Battery anode with preloaded metals
A method is presented for fabricating an anode preloaded with consumable metals. The method provides a material (X), which may be one of the following materials: carbon, metals able to be electrochemically alloyed with a metal (Me), intercalation oxides, electrochemically active organic compounds, and combinations of the above-listed materials. The method loads the metal (Me) into the material (X). Typically, Me is an alkali metal, alkaline earth metal, or a combination of the two. As a result, the method forms a preloaded anode comprising Me/X for use in a battery comprising a M1 Y M2 Z (CN) N .M H 2 O cathode, where M1 and M2 are transition metals. The method loads the metal (Me) into the material (X) using physical (mechanical) mixing, a chemical reaction, or an electrochemical reaction. Also provided is preloaded anode, preloaded with consumable metals.
1. A method for fabricating an anode preloaded with consumable metals, the method comprising:
providing a material (X) selected from the group consisting of carbon, metals able to be electrochemically alloyed with a metal (Me), intercalation oxides, electrochemically active organic compounds, and combinations of the above-listed materials;
loading the metal (Me) into the material (X), where Me is selected from the group consisting of alkali metals, alkaline earth metals, terbium (Tb), silver (Ag), aluminum (Al) and combinations thereof;
forming a preloaded anode comprising Me/X for use in a battery comprising a M1 Y M2 Z (CN) N .M H 2 O cathode;
where M1 and M2 are independently selected from the group consisting of transition metals, calcium (Ca) and magnesium (Mg);
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;
wherein loading the metal (Me) into the material (X) includes using an electrochemical reaction as follows:
forming an electrode of X and a counter electrode of Me, both inserted into an electrolyte;
performing a plurality of charge and discharge operations, where the charge operation uses an external current source to create a positive voltage potential from the electrode to the counter electrode, and where the discharge operation connects an external load between the electrode and counter electrode;
in response to the charge and discharge operations, inserting Me particles into the material (X); and,
wherein forming the preloaded anode includes forming a Me/X compound, where Me is chemically reacted with X.
2. The method of claim 1 further comprising:
consuming the metal (Me) in the preloaded anode; and,
forming a stabilized anode comprising the material (X).
3. The method of claim 1 wherein forming the electrode of X includes X being selected from the group of hard carbon, tin, antimony, Na 2 Ti 3 O 7 , Li 4 Ti 5 O 12 , and Fe 3 O 4 ; and,
wherein forming the counter electrode of Me includes Me being selected from the group consisting of lithium and sodium.
4. The method of claim 1 wherein Me is selected from the group consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), calcium (Ca), strontium (Sr), barium (Ba), and magnesium (Mg).
5. The method of claim 1 wherein M1 and M2 are each independently selected from the group consisting of titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn).
6. A preloaded battery with an anode preloaded with consumable metals, the preloaded battery comprising:
a non-aqueous electrolyte;
a preloaded anode comprising:
a conductive current collector;
Me/X overlying the current collector, where X is a material selected from the group consisting of carbon, metals able to be electrochemically alloy with metal (Me), intercalation oxides, electrochemically active organic compounds, and combinations of the above-listed materials, and Me is a metal is selected from the group consisting of alkali metals, alkaline earth metals, terbium (Tb), silver (Ag), aluminum (Al) and combinations thereof;
a cathode comprising:
a conductive current collector;
M1 Y M2 Z (CN) N .M H 2 O overlying the current collector;
where M1 and M2 are independently selected from the group consisting of transition metals, calcium (Ca) and magnesium (Mg);
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; and,
an ion-permeable membrane immersed in the non-aqueous electrolyte, interposed between the anode and the cathode.
7. The preloaded battery of claim 6 wherein Me is selected from the group consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), calcium (Ca), strontium (Sr), barium (Ba), and magnesium (Mg).
8. The preloaded battery of claim 6 wherein Me/X is selected from the group consisting of:
Li R VO 2 , where 0<R<1;
Na s MnO 2 , where 0<s<1;
a Na—Sn alloy;
a mixture of lithium powder and tin particles;
a mixture of sodium particles and hard carbon powder;
a compound of hard carbon and lithium;
a compound of hard carbon and sodium;
a Li—Sn alloy;
a Li—Sb alloy;
a Na—Sb alloy;
a compound of Fe 3 O 4 and Li; and,
a compound of Fe 3 O 4 and Na.
9. The preloaded battery of claim 6 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).
10. A method for fabricating an anode preloaded with consumable metals, the method comprising:
providing a material (X) selected from the group consisting of carbon, metals able to be electrochemically alloyed with a metal (Me), intercalation oxides, electrochemically active organic compounds, and combinations of the above-listed materials;
loading the metal (Me) into the material (X), where Me is selected from the group consisting of alkali metals, alkaline earth metals, and a combination of alkali and alkaline earth metals;
forming a preloaded anode comprising Me/X for use in a battery comprising a M1 Y M2 Z (CN) N .M H 2 O cathode;
where M1 and M2 are independently selected from the group consisting of transition metals, calcium, and magnesium;
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;
wherein loading the metal (Me) into the material (X) includes using a chemical reaction that reduces X with Me-containing reductive agents; and,
wherein forming the preloaded anode includes forming a Me/X compound where Me is chemically reacted with X.
11. The method of claim 10 wherein reducing X with Me-containing reductive agents includes a process selected from the group consisting of:
reducing VO 2 with n-butyl lithium to form Li R VO 2 , where 0<R<1;
reducing MnO 2 with tert-butyl alkoxide-activated NaH in tetrahydrofuran to form Na s MnO 2 , where 0<s<1;
reducing TiO 2 with NaH to form NaTiO 2 ; and,
mixing Sn particles in melted Na to form a Na—Sn alloy.
12. A method for fabricating an anode preloaded with consumable metals, the method comprising:
providing a material (X) selected from the group consisting of carbon, metals able to be electrochemically alloyed with a metal (Me), intercalation oxides, electrochemically active organic compounds, and combinations of the above-listed materials;
loading the metal (Me) into the material (X), where Me is selected from the group consisting of alkali metals, alkaline earth metals, and a combination of alkali and alkaline earth metals;
forming a preloaded anode comprising Me/X for use in a battery comprising a M1 Y M2 Z (CN) N .M H 2 O cathode;
where M1 and M2 are independently selected from the group consisting of transition metals, calcium, and magnesium;
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;
wherein loading the metal (Me) into the material (X) includes mechanically mixing Me and X particles in an inert atmosphere, without creating a chemical reaction between the Me and X particles.
13. The method of claim 12 wherein mechanically mixing Me and X particles includes a process selected from the group consisting of mixing a lithium powder with tin particles in an atmosphere of Ar by ball-milling, and mixing sodium particles with hard carbon powders in an industrial blender at a temperature above 100 degrees C. and subsequently cooling to room temperature.
14. A method for fabricating an anode preloaded with consumable metals, the method comprising:
providing a material (X) selected from the group consisting of carbon, metals able to be electrochemically alloyed with a metal (Me), intercalation oxides, electrochemically active organic compounds, and combinations of the above-listed materials;
loading the metal (Me) into the material (X), where Me is selected from the group consisting of alkali metals, alkaline earth metals, and a combination of alkali and alkaline earth metals;
forming a preloaded anode comprising Me/X for use in a battery comprising a M1 Y M2 Z (CN) N .M H 2 O cathode;
where M1 and M2 are independently selected from the group consisting of transition metals, calcium, and magnesium;
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;
wherein loading the metal (Me) into the material (X) includes using an electrochemical reaction that directly contacts Me and X in a Me-ion conductive solution; and,
wherein forming the preloaded anode includes forming a Me/X compound, where Me is chemically reacted with X.