CN111261946B - Aluminum ion battery electrolyte solution and battery - Google Patents
Aluminum ion battery electrolyte solution and battery Download PDFInfo
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- CN111261946B CN111261946B CN201811457153.3A CN201811457153A CN111261946B CN 111261946 B CN111261946 B CN 111261946B CN 201811457153 A CN201811457153 A CN 201811457153A CN 111261946 B CN111261946 B CN 111261946B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses an aluminum ion battery electrolyte solution and a battery. The electrolyte solution of the aluminum ion battery consists of a carbonate solvent, an amide cosolvent and an aluminum ion carrier. The carbon electrode cathode and the aluminum anode are immersed in the electrolyte solution to obtain the aluminum ion solid-liquid battery which is a secondary battery capable of being repeatedly charged and discharged, has the advantages of high energy density, high cost performance, safety superior to that of a lithium ion battery, rapid charging and discharging and the like, is suitable for being used as a power battery of a passenger vehicle, and can also be used as an energy storage device matched with a renewable energy power generation device.
Description
Technical Field
The invention belongs to the field of energy sources, and particularly relates to an aluminum ion electrolyte solution and a battery.
Background
The excellent safety performance, high energy density, and long charge-discharge cycle life make aluminum ion batteries considered as next-generation power batteries that are possible replacements for lithium ion batteries. Current research on aluminum ion batteries has focused primarily on electrode materials, particularly carbon cathode materials associated with aluminum anodes. Many researchers have attempted to improve the overall energy density and overall performance of the battery by improving carbon cathode materials, with less attention being paid to the electrolyte solution. For example, the aluminum ion battery was published in 2015 by Dacrogen, university of Stanford, USA, and the ion carrier in the electrolyte solution used was AlCl3Urea is used as an adjuvant. The aluminum chloride in organic solution has covalent compound property and cannot be ionized directly like ionic compound, so that AlCl3The electrochemical activity is weak and the conductivity is relatively low. The development lag of the electrolyte solution has become a bottleneck limiting the aluminum ion battery to enter into commercial application.
Disclosure of Invention
The invention aims to provide an aluminum ion battery electrolyte solution and a battery.
The present invention has been made in an attempt to provide an electrolyte solution for an aluminum ion battery and to apply the electrolyte solution to a solid-liquid type aluminum ion battery. The technical scheme adopted by the invention is as follows:
in a first aspect, the invention provides an aluminum ion battery electrolyte solution, which consists of a carbonate solvent, an amide cosolvent and an aluminum ion carrier, wherein the weight ratio of the carbonate solvent to the amide cosolvent is 6:1 to 9: 1; the aluminum ionophore accounts for 10-20% of the total weight of the solution.
The carbonate solvent may be one or more of carbonate compounds, including but not limited to Propylene Carbonate (PC), Ethylene Carbonate (EC), diethyl carbonate (DEC), Methyl Phenyl Carbonate (MPC), gamma-butyrolactone (GBL).
The amide cosolvent may be one or several of formamide, acetamide, propionamide and caproamide.
The aluminum ionophore can be one or more of organic acid aluminum salts, including but not limited to aluminum bromide, aluminum thiocyanate, aluminum triflate, aluminum methanesulfonate; wherein the aluminum bromide is an essential component of the aluminum ionophore, and the content of the aluminum ionophore is not less than 30 percent.
Further, the aluminum bromide can be prepared by adopting a commercial product or the following method:
mixing and uniformly stirring aluminum powder and bromine (namely liquid elemental bromine) according to the formula (1) chemical metering ratio, adding 3-5 times of carbonate compound solvent, and oscillating in a closed container until the aluminum powder and the bromine react and dissolve to obtain a carbonate solution of aluminum bromide;
2Al+3Br2＝2AlBr3 (1)。
further, the aluminum thiocyanate, the aluminum trifluoromethanesulfonate and the aluminum methanesulfonate can be prepared by the following methods:
respectively dissolving sodium thiocyanate, sodium trifluoromethanesulfonate and sodium methanesulfonate in absolute alcohol or other organic solvents to obtain sodium salt solutions, and dissolving aluminum trichloride in absolute alcohol or other organic solvents to obtain aluminum trichloride solutions; respectively mixing an aluminum trichloride solution with four sodium salt solutions one by one while stirring, wherein the solute mole numbers of the two mixed solutions are in accordance with the stoichiometric ratio of formulas (2) to (5) (namely, the stoichiometric ratio in a reaction formula corresponding to a prepared target product needs to be selected), so as to obtain aluminum thiocyanate, aluminum trifluoromethanesulfonate, an aluminum methanesulfonate solution and a NaCl suspension, filtering, precipitating or centrifuging to remove NaCl precipitates, and evaporating a clear solution to dryness, so as to obtain a target compound:
3NaSCN+AlCl3＝Al(SCN)3+3NaCl↓ (2)
3NaCF3SO3+AlCl3＝Al(CF3SO3)3+3NaCl↓ (3)
3NaCF3SO2+AlCl3＝Al(CF3SO2)3+3NaCl↓ (4)
3NaCH3O2S+AlCl3＝Al(CH3O2S)3+3NaCl↓ (5)。
in a second aspect, the present invention provides a solid-liquid battery using the electrolyte solution of the aluminum-ion battery according to any one of the above schemes, and the solid-liquid battery has a specific structure: placing a carbon electrode cathode and an aluminum anode in a sealed electrolyte tank in a matched manner, and immersing the carbon electrode cathode and the aluminum anode in the electrolyte solution of the aluminum ion battery, wherein the carbon electrode cathode and the aluminum anode are separated by a diaphragm or keep a distance of 0.5-1.5 mm; the carbon electrode and the aluminum anode are respectively used as a battery cathode and a battery anode; the battery is a secondary battery, a carbon electrode cathode and an aluminum anode are respectively connected to a negative electrode and a positive electrode of an external power supply for charging, and the carbon electrode cathode and the aluminum anode are respectively connected to the negative electrode and the positive electrode of an external circuit after charging is finished, so that the battery is in a standby state; the battery can be recharged for reuse after being discharged.
In a third aspect, the present invention provides a battery assembling and using method of the solid-liquid battery, which comprises the following steps:
1) preparing a carbonate solvent, an amide cosolvent and an aluminum ion carrier into an electrolyte solution according to a proportion;
2) after the aluminum anode is soaked in the organic acid solution, the aluminum anode and the carbon electrode cathode are arranged and assembled in place, the aluminum anode and the carbon electrode cathode are placed into an electrolyte tank, and electrolyte solution is filled into the electrolyte tank to submerge the electrodes;
3) keeping the electrolyte tank, the electrodes and the electrolyte solution at the constant temperature of 90-110 ℃ for 1-2 hours and vacuumizing;
4) and after heating and vacuumizing are finished, taking out the battery, sealing the electrolyte tank, and respectively connecting the aluminum anode and the carbon electrode cathode to the positive electrode and the negative electrode of an external power supply for charging.
The solvent may be one or more of carbonate compounds, including but not limited to Propylene Carbonate (PC), Ethylene Carbonate (EC), diethyl carbonate (DEC), Methyl Phenyl Carbonate (MPC), gamma-butyrolactone (GBL).
The cosolvent can be one or more of formamide, acetamide, propionamide and caproamide.
The ion carrier can be one or more of organic acid aluminum salts such as aluminum bromide, aluminum thiocyanate, aluminum trifluoromethanesulfonate and the like. Wherein the aluminum bromide is an essential component, and the content of the aluminum bromide in the ionophore is not less than 30%.
The aluminum anode is a battery anode made of a metal aluminum plate or a metal aluminum bar, and the shape of the aluminum anode needs to be matched with that of a carbon electrode.
The organic acid solution can be one or more of methanesulfonic acid, trifluoromethanesulfonic acid and trifluoromethanesulfonic acid which are dissolved in absolute alcohol.
In addition, if the battery works in seawater, when the battery is discharged and needs electricity urgently, extra electric energy can be obtained through the following steps:
1) switching the position of the anode and the cathode of the battery, namely connecting the metal aluminum anode to the cathode of an external circuit, and connecting the carbon electrode to the anode of the external circuit;
2) opening the electrolytic bath to allow the electrodes to directly contact the seawater and keeping the battery open to the environmental seawater; the seawater reacts with the metal aluminum electrode and the carbon electrode to form current and do work.
The electrolyte solution of the aluminum ion battery provided by the invention has the advantages of high electrochemical activity and high conductivity, and is suitable for various aluminum ion batteries. The aluminum ion solid-liquid battery based on the electrolyte solution has the advantages of high energy density, high cost performance, safety superior to that of a lithium ion battery, rapid charge and discharge and the like, is suitable for being used as a power battery of a passenger vehicle, and can also be used as an energy storage device matched with a renewable energy power generation device. When the power battery is used for a power battery of marine equipment, extra power supply can be provided by introducing seawater and switching the connection of the positive electrode and the negative electrode when the power is exhausted, and the power battery has special significance for marine observation equipment and submersible vehicles.
Detailed Description
The invention will be further illustrated and described with reference to specific embodiments. The technical features of the various implementations may be combined without conflict with each other and do not constitute a limitation to the present invention.
The invention provides an aluminum ion battery electrolyte solution, which consists of a carbonate solvent, an amide cosolvent and an aluminum ion carrier, wherein the weight ratio of the carbonate solvent to the amide cosolvent is 6:1 to 9: 1; the aluminum ionophore accounts for 10-20% of the total weight of the solution.
The carbonate solvent is one or more of carbonate compounds, including but not limited to Propylene Carbonate (PC), Ethylene Carbonate (EC), diethyl carbonate (DEC), Methyl Phenyl Carbonate (MPC), gamma-butyrolactone (GBL).
The carbonate solvent has good electrochemical stability and low melting point, and is widely used in lithium ion batteries. The anode of the aluminum ion battery is metallic aluminum, the cathode is carbon, and the carbonate is inert to the two electrode materials and cannot corrode the electrodes, so that the carbonate solvent is also suitable for the aluminum ion battery. The performance of the solvent formed by compatibility of various carbonates is that single-component carbonates are used, and various carbonate formulations are used as much as possible.
Considering that the electrolyte solution usually needs to be dehydrated by heating before use, carbonates with low melting point and high boiling point are preferably used in the solvent formulation, such as: propylene Carbonate (PC), melting point-42.9 ℃, boiling point 241.7 ℃; diethyl carbonate (DEC), melting point-43 deg.C, boiling point 127 deg.C; methyl Phenyl Carbonate (MPC), melting point-43 deg.C, boiling point 130 deg.C; gamma-butyrolactone (GBL), melting point-42 ℃ and boiling point 206 ℃. The low melting point is beneficial to keeping good working performance of the battery in an extreme low temperature environment, and the high boiling point is beneficial to improving the safety coefficient. In addition to temperature considerations, solvent formulations also take into account viscosity, compatibility with other components, and solubility in the ionophore.
The amide cosolvent is one or more of formamide, acetamide, propionamide and caproamide. The cosolvent has the functions of increasing the solubility of the ionophore in the electrolyte solution and inhibiting the generation of other byproducts in the charging and discharging process. The amide compounds have large molecular polarity and high solubility to ionic organic and inorganic compounds. Because of the strong association ability of hydrogen bonds between amide molecules, the melting point of the amide is higher than that of compounds with similar molecular mass. Due to their high electrochemical activity and their specific solubility, the use of formamide as a cosolvent is recommended. The weight ratio of the carbonate solvent to the amide cosolvent is 6:1 to 9: 1.
The aluminum ion carrier is one or more of organic acid aluminum salts such as aluminum bromide, aluminum thiocyanate, aluminum trifluoromethanesulfonate and aluminum methanesulfonate. Wherein the aluminum bromide is an essential component, and the content of the aluminum bromide in the ionophore is not less than 30%.
The aluminum bromide can be a commercial product and can also be prepared by the following method: mixing and uniformly stirring aluminum powder and bromine (liquid simple substance bromine) according to the formula (1) chemical weight ratio, adding 3-5 times of carbonate solvent, and oscillating in a closed container until the aluminum powder and the bromine react and dissolve to obtain the carbonate solution of aluminum bromide. And adding other components into the solution to obtain the electrolyte solution of the aluminum ion battery. The solution method for preparing the aluminum bromide avoids the hydrolysis of the aluminum bromide on one hand, and simultaneously, the product does not need to be separated from the solution, thereby greatly reducing the cost.
2Al+3Br2＝2AlBr3 (1)
The organic aluminum salts such as aluminum thiocyanate, aluminum trifluoromethanesulfonate and aluminum methanesulfonate can be commercial products and can also be prepared by the following method: respectively dissolving sodium thiocyanate, sodium trifluoromethanesulfonate and sodium methanesulfonate in absolute alcohol or other organic solvents to obtain sodium salt solutions, and dissolving aluminum trichloride in absolute alcohol or other organic solvents to obtain aluminum trichloride solutions; respectively mixing an aluminum trichloride solution with four sodium salt solutions one by one while stirring, wherein the solute mole numbers of the two mixed solutions meet the stoichiometric ratio of formulas (2) to (5) (different target products are prepared by selecting different proportions, namely selecting the stoichiometric ratio in a reaction formula corresponding to the prepared target products), obtaining aluminum thiocyanate, aluminum trifluoromethanesulfonate, aluminum methanesulfonate solution and NaCl suspension, filtering, precipitating or centrifuging to remove NaCl precipitates, and evaporating clear liquid to dryness to obtain a target compound:
3NaSCN+AlCl3＝Al(SCN)3+3NaCl↓ (2)
3NaCF3SO3+AlCl3＝Al(CF3SO3)3+3NaCl↓ (3)
3NaCF3SO2+AlCl3＝Al(CF3SO2)3+3NaCl↓ (4)
3NaCH3O2S+AlCl3＝Al(CH3O2S)3+3NaCl↓ (5)
in the above-mentioned ionophore, aluminum bromide is an essential component, and its weight ratio in the ionophore is not less than 30%. Another ionophore suggested the use of aluminum methanesulfonate for cost performance and safety reasons.
The second aspect of the invention provides a solid-liquid battery using the electrolyte solution of the aluminum ion battery. The specific structure of the battery is as follows: placing a carbon electrode cathode and an aluminum anode in a sealed electrolyte tank in a matched manner, and immersing the carbon electrode cathode and the aluminum anode in an electrolyte solution, wherein the carbon electrode cathode and the aluminum anode are separated by a diaphragm or keep a distance of 0.5-1.5 mm; the carbon electrode and the aluminum anode are respectively used as a battery cathode and a battery anode; the battery is a secondary battery, a carbon electrode cathode and an aluminum anode are respectively connected to a negative electrode and a positive electrode of an external power supply for charging, and the carbon electrode cathode and the aluminum anode are respectively connected to the negative electrode and the positive electrode of an external circuit after charging is finished, so that the battery is in a standby state; the battery can be recharged for reuse after being discharged.
The structure of the solid-liquid battery is similar to that of the lead-acid battery which is commonly used at present, and the aluminum anode and the carbon cathode are mutually separated electrode plates or electrode rods which are soaked in the same electrolyte solution. The solid-liquid structure of the lead-acid battery is different from that of most lithium ion batteries and aluminum ion batteries at present, the solid-liquid structure of the lead-acid battery generally adopts a liquid film structure, a positive electrode material and a negative electrode material are rolled into a cylinder shape, and the middle of the positive electrode material and the negative electrode material are separated by a diaphragm. Compared with a liquid film structure, the solid-liquid structure is solid and durable, and the hidden danger that the diaphragm is easily pierced by needle crystals formed by charge-discharge reaction is avoided.
The third aspect of the invention provides an assembly and use method of the aluminum ion solid-liquid battery, which comprises the following steps:
1) preparing a carbonate solvent, an amide cosolvent and an aluminum ion carrier into an electrolyte solution according to a proportion, wherein the weight ratio of the carbonate solvent to the amide cosolvent is 6:1 to 9: 1; the aluminum ionophore accounts for 10-20% of the total weight of the solution. When in preparation, the carbonate solution of the aluminum bromide can be prepared according to the method, and then other components are added into the carbonate solution of the aluminum bromide.
The carbonate solvent is one or more of carbonate compounds, including but not limited to Propylene Carbonate (PC), Ethylene Carbonate (EC), diethyl carbonate (DEC), Methyl Phenyl Carbonate (MPC), gamma-butyrolactone (GBL).
The carbonic ester as solvent has good compatibility and chemical stability with carbon electrode and carbon/aluminum composite electrode, and has no corrosion to electrode material.
The amide cosolvent is one or more of formamide, acetamide, propionamide and caproamide. The amide compounds have large molecular polarity and high solubility to ionic organic and inorganic compounds.
The aluminum ion carrier is one or more of organic acid aluminum salts such as aluminum bromide, aluminum thiocyanate, aluminum trifluoromethanesulfonate and the like. Wherein the aluminum bromide is an essential component, and the content of the aluminum bromide in the ionophore is not less than 30%.
The aluminum salts used as the ion carriers are all ionic compounds, have higher solubility in carbonate-amide solvent systems, and enable the solution to have higher conductivity. Among the several ionophores, aluminum bromide is of crucial importance and is the active component in electrochemical reactions during charging and discharging.
2) After the aluminum anode is soaked in the organic acid solution, the aluminum anode and the carbon electrode cathode are arranged and assembled in place, the aluminum anode and the carbon electrode cathode are placed into an electrolyte tank, and electrolyte solution is filled into the electrolyte tank to submerge the electrodes.
The organic acid solution is one or more of methanesulfonic acid, trifluoromethanesulfonic acid and trifluoromethanesulfonic acid dissolved in absolute alcohol.
Both the metal aluminum anode and the carbon/aluminum composite anode form an inert oxide film on the surface after contacting with air, thereby greatly reducing the electrochemical activity of the anode material. In order to make the charging and discharging reaction proceed smoothly, the oxide film on the surface of the electrode needs to be removed by using an organic acid solution, and the reaction mechanism is shown as formula (6), namely: organic acid and amphoteric oxide aluminium oxide generate aluminium salt and water, wherein the aluminium salt becomes an ion carrier in the electrolyte solution, and the water is removed in the subsequent heating and vacuumizing processes.
Al2O3+6CH4O3S＝2Al(CH3O3S)3+3H2O (6)
2Al+6CH4O3S＝2Al(CH3O3S)3+3H2 (7)
The organic acid dissolves aluminum oxide in the formula (6), and corrodes the aluminum anode in the formula (7). The dosage of the organic acid is not large, so that the shape and the size of the aluminum anode are not greatly influenced; the released hydrogen gas is removed in the next evacuation process. The residual small amount of organic acid will react with amide cosolvent to produce alcohol, which is converted into part of solvent.
3) And heating the electrolyte tank together with the electrode and the solution at the constant temperature of 90-110 ℃ for 1-2 hours and vacuumizing.
The purpose of heating and vacuum is to remove water and volatile solvents from the electrolyte solution. Part of the water comes from the reaction (6), and in addition, the solvent absorbs water from the environment during storage and transportation.
4) And after heating and vacuumizing are finished, the battery is taken out of the vacuum oven, the electrolyte tank is sealed, and the aluminum anode and the carbon electrode cathode are respectively connected to the positive electrode and the negative electrode of an external power supply for charging.
The first charging process suggests a multiplying voltage, i.e. 4-5V, for charging in order to activate the aluminum anode. The charging voltage gram is set at 1.8-2V.
The reaction of the aluminum ion secondary battery during the charging process is as follows:
br formed by electric current after dissolution of aluminium bromide-Ions react with Al in a charging reaction3+The transport of ions from the anode to the cathode, i.e.: br-The ions lose electrons at the anode and are reduced to elemental bromine, as shown in formula (8):
2Br--2e-＝Br2E0＝-1.0873V (8)
the elemental bromine reacts with the metallic aluminum to produce aluminum bromide, which is subsequently ionized in solution to form Al3+Ion:
3Br2+2Al＝2AlBr3 (9)
AlBr3＝Al3++3Br- (10)
formed Al3+The ions migrate to the cathode under the action of the external electric field and are embedded into the carbon cathode:
Al0→Al3++3e-(Positive electrode reaction, E)0＝-1.662V) (11)
C6+Al3++3e-→AlC6(negative electrode reaction) (12)
The reactions (8) to (10) promote the dissolution of aluminum in the reaction (11)Acting but Br in the whole system-The concentration of the ions remains unchanged. In this sense, Br is present during charging-The ions are the catalyst for the dissolution of the aluminum metal present in the anode.
The main reactions of the charging process are (11) and (12): under the action of an external electric field, Al3+Ions dissolve from the aluminum anode and intercalate into the carbon cathode material; the positive electrode releases electrons and enters the negative electrode through an external circuit.
And (3) discharging: the negative electrode releases electrons (enters the positive electrode) through an external circuit, and the negative electrode releases Al into the electrolyte3+Ions are formed and precipitated on the metallic aluminum anode.
Al3++3e-→Al0(Positive electrode reaction) (13)
AlC6→C6+Al3++3e-(negative electrode reaction) (14)
The overall cell reaction is:
the charging voltage is recommended to be controlled between 1.0V and 2.0V according to the standard electrode potential of the relevant substance given by the formulas (8) and (11). During the first charging, in order to overcome the surface chemical inertia of the electrode, the electrode needs to be activated by adopting higher voltage. The initial charge activation voltage is recommended to be 4-5V.
During charging and discharging, Al3+The principle model of the movement between the anode and the cathode is called a rocking chair type or a teeterboard type, and the principle model is suitable for explaining the working principle of the aluminum ion secondary battery under normal conditions.
After charging, the aluminum anode and the carbon cathode are respectively connected to the positive pole and the negative pole of an external circuit, and the battery is in a standby state. In this case, the battery is a rechargeable secondary aluminum ion battery.
The fourth aspect of the present invention provides a method for obtaining additional electric energy from the above solid-liquid battery, that is: if the battery works in seawater, when the battery is discharged and needs electricity urgently, the extra electric energy can be obtained through the following steps:
1) switching the positive and negative electrodes of the battery to positions, namely: connecting a metal aluminum electrode to the negative electrode of an external circuit, and connecting a carbon electrode to the positive electrode of the external circuit;
2) the electrolyte tank is opened to allow the electrodes to directly contact the seawater and to maintain the cell open to the ambient seawater. The seawater reacts with the metal aluminum electrode and the carbon electrode to form current and do work.
The electrochemical reaction at discharge is:
negative electrode: (metallic aluminum electrode): 4 Al-12 e-＝4Al3+ (16)
And (3) positive electrode: (carbon electrode): 3O2+6H2O+12e-＝12OH- (17)
The general reaction formula is as follows: 4Al +3O2+6H2O＝4Al(OH)3↓ (18)
The discharge process causes the aluminum metal cathode to be gradually dissolved, and the carbon electrode and the metallic nickel particles attached thereto function as a catalyst and conduct current. The essence of this mode of operation is a disposable seawater/aluminum battery that cannot be recharged after discharge.
The present invention will be described in detail with reference to examples. Examples 1 to 4 are examples of producing an electrolyte solution for an aluminum ion battery, and some of the raw materials used in the examples may be commercial products or may be produced in the manner described in examples 5 to 9. Examples 10 to 12 are examples of producing a solid-liquid battery. Example 13 is a way to derive additional energy from such a solid-liquid battery.
Example 1
And taking 5 kg of propylene carbonate, adding 1 kg of ethylene carbonate, 1 kg of formamide, 0.4 kg of aluminum bromide and 0.4 kg of aluminum thiocyanate, and stirring until the materials are completely dissolved to obtain the electrolyte solution of the aluminum ion battery.
Example 2
And taking 8 kg of diethyl carbonate, adding 1 kg of ethylene carbonate, 1 kg of acetamide, 0.85 kg of aluminum bromide and 1.75 kg of aluminum trifluoromethanesulfonate, and stirring until the mixture is completely dissolved to obtain the electrolyte solution of the aluminum ion battery.
Example 3
And stirring 8 kg of methyl phenyl carbonate, 1 kg of propionamide, 0.6 kg of aluminum bromide and 1.2 kg of aluminum trifluoro-methane sulfinate until the aluminum trifluoro-methane sulfinate is completely dissolved to obtain the electrolyte solution of the aluminum ion battery.
Example 4
And (3) taking 7 kg of gamma-butyrolactone, 1 kg of caproamide, 0.5 kg of aluminum bromide and 1.0 kg of aluminum methanesulfonate, and stirring until the materials are completely dissolved to obtain the electrolyte solution of the aluminum ion battery.
Example 5
90.3 g of Propylene Carbonate (PC), 8 g of liquid bromine and 2.7 g of metal aluminum powder are sequentially added into a polytetrafluoroethylene plastic bottle, and a bottle cap is tightly covered. Placing the bottle on an oscillator to oscillate for 4 hours to obtain AlBr with the concentration of 10%3And (3) solution.
Example 6
Weighing 81.07 g of sodium thiocyanate, dissolving in 1L of absolute alcohol, and stirring until the sodium thiocyanate is completely dissolved; 133.34 g of aluminum trichloride was dissolved in 1.5L of anhydrous alcohol and stirred until completely dissolved. And (3) rapidly mixing the two solutions while stirring, continuously stirring for 10 minutes, filtering, precipitating or centrifuging to remove precipitates, and evaporating clear liquid to dryness to obtain 201.22 g of aluminum thiocyanate.
Example 7
172.06 g of sodium trifluoromethanesulfonate is weighed and dissolved in 1.7L of absolute alcohol, and stirred until the sodium trifluoromethanesulfonate is completely dissolved; 133.34 g of aluminum trichloride was dissolved in 1.5L of anhydrous alcohol and stirred until completely dissolved. And (3) rapidly mixing the two solutions while stirring, continuously stirring for 10 minutes, filtering, precipitating or centrifuging to remove precipitates, and evaporating clear liquid to dryness to obtain 474.19 g of aluminum trifluoromethanesulfonate.
Example 8
156.06 g of sodium trifluoromethanesulfonate is weighed and dissolved in 1.5L of absolute alcohol, and stirred until the sodium trifluoromethanesulfonate is completely dissolved; 133.34 g of aluminum trichloride was dissolved in 1.5L of anhydrous alcohol and stirred until completely dissolved. And (3) rapidly mixing the two solutions while stirring, continuously stirring for 10 minutes, filtering, precipitating or centrifuging to remove precipitates, and evaporating clear liquid to dryness to obtain 426.19 g of aluminum trifluoromethanesulfonate.
Example 9
306.3 g of sodium methanesulfonate is weighed and dissolved in 1.0L of absolute alcohol, and stirred until the sodium methanesulfonate is completely dissolved; 133.34 g of aluminum trichloride was dissolved in 1.5L of anhydrous alcohol and stirred until completely dissolved. And (3) rapidly mixing the two solutions while stirring, continuously stirring for 10 minutes, filtering, precipitating or centrifuging to remove precipitates, and evaporating clear liquid to dryness to obtain 264.28 g of aluminum methylsulfonate.
Example 10
1) 6 kg of propylene carbonate, 1 kg of formamide, 0.4 kg of aluminum bromide and 0.4 kg of aluminum methanesulfonate are stirred to be completely dissolved, so as to obtain the electrolyte solution of the aluminum ion battery.
2) Immersing the carbon/aluminum composite anode in absolute alcohol solution containing 10% methanesulfonic acid to ensure that the electrode is saturated with the solution; then the carbon/aluminum composite anode and the porous carbon cathode are arranged and assembled in place, and are placed into an electrolyte tank, and electrolyte solution is filled into the electrolyte tank to submerge the electrodes.
3) And putting the electrolyte tank, the electrode and the solution into a vacuum oven at 90 ℃ and keeping the temperature for 2 hours.
4) And after heating and vacuumizing are finished, the battery is taken out of the vacuum oven, the electrolyte tank is sealed, and the carbon/aluminum composite anode and the porous carbon cathode are respectively connected to the anode and the cathode of an external power supply for charging.
Example 11
1) And stirring 9 kg of diethyl carbonate, 1 kg of acetamide, 0.85 kg of aluminum bromide and 1.75 kg of aluminum trifluoromethanesulfonate until the diethyl carbonate, the acetamide, the aluminum bromide and the aluminum trifluoromethanesulfonate are completely dissolved to obtain the electrolyte solution of the aluminum ion battery.
2) Immersing the carbon/aluminum composite anode in absolute alcohol solution containing 10% of trifluoromethanesulfonic acid to make the electrode saturated with the solution; then the carbon/aluminum composite anode and the porous carbon cathode are arranged and assembled in place, and are placed into an electrolyte tank, and electrolyte solution is filled into the electrolyte tank to submerge the electrodes.
3) The electrolyte tank, the electrode and the solution are placed in a vacuum oven at 110 ℃ and the temperature is kept constant for 1 hour.
4) And after heating and vacuumizing are finished, the battery is taken out of the vacuum oven, the electrolyte tank is sealed, and the carbon/aluminum composite anode and the porous carbon cathode are respectively connected to the anode and the cathode of an external power supply for charging.
Example 12
1) And taking 8 kg of gamma-butyrolactone, 1 kg of propionamide, 0.6 kg of aluminum bromide and 1.2 kg of aluminum trifluoromethane sulfinate, and stirring until the gamma-butyrolactone, the propionamide, the aluminum bromide and the aluminum trifluoromethane sulfinate are completely dissolved to obtain the electrolyte solution of the aluminum ion battery.
2) Immersing the carbon/aluminum composite anode in anhydrous alcohol solution containing 10% trifluoromethane sulfinic acid to ensure that the electrode is saturated with the solution; then the carbon/aluminum composite anode and the porous carbon cathode are arranged and assembled in place, and are placed into an electrolyte tank, and electrolyte solution is filled into the electrolyte tank to submerge the electrodes.
3) The electrolyte tank, the electrode and the solution are placed in a vacuum oven at 100 ℃ and the temperature is kept constant for 1.5 hours.
4) And after heating and vacuumizing are finished, the battery is taken out of the vacuum oven, the electrolyte tank is sealed, and the carbon/aluminum composite anode and the porous carbon cathode are respectively connected to the anode and the cathode of an external power supply for charging.
Example 13
1) The battery works in seawater, after the electric quantity is exhausted, the metal aluminum electrode is connected to the negative electrode of the external circuit, and the carbon electrode is connected to the positive electrode of the external circuit, so that the exchange of the positive electrode and the negative electrode is realized.
2) The electrolyte tank is opened to allow the electrodes to directly contact the seawater and to maintain the cell open to the ambient seawater. The seawater reacts with the metal aluminum electrode and the carbon electrode to form current and do work.
The above-described embodiments are merely preferred embodiments of the present invention, which should not be construed as limiting the invention. Various changes and modifications may be made by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present invention. Therefore, the technical scheme obtained by adopting the mode of equivalent replacement or equivalent transformation is within the protection scope of the invention.
Claims (6)
1. An aluminum ion battery electrolyte solution is characterized by comprising a carbonate solvent, an amide cosolvent and an aluminum ion carrier, wherein the weight ratio of the carbonate solvent to the amide cosolvent is 6:1 to 9: 1; the aluminum ion carrier accounts for 10-20% of the total weight of the solution;
the aluminum ionophore comprises one or more of aluminum bromide, aluminum thiocyanate, aluminum trifluoromethanesulfonate and aluminum methanesulfonate; wherein the aluminum bromide is an essential component of the aluminum ionophore, and the content of the aluminum bromide in the aluminum ionophore is not less than 30%.
2. The electrolyte solution for aluminum ion batteries according to claim 1, wherein said carbonate-based solvent is one or more carbonate-based compounds selected from the group consisting of Propylene Carbonate (PC), Ethylene Carbonate (EC), diethyl carbonate (DEC), Methyl Phenyl Carbonate (MPC), and gamma-butyrolactone (GBL).
3. The electrolyte solution of an aluminum ion battery according to claim 1, wherein the amide cosolvent is one or more of formamide, acetamide, propionamide, and caproamide.
4. The aluminum-ion battery electrolyte solution of claim 1 wherein the aluminum bromide is prepared by the method comprising:
mixing and uniformly stirring aluminum powder and bromine according to the formula (1) chemical metering ratio, adding 3-5 times of carbonate compound solvent, and oscillating in a closed container until the aluminum powder reacts with the bromine and is dissolved, thereby obtaining a carbonate solution of aluminum bromide;
2Al+3Br2＝2AlBr3 (1)。
5. the aluminum ion battery electrolyte solution of claim 1 wherein the aluminum thiocyanate, aluminum triflate, aluminum methanesulfonate, was prepared by the following method:
respectively dissolving sodium thiocyanate, sodium trifluoromethanesulfonate and sodium methanesulfonate in absolute ethyl alcohol or other organic solvents to obtain sodium salt solutions, and dissolving aluminum trichloride in absolute ethyl alcohol or other organic solvents to obtain aluminum trichloride solutions; respectively mixing an aluminum trichloride solution with four sodium salt solutions one by one while stirring, wherein the solute mole numbers of the two mixed solutions meet the stoichiometric ratio of formulas (2) to (5), so as to obtain an aluminum thiocyanate, an aluminum trifluoromethanesulfonate solution and a NaCl suspension, filtering, precipitating or centrifuging to remove NaCl precipitates, and evaporating a clear solution to dryness, so as to obtain a target compound:
3NaSCN+AlCl3＝Al(SCN)3+3NaCl↓ (2)
3NaCF3SO3+AlCl3＝Al(CF3SO3)3+3NaCl↓ (3)
3NaCF3SO2+AlCl3＝Al(CF3SO2)3+3NaCl↓ (4)
3NaCH3O2S+AlCl3＝Al(CH3O2S)3+3NaCl↓ (5)。
6. an aluminum ion battery adopting the electrolyte solution of the aluminum ion battery as claimed in any one of claims 1 to 5, wherein a carbon electrode cathode and an aluminum anode are matched and arranged in a sealed electrolyte tank, and are both immersed in the electrolyte solution of the aluminum ion battery, and are separated by a diaphragm or kept at a distance of 0.5-1.5 mm; the carbon electrode and the aluminum anode are respectively used as a battery cathode and a battery anode; the battery is a secondary battery, a carbon electrode cathode and an aluminum anode are respectively connected to a negative electrode and a positive electrode of an external power supply for charging, and the carbon electrode cathode and the aluminum anode are respectively connected to the negative electrode and the positive electrode of an external circuit after charging is finished, so that the battery is in a standby state; the battery can be recharged for reuse after being discharged.
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