of claim 65 , wherein the cathode comprises Mn 5 O 8 , and the Mn 5 O 8 comprises a powder having a mean particle diameter of about 50 μm or less.
68 . The method of any one of claims 57 - 67 , wherein the cathode further comprises carbon powder.
69 . The method of claim 68 , wherein the cathode further comprises about 15 wt % or less of the carbon powder by weight of the cathode.
70 . The method of claim 69 , wherein the carbon powder comprises acetylene black, furnace black, channel black, graphite, activated carbon, graphene, or any combination thereof.
71 . The method of any one of claims 62 - 70 , wherein the cathode further comprises an additive that stabilizes the crystal lattice structure of manganese oxide.
72 . The method of claim 71 , wherein the additive comprises TiS 2 , TiB 2 , Bi 2 O 3 , or any combination thereof.
73 . The method of claim 72 , wherein the additive is present at a concentration of about 20 wt % or less by weight of the cathode.
74 . The method of any one of claims 57 - 73 , wherein the cathode is doped with Al, B, or any combination thereof.
75 . The method of any one of claims 57 - 74 , wherein the anode material comprises a metal that undergoes an increase in its oxidation state of 1 or more during the discharge of the electrochemical cell.
76 . The method of any one of claims 57 - 75 , wherein the anode comprises zinc metal, magnesium metal, or a combination thereof.
77 . The method of any one of claims 57 - 76 , wherein the divalent cation is Zn 2+ , and the anode comprises zinc metal.
78 . The method of any one of claims 57 - 77 , wherein the anode material, the cathode material, or both further comprises a binder.
79 . The method of claim 78 , wherein the binder comprises polyacrylonitrile, polyvinyl alcohol, polyvinyl chloride, polyethylene oxide, polytetrafluoroethylene, polyvinylidene difluoride, polymethylmethacrylate, or any combination thereof.
80 . The method of either of claim 78 or 79 , wherein the binder is present at a concentration of from about 3 wt % to about 15 wt % by weight of the cathode or anode.
81 . The method of any one of claims 57 - 80 , further comprising providing a cathode current collector, an anode current collector, or both.
82 . The method of claim 81 , wherein the cathode current collector, the anode current collector, or both comprises one or more electrically conductive metals or an electrically conductive polymer material.
83 . The method of either of claim 81 or 82 , wherein the cathode current collector, the anode current collector, or both comprises a woven material, a non-woven material, or a combination thereof.
84 . The method of claim 83 , wherein the cathode current collector, the anode current collector, or both comprises a sheet of non-woven material that optionally comprises perforations.