Aluminum-air composite battery and preparation method

Patent metadata

Field	Value
Publication number	US-12308420-B1
Application number	US-202418957235-A
Country	US
Kind code	B1
Filing date	Nov 22, 2024
Priority date	Jan 10, 2024
Publication date	May 20, 2025
Grant date	May 20, 2025

Abstract

The present invention discloses an aluminum-air composite battery and a preparation method, which relates to the technical field of batteries. The present invention includes an aluminum-ion battery anode, an aluminum-ion battery cathode, an aluminum-air battery cathode and an alkaline electrolyte; MnO 2 , SiO 2 , TiO 2 , Mg, Ga, Sn, Bi, Zn and Al are mixed in proportion, melted in an inert gas environment, then refined and poured to prepare the aluminum-ion battery anode; α-MnO 2 , nickel oxide and anhydrous ethanol are mixed and calcined, and then mixed with Ketjen black, activated carbon, polytetrafluoroethylene dispersion and anhydrous ethanol into pulp; and the pulp is coated on a nickel fiber felt, pressed by a die and dried to prepare the aluminum-ion battery cathode.

First claim

What is claimed is:

1. An aluminum-air composite battery, comprising an aluminum-ion battery anode, an aluminum-ion battery cathode, an aluminum-air battery cathode and an alkaline electrolyte, wherein MnO 2 , SiO 2 , TiO 2 , Mg, Ga, Sn, Bi, Zn and Al are mixed in proportion, melted in an inert gas environment, then refined and poured to prepare the aluminum-ion battery anode;
α-MnO 2 , nickel oxide and anhydrous ethanol are mixed and calcined, and then mixed with Ketjen black, activated carbon, polytetrafluoroethylene dispersion and anhydrous ethanol into pulp; and the pulp is coated on a nickel fiber felt, pressed by a die and dried to prepare the aluminum-ion battery cathode;
a potassium permanganate solution is mixed with a carbon carrier; the mixture is processed by hydrothermal synthesis, filtration, washing and drying to make powder; the powder is mixed with polyvinylidene fluoride and N-methylpyrrolidone and coated on a waterproof conductive cloth; and after drying and aging, the aluminum-air battery cathode is prepared;
the alkaline electrolyte is prepared from indium sulfate, potassium citrate, sodium stannate, zinc oxide, glucose, potassium fluoride, casein, polyoxypropylene glycerol ether and a sodium hydroxide solution.

2. The aluminum-air composite battery according to claim 1 , wherein the aluminum-ion battery anode comprises the following raw materials by weight percentage: 0.8% of MnO 2 , 0.2% of SiO 2 , 0.01% of TiO 2 , 0.35% of Mg, 0.07% of Ga, 0.02% of Sn, 0.03% of Bi, 0.35% of Zn and the balance of Al.

3. The aluminum-air composite battery according to claim 2 , wherein a manufacturing process of the aluminum-ion battery anode comprises: heating Al metal in a crucible; when temperature rises to 720-735° C., adding MnO 2 , SiO 2 , TiO 2 , Ga, Sn, Bi and Zn metals and fully stirring slowly; when the temperature rises to 760-795° C., adding Mg metal; introducing inert gas into a melt, and keeping the temperature for 30-90 min; sprinkling a powdered flux for skimming; then casting in a die for cooling forming; keeping the temperature of an ingot in a cyclone boiler at 450-500° C. for 8-12 h and then immediately immersing in water, so that microalloy elements are solubilized in an Al matrix; sawing off a head and a tail of the ingot; removing a surface oxide; and cold-rolling to a required thickness.

4. The aluminum-air composite battery according to claim 1 , wherein the aluminum-ion battery cathode has the following raw materials by weight percentage: 28.4% of α-MnO 2 , 13.6% of nickel oxide, 17% of Ketjen black and 41% of activated carbon, wherein a dosage ratio of α-MnO 2 and nickel oxide with anhydrous ethanol is 3:10, and a dosage ratio of polytetrafluoroethylene dispersion and anhydrous ethanol in the mixed pulp is 1.2:5.

5. The aluminum-air composite battery according to claim 4 , wherein a manufacturing process of the aluminum-ion battery cathode comprises: mixing α-MnO 2 , nickel oxide and anhydrous ethanol, and then making anhydrous ethanol volatilize to obtain a mixture; heating the mixture at a rate of 10-18° C./min to 750-820° C. for calcining; keeping the temperature for 10-15 h to obtain a nickel-manganese-based composite material; mixing the nickel-manganese-based composite material, Ketjen black, activated carbon, polytetrafluoroethylene dispersion and anhydrous ethanol into pulp; coating the pulp on a nickel fiber felt by 0.5-1 mm; and pressing and drying successively.

6. The aluminum-air composite battery according to claim 1 , wherein the aluminum-air battery cathode comprises the following raw materials by weight percentage: 13.5% of potassium permanganate solution, 16.5% of carbon carrier mixture, 18% of polyvinylidene fluoride and 52% of N-methylpyrrolidone.

7. The aluminum-air composite battery according to claim 6 , wherein a manufacturing process of the aluminum-air battery cathode comprises: dissolving potassium permanganate in deionized water to prepare a potassium permanganate solution; then adding a carbon carrier to the potassium permanganate solution; stirring for 30-100 min to obtain an evenly dispersed potassium permanganate-carbon solution; conducting a high-temperature hydrothermal reaction for the potassium permanganate-carbon solution, and then filtering to obtain filter residues; washing and drying the filter residues for 4 times to obtain carbon-supported manganese dioxide catalyst powder; evenly mixing the carbon-supported manganese dioxide catalyst powder with polyvinylidene fluoride and then fully grinding; adding N-methylpyrrolidone; continuing to grind into pasty pulp; evenly coating the pulp on the surface of the waterproof conductive cloth by 0.1-0.3 mm; drying at 50-80° C. for 8-12 h; and aging at 100-120° C. for 6-9 h.

8. The aluminum-air composite battery according to claim 1 , wherein the alkaline electrolyte comprises the following raw materials by weight percentage: 0.12% of indium sulfate, 2% of potassium citrate, 0.4% of sodium stannate, 0.3% of zinc oxide, 0.35% of glucose, 6% of potassium fluoride, 0.15% of casein, 0.05% of polyoxypropylene glycerol ether and the balance of sodium hydroxide solution.

9. The aluminum-air composite battery according to claim 8 , wherein a manufacturing process of the alkaline electrolyte comprises: evenly mixing indium sulfate, potassium citrate, sodium stanylate, zinc oxide, glucose, potassium fluoride, casein and polyoxypropylene glycerol ether to prepare a corrosion inhibitor; adding the corrosion inhibitor to the sodium hydroxide solution; stirring for 20-35 min, so that the corrosion inhibitor is mixed evenly at a temperature of 60-82° C.; and then cooling to room temperature.

10. A preparation method of the aluminum-air composite battery, comprising the following steps:
S 1 , preparing the aluminum-ion battery anode from MnO 2 , SiO 2 , TiO 2 , Mg, Ga, Sn, Bi, Zn and Al as raw materials;
S 2 , preparing the aluminum-ion battery cathode from α-MnO 2 , nickel oxide, Ketjen black, activated carbon, polytetrafluoroethylene dispersion, anhydrous ethanol and the nickel fiber felt as raw materials;
S 3 , preparing the aluminum-air battery cathode from the potassium permanganate solution, the carbon carrier, polyvinylidene fluoride, N-methylpyrrolidone and the waterproof conductive cloth as raw materials;
S 4 , preparing the alkaline electrolyte from indium sulfate, potassium citrate, sodium stannate, zinc oxide, glucose, potassium fluoride, casein, polyoxypropylene glycerol ether and sodium hydroxide solution as raw materials; and
S 5 , assembling the aluminum-ion battery anode, the aluminum-ion battery cathode, the aluminum-air battery cathode and the alkaline electrolyte to prepare the aluminum-air composite battery.

Assignees

• Univ Hainan
• China Huadian Co Ltd
• Hainan Lvran Clean Energy Co Ltd
• Huadian Water Tech Co Ltd

Inventors

• Zheng Xuerong
• Deng Yida
• Huang Wenjie
• Wang Yang
• Chen beiyang
• Wang Haozhi
• Zhao Caiyun
• Liu Feng
• Li Rui

Classifications

• H01M4/0471

  involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis · CPC title

• H01M4/463

  Aluminium based · CPC title

• H01M4/381

  Alkaline or alkaline earth metals elements (H01M4/40 takes precedence) · CPC title

• H01M4/9016

  Oxides, hydroxides or oxygenated metallic salts · CPC title

• H01M4/387

  Tin or alloys based on tin · CPC title