Rechargeable metal-ion battery with non-aqueous hybrid ion electrolyte
A method is provided for forming a rechargeable metal-ion battery with a non-aqueous hybrid ion electrolyte. The method provides a transition metal hexacyanometallate (TMHCM) cathode (A X M1 Y M2 Z (CN) N .M H 2 O), where “A” is from a first group of metals, and M1 and M2 are transition metals. The electrolyte includes a first type of cation from the first group of metals, different than “A”. The method connects the cathode and anode to external circuitry to perform initial charge/discharge operations. As a result, a hybrid ion electrolyte is formed including the first type of cation and “A” cations. Subsequently, cations are inserted into the anode during charging, which alternatively may be only “A” cations, only the first type of cation, or both the “A” cations and the first type of cation. Only “A” cations, only the first type, or both “A” and the first type of cation are inserted into the TMHCM during discharge.
1. A rechargeable metal-ion battery with a hybrid ion electrolyte, the battery comprising:
a cathode comprising hexacyanometallate (HCM) particles overlying a current collector, the HCM particles having a chemical formula A X M1 Y M2 Z (CN) N .M H 2 O;
where “A” is selected from a first group of metals;
where M1 and M2 are selected from a second group of metals;
where X is less than or equal to 2;
where Y is less than or equal to 1;
where Z is less than or equal to 1;
where N is less than or equal to 6;
where M is less than or equal to 20;
a hybrid ionic non-aqueous electrolyte including a first type of cation selected from the first group of metals and a second type of cation selected from the first group of metals and different than the first type of cation; and,
an anode.
2. The battery of claim 1 wherein the anode is a material selected from the group consisting of carbonaceous materials, alkali metals, alkaline earth metals, alloys including tin, alloys including lead, alloys including silicon, alloys including phosphorous, alloys including germanium, titanates including alkali metals, titanates including alkaline earth metals, and combinations thereof.
3. The battery of claim 1 wherein the first group of metals is selected from the group of metals consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), calcium (Ca), strontium (Sr), barium (Ba), silver (Ag), aluminum (Al), magnesium (Mg), and combinations thereof.
4. The battery of claim 1 wherein M1 and M2 are each independently derived, as selected from the group consisting of titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), Ca, Mg, strontium (Sr), and barium (Ba).
5. The battery of claim 1 wherein each of the first and second types of cations in the electrolyte each comprise at least 1% in molar ratio as compared to the total ion concentration of cations in the electrolyte.
6. The battery of claim 1 wherein the cathode HCM particles include cations from only the first type of cation when the battery is in the discharged state.
7. The battery of claim 1 wherein the cathode HCM particles include cations from both the first and second types of cations, when the battery is in a discharged state.
8. The battery of claim 1 wherein the anode includes cations from only the first type of cation, when the battery is in a charged state.
9. The battery of claim 1 wherein the anode includes cations from both the first and second type of cations, when the battery is in a charged state.
10. A method for forming a rechargeable metal-ion battery with a non-aqueous hybrid ion electrolyte, the method comprising:
providing a transition metal hexacyanometallate (TMHCM) cathode having a chemical formula A X M1 Y M2 Z (CN) N .M H 2 O, where “A” is selected from a first group of metals and M1 and M2 are transition metals, an electrolyte includes a first type of cation selected from the first group of metals and different than “A”, and an anode; and,
where X is less than or equal to 2;
where Y is less than or equal to 1;
where Z is less than or equal to 1;
where N is less than or equal to 6;
where M is less than or equal to 20;
connecting the cathode and anode to a current source to perform an initial charge operation;
connecting the cathode and anode to a load to perform an initial discharge operation; and,
forming a hybrid ion non-aqueous electrolyte including the first type of cation and “A” cations.
11. The method of claim 10 wherein providing the anode includes providing an anode made from a material selected from the group consisting of carbonaceous materials, alkali metals, alkaline earth metals, alloys including tin, alloys including lead, alloys including silicon, alloys including phosphorous, alloys including germanium, titanates including alkali metals, titanates including alkaline earth metals, and combinations thereof.
12. The method of claim 10 wherein providing the cathode includes the first group of metals being selected from the group of metals consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), calcium (Ca), strontium (Sr), barium (Ba), silver (Ag), aluminum (Al), magnesium (Mg), and combinations thereof.
13. The method of claim 10 wherein forming the hybrid ion electrolyte includes each of the first and second types of cations in the electrolyte comprising at least 1% in molar ratio as compared to the total ion concentration of cations in the electrolyte.
14. The method of claim 10 further comprising:
subsequent to the initial charge and discharge operations, connecting the cathode and anode to a current source and charging the battery;
inserting cations into the anode selected from a group consisting of:
a) only “A” cations;
b) only the first type of cation; and,
c) both the “A” cations and the first type of cation.
15. The method of claim 14 further comprising:
subsequent to charging the battery, connecting the cathode and anode to a load and discharging the battery; and,
inserting cations into the TMHCM particles selected from a group consisting of:
a) only “A” cations;
b) only the first type of cation; and,
c) both “A” cations and the first type of cation.
16. A method for operating a rechargeable metal-ion battery with a non-aqueous hybrid ion electrolyte, the method comprising:
providing a transition metal hexacyanometallate (TMHCM) cathode having a chemical formula A X M1 Y M2 Z (CN) N .M H 2 O, where “A” is selected from a first group of metals, hybrid ionic a non-aqueous electrolyte including both “A” cations and a first type of cation selected from the first group of metals and different than “A”, and an anode;
wherein providing the cathode includes:
M1 and M2 are transition metals;
where X is less than or equal to 2;
where Y is less than or equal to 1;
where Z is less than or equal to 1;
where N is less than or equal to 6;
where M is less than or equal to 20;
subsequent to an initial charging and discharge cycle, connecting the cathode and anode to a current source and charging the battery; and
inserting cations into the anode selected from a group consisting of:
a) only “A” cations;
b) only the first type of cation;
b) both “A” cations the first type of cation;
subsequent to charging the battery, connecting the cathode and anode to a load and discharging the battery; and,
inserting cations into the TMHCM particles selected from a group consisting of;
a) only “A” cations;
b) only the first type of cation; and,
c) both “A” cations and the first type of cation.
17. The method of claim 16 wherein providing the cathode includes the first group of metals comprising lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), calcium (Ca), strontium (Sr), barium (Ba), silver (Ag), aluminum (Al), magnesium (Mg), and combinations thereof.
18. The method of claim 16 wherein providing the anode includes providing an anode made from a material selected from the group consisting of carbonaceous materials, alkali metals, alkaline earth metals, alloys including tin, alloys including lead, alloys including silicon, alloys including phosphorous, alloys including germanium, titanates including alkali metals, titanates including alkaline earth metals, and combinations thereof.
19. A method for forming a rechargeable metal-ion battery with a non-aqueous hybrid ion electrolyte, the method comprising:
providing a transition metal hexacyanometallate (TMHCM) cathode having a chemical formula A X M1 Y M2 Z (CN) N .M H 2 O, where “A” is selected from a first group of metals and M1 and M2 are transition metals, an electrolyte, and an anode
where X is less than or equal to 2;
where Y is less than or equal to 1;
where Z is less than or equal to 1;
where N is less than or equal to 6;
where M is less than or equal to 20;
including a first type of cation selected from the first group of metals and different than “A”;
connecting the cathode and anode to a current source to perform an initial charge operation;
connecting the cathode and anode to a load to perform an initial discharge operation; and,
forming a hybrid ion non-aqueous electrolyte including the first type of cation and “A” cations.
20. The method of claim 19 wherein providing the anode includes providing an anode made from a material selected from the group consisting of carbonaceous materials, alkali metals, alkaline earth metals, alloys including tin, alloys including lead, alloys including silicon, alloys including phosphorous, alloys including germanium, titanates including alkali metals, titanates including alkaline earth metals, and combinations thereof.
21. The method of claim 19 wherein providing the cathode includes the first group of metals being selected from the group of metals consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), calcium (Ca), strontium (Sr), barium (Ba), silver (Ag), aluminum (Al), magnesium (Mg), and combinations thereof.
22. A rechargeable metal-ion battery with a hybrid ion electrolyte, the battery comprising:
a cathode comprising transition metal hexacyanometallate (TMHCM) particles overlying a current collector, the TMHCM particles having a chemical formula A X M1 Y M2 Z (CN) N .M H 2 O;
where “A” is selected from a first group of metals;
where M1 and M2 are transition metals;
where X is less than or equal to 2;
where Y is less than or equal to 1;
where Z is less than or equal to 1;
where N is less than or equal to 6;
where M is less than or equal to 20;
a hybrid ionic electrolyte including a first type of cation selected from the first group of metals and a second type of cation selected from the first group of metals and different than the first type of cation; and,
an anode made from a material selected from the group consisting of graphite, hard carbon, carbon black, carbon cloth, carbon paper, alkali metals, alkaline earth metals, alloys including tin, alloys including lead, alloys including silicon, alloys including phosphorous, alloys including germanium, titanates including alkali metals, titanates including alkaline earth metals, and combinations thereof.
23. A rechargeable metal-ion battery with a hybrid ion electrolyte, the battery comprising:
a cathode comprising transition metal hexacyanometallate (TMHCM) particles overlying a current collector, the TMHCM particles having a chemical formula A X M1 Y M2 Z (CN) N .M H 2 O;
where “A” is selected from a first group of metals;
where M1 and M2 are transition metals;
where X is less than or equal to 2;
where Y is less than or equal to 1;
where Z is less than or equal to 1;
where N is less than or equal to 6;
where M is less than or equal to 20;
a hybrid ionic electrolyte including a first type of cation selected from the first group of metals, a second type of cation selected from the first group of metals and different than the first type of cation, and wherein at least one of the first type of cation and second type of cation is a multivalent cation; and,
an anode.
24. The battery of claim 23 wherein both the first type of cation and second type of cation are multivalent cations.