Metal and metallic ion mixed batteries and a method for increasing cycle lifetime thereof
The present invention provides a metal and metallic ion mixed battery, which contains a positive electrode, a negative electrode, and an electrolyte, the positive electrode contains a positive electrode material with a metallic component of the battery; It only coats a small amount of negative electrode active materials that can form a metallic ion battery on the negative electrode and makes the negative electrode of the battery included dual advantages of metal and metallic ion battery; when charging, the metallic ions from the positive electrode are embedded in the negative electrode active material to make the battery have the characteristics of a metallic ion battery, and then continue to deposit on the current collector to form a metal battery. After several cycles, the battery can be charged and discharged stably and retains more than 99% of Coulombic efficiency, enhancing the overall energy density of the battery.
1 . A metal and metallic ion mixed battery, containing:
a positive electrode containing a positive electrode material on the positive electrode, the positive electrode material comprising at least one battery metal component;
a negative electrode containing a negative electrode active material which lithiation/sodiation the metal components contained in the corresponding positive electrode material; and
an electrolyte interposed between the positive electrode and the negative electrode; wherein
the ratio (Anode(Negative)/Cathode(Positive), A/C) of the supplied battery metal amount of the negative electrode active material to that of the positive electrode material is 0<A/C<1.
2 . The metal and metallic ion mixed battery according to claim 1 , wherein: the metal and metallic ion mixed battery forms a metal layer in the negative electrode area after at least one charge.
3 . The metal and metallic ion mixed battery according to claim 1 , wherein:
the battery metal component comprises lithium or sodium;
the positive electrode comprises a metal foil;
the positive electrode materials contain nickel-cobalt-aluminum positive electrode materials, nickel-cobalt-manganese positive electrode materials, lithium cobaltate positive electrode materials, sodium cobaltate positive electrode materials, lithium manganate positive electrode materials, sodium manganate positive electrode materials, metal-doped lithium manganate positive electrode materials, metal-doped sodium manganate positive electrode materials, lithium-manganese phosphate positive electrode materials, metal-doped sodium manganate positive electrode materials, lithium-iron phosphate positive electrode materials, sodium-iron phosphate positive electrode materials, metal-doped lithium-iron phosphate positive electrode materials, metal-doped sodium-iron phosphate positive electrode materials, lithium sulfide positive electrode materials, or Prussian blue positive electrode materials;
the negative electrode contains a current collector, carbon material, sodium titanate, molybdenum disulfide, titanium disulfide, iron disulfide, antimony, tin, tin disulfide, ferrous sulfate, nickel phosphide, antimony trisulfide, antimony oxide, or a tin-antimony alloy;
the negative electrode active material comprises a carbon-containing compound, tin, tin-containing compound or oxide, silicon, silicon-containing compound or oxide, aluminum-containing compound, germanium, germanium-containing compound or oxide, lithium-titanium oxide, or a combination thereof; or
the electrolyte contains a liquid electrolyte or a solid electrolyte.
4 . The metal and metallic ion mixed battery according to claim 2 , wherein:
the battery metal component comprises lithium or sodium;
the positive electrode comprises a metal foil;
the positive electrode materials contain nickel-cobalt-aluminum positive electrode materials, nickel-cobalt-manganese positive electrode materials, lithium cobaltate positive electrode materials, sodium cobaltate positive electrode materials, lithium manganate positive electrode materials, sodium manganate positive electrode materials, metal-doped lithium manganate positive electrode materials, metal-doped sodium manganate positive electrode materials, lithium-manganese phosphate positive electrode materials, metal-doped sodium manganate positive electrode materials, lithium-iron phosphate positive electrode materials, sodium-iron phosphate positive electrode materials, metal-doped lithium-iron phosphate positive electrode materials, metal-doped sodium-iron phosphate positive electrode materials, lithium sulfide positive electrode materials, or Prussian blue positive electrode materials;
the negative electrode contains a current collector, carbon material, sodium titanate, molybdenum disulfide, titanium disulfide, iron disulfide, antimony, tin, tin disulfide, ferrous sulfate, nickel phosphide, antimony trisulfide, antimony oxide, or a tin-antimony alloy;
the negative electrode active material comprises a carbon-containing compound, tin, tin-containing compound or oxide, silicon, silicon-containing compound or oxide, aluminum-containing compound, germanium, germanium-containing compound or oxide, lithium-titanium oxide, or a combination thereof; or
the electrolyte contains a liquid electrolyte or a solid electrolyte.
5 . The metal and metallic ion mixed battery according to claim 3 , wherein:
the battery metal component comprises lithium or sodium;
the positive electrode comprises a metal foil;
the positive electrode materials contain nickel-cobalt-aluminum positive electrode materials, nickel-cobalt-manganese positive electrode materials, lithium cobaltate positive electrode materials, sodium cobaltate positive electrode materials, lithium manganate positive electrode materials, sodium manganate positive electrode materials, metal-doped lithium manganate positive electrode materials, metal-doped sodium manganate positive electrode materials, lithium-manganese phosphate positive electrode materials, metal-doped sodium manganate positive electrode materials, lithium-iron phosphate positive electrode materials, sodium-iron phosphate positive electrode materials, metal-doped lithium-iron phosphate positive electrode materials, metal-doped sodium-iron phosphate positive electrode materials, lithium sulfide positive electrode materials, or Prussian blue positive electrode materials;
the negative electrode contains a current collector, carbon material, sodium titanate, molybdenum disulfide, titanium disulfide, iron disulfide, antimony, tin, tin disulfide, ferrous sulfate, nickel phosphide, antimony trisulfide, antimony oxide, or a tin-antimony alloy;
the negative electrode active material comprises a carbon-containing compound, tin, tin-containing compound or oxide, silicon, silicon-containing compound or oxide, aluminum-containing compound, germanium, germanium-containing compound or oxide, lithium-titanium oxide, or a combination thereof; or
the electrolyte contains a liquid electrolyte or a solid electrolyte.
6 . The metal and metallic ion mixed battery according to claim 4 , wherein:
the metal foil of the positive electrode contains an aluminum foil;
the current collector of the negative electrode contains a copper foil;
the carbon material of the negative electrode comprises hard carbon, soft carbon, coke, bitumen, nano carbon tubing, N-doped carbon, P-doped carbon, B-doped carbon or a combination thereof; and
the solid electrolyte comprises a sulfide solid electrolyte, an oxide solid electrolyte and a polymer solid electrolyte, or a combination thereof.
7 . A method for increasing the cycle lifetime of the battery, comprising the steps of:
providing a metal and metallic ion mixed battery as claimed in claim 1 ;
charging the metal and metallic ion mixed battery so that the positive electrode material releases the battery metal component therein; and
during the charging process, the battery metal component passes through the electrolyte and contacts the negative electrode active material contained in the negative electrode so that the negative electrode active material lithiation/sodiation and forms a metal layer in the negative electrode area to obtain the metal and metallic ion mixed battery having both metal and metallic ion battery characteristics.