CN115911369A - Organic positive electrode of aluminum ion battery and aluminum ion battery - Google Patents
Organic positive electrode of aluminum ion battery and aluminum ion battery Download PDFInfo
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Abstract
The invention discloses an organic anode of an aluminum ion battery and the aluminum ion battery, and relates to the technical field of secondary batteries. By introducing the p-type organic compound into the positive electrode, the p-type organic compound has higher working voltage than other organic materials by utilizing the unique anionic redox characteristic of the p-type organic compound; the p-type organic compound does not generate the damage of old chemical bonds and the formation of new chemical bonds in the reversible coordination-dissociation process with coordination ions, and shows good chemical stability and fast reaction kinetics. In addition, the p-type polymer cathode material has low solubility in the ionic liquid electrolyte and shows excellent charge-discharge cycle stability.
Description
Technical Field
The invention relates to the technical field of secondary batteries, in particular to an organic positive electrode of an aluminum ion battery and the aluminum ion battery.
Background
With the large-scale application of electrochemical energy storage technology, the disadvantages of lithium ion batteries in terms of their resource reserves, inherent safety risks and high costs develop. Currently, various novel metal ion batteries (sodium ion, potassium ion, zinc ion, magnesium ion, aluminum ion, etc.) are widely studied as substitutes of the latter lithium ion battery age. Among them, the aluminum ion battery has the highest volumetric energy density and high mass energy density. In addition, aluminum is the most abundant metal element in the earth crust, and the intrinsic safety of aluminum makes the aluminum ion battery a next-generation large-scale energy storage technology with great potential. At the present stage, one of the major obstacles to be overcome by aluminum ion batteries is the development of high-kinetic and high-stability cathode materials.
At present, graphite-based positive electrode materials are matched with ionic liquid electrolyte, and the aluminum ion battery system is most widely applied. However, limited by their large size of active carriers ([ AlCl) 4 - ]) Resulting in its comparatively low discharge capacity and large volume expansion. In addition, various novel cathode materials, including transition metal oxides, sulfides, selenides, tellurides, prussian blue, etc., have been developed to further improve the capacity and energy density of the aluminum ion battery. However, due to Al 3+ With high charge density, strong electrostatic interactions with the positive electrode result in poor kinetics. Also, during intercalation/deintercalation, large volume changes also cause the cathode structure to collapse, resulting in deterioration of cycle performance. In contrast, organic materials exhibit fast kinetics and high cycling stability by virtue of their unique coordination chemistry mechanisms and flexible structures. In addition, the organic material mainly comprises sustainable elements such as C, H, O, N and the like, so that the limitation of mineral resources is avoided.
However, the existing organic positive electrodes generally exhibit a low operating voltage, resulting in a limitation in practical applications thereof. Therefore, the design and development of a novel high-voltage organic cathode material-based aluminum ion battery have very important significance.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide an organic anode of an aluminum ion battery and the aluminum ion battery, and aims to solve the problem of low working voltage of the organic aluminum ion battery and realize quick charge and discharge and good cycle performance.
The invention is realized by the following steps:
the invention provides an organic anode of an aluminum ion battery, which comprises 40-80 parts of organic active substances, 10-50 parts of conductive agents and 8-12 parts of binders in parts by mass;
wherein the organic active substance is a p-type organic compound or a polymer obtained by reacting the p-type organic compound.
In an alternative embodiment, the organic active material is 50 to 70 parts, the conductive agent is 20 to 40 parts, and the binder is 8 to 12 parts.
In an alternative embodiment, the p-type organic compound is a heterocyclic compound or a derivative thereof, and the heterocyclic compound contains an element of N, S or O;
preferably, the p-type organic compound is selected from at least one of phenothiazine, phenoxazine, thianthrene, thiophene, piperazine, promethazine, flavin, and pteridine.
In an alternative embodiment, the polymer is obtained by grafting a p-type organic compound onto a stable polymer chain, or by reaction with other organic compounds;
wherein the stable polymer chain is selected from at least one of organic polynorbornene, polyvinyl benzyl chloride and polyethylene.
In an alternative embodiment, the organic active is selected from at least one of poly-3-vinyl-N-methylphenoxazine, phenothiazine, 5, 10-dihydro-5, 10-diphenylphenazine, thianthrene, benzothiophene, and poly-N-propylphenothiazine.
In an alternative embodiment, the conductive agent is selected from at least one of acetylene black, conductive carbon black, ketjen black, graphene, and carbon nanotubes;
the binder is at least one selected from polyvinylidene fluoride, sodium carboxymethylcellulose, sodium alginate, sodium polyacrylate and styrene butadiene rubber.
In a second aspect, the present invention provides an aluminum ion battery comprising an anode, an electrolyte and a cathode, the cathode being prepared from the organic cathode of the aluminum ion battery of any one of the preceding embodiments.
In an alternative embodiment, the process for preparing the positive electrode comprises: preparing materials according to the composition of the organic anode of the aluminum ion battery, mixing and dissolving to obtain a material to be coated, coating the material to be coated on a conductive current collector, and drying;
preferably, the drying is vacuum drying at 50-120 deg.C for 5-15h;
preferably, the solvent used in the dissolving process is N-methyl pyrrolidone;
preferably, the conductive current collector is made of molybdenum foil;
preferably, the method further comprises the step of punching the dried pole piece into a positive electrode with a required size.
In an alternative embodiment, the negative electrode is a surface-treated aluminum metal material, and the organic positive electrode and the negative electrode of the aluminum ion battery are separated by a glass fiber diaphragm;
preferably, the surface treatment mode is at least one of mechanical grinding, chemical erosion, ion liquid soaking or surface coating artificial solid electrolyte interface film; the thickness of the metal aluminum material is 20-500 μm;
more preferably, the process for preparing the artificial solid electrolyte interface membrane comprises: mixing the montmorillonite substituted by aluminum cations with a binder, and coating the mixture on a metal aluminum material to form the aluminum-based composite material;
the thickness of the artificial solid electrolyte interface film is 1 μm to 10 μm.
In an alternative embodiment, the electrolyte is an anhydrous aluminum chloride-based ionic liquid;
preferably, the preparation process of the anhydrous aluminum chloride-based ionic liquid comprises the following steps: the anhydrous aluminum chloride and the ligand are mixed according to the proportion of 1-1.5; the ligand is at least one selected from 1-ethyl-3-methylimidazolium chloride salt, urea and acetamide.
The invention has the following beneficial effects: by introducing a p-type organic compound into the positive electrode, the positive electrode of the p-type organic compound can lose electrons in the charging process and shows the cationic characteristic, and the coordination is realized on anions in the electrolyte; during the subsequent discharge process, the coordinated anions can be reversibly dissociated, and the organic positive electrode returns to electric neutrality. The invention utilizes the unique anion redox property of the p-type organic compound and has higher working voltage than other organic materials; the p-type organic compound does not generate the damage of old chemical bonds and the formation of new chemical bonds in the reversible coordination-dissociation process with coordination ions, and shows good chemical stability and fast reaction kinetics. In addition, the p-type polymer cathode material has low solubility in the ionic liquid electrolyte and shows excellent charge-discharge cycle stability.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
Fig. 1 is a cyclic voltammogram of the aluminum ion battery prepared in example 1;
FIG. 2 is a charge and discharge curve of the battery described in example 1;
fig. 3 is a cycle performance test chart of the aluminum ion battery prepared in example 1;
FIG. 4 is a charge and discharge curve of the battery described in example 2;
FIG. 5 is a graph showing the cycle performance test of the battery according to example 3;
FIG. 6 is a graph showing the cycle performance test of the battery according to example 4;
FIG. 7 is a charge and discharge curve of the battery described in example 5;
FIG. 8 is a charge and discharge curve of the battery described in example 6;
fig. 9 is a charge and discharge curve of the battery described in comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The embodiment of the invention provides an organic positive electrode of an aluminum ion battery, which comprises 40-80 parts of organic active substances, 10-50 parts of conductive agents and 8-12 parts of binders in parts by mass; wherein the organic active substance is a p-type organic compound or a polymer obtained by reacting the p-type organic compound.
The organic active substance is an organic small molecule containing a p-type redox active site or an organic polymer using the small molecule as an active monomer; the positive electrode of the p-type organic compound can lose electrons in the charging process, shows the cationic characteristic and realizes coordination in anions in the electrolyte; during the subsequent discharge process, the coordinated anions can be reversibly dissociated, and the organic positive electrode returns to electric neutrality.
In some embodiments, the organic active material is 50 to 70 parts, the conductive agent is 20 to 40 parts, and the binder is 8 to 12 parts. By optimizing the use amount of each component of the organic anode of the aluminum ion battery, the performance of the anode is further improved, the working voltage is reduced, and the charge and discharge performance is improved.
In some embodiments, the p-type organic compound is a heterocyclic compound or a derivative thereof, the heterocyclic compound contains N, S or O elements, and the heteroatom may be N, S or O, which is not limited herein. Preferably, the p-type organic compound is at least one selected from phenothiazine, phenoxazine, thianthrene, thiophene, piperazine, promethazine, flavin and pteridine, and the raw materials are all suitable for being used as organic active substances to prepare the organic positive electrode of the aluminum ion battery, so that the positive electrode can have good electrochemical performance.
Further, the polymer is obtained by grafting a p-type organic compound on a stable polymer chain, or reacting with other organic compounds, and can be linearly connected or crosslinked through a cross-coupling reaction, or copolymerized with other organic small molecules. Wherein, the stable polymer chain is selected from at least one of organic polynorbornene, polyethylene benzyl chloride and polyethylene, and can be any one or more of the above.
In some embodiments, the organic active is selected from at least one of poly-3-vinyl-N-methylphenoxazine, phenothiazine, 5, 10-dihydro-5, 10-diphenylphenazine, thianthrene, benzothiophene, and poly-N-propylphenothiazine. The above materials can be commercially available raw materials or autonomously synthesized, are all suitable to be used as an organic active substance of a positive electrode material, and can endow the battery material with very excellent electrochemical performance after being used in an aluminum ion battery.
In some embodiments, the conductive agent is selected from at least one of acetylene black, conductive carbon black, ketjen black, graphene, and carbon nanotubes, and the conductive agent may be any one of the above, and is suitable for use in preparing the cathode material. The binder is at least one selected from polyvinylidene fluoride, sodium carboxymethylcellulose, sodium alginate, sodium polyacrylate and styrene butadiene rubber, can be any one of the above, and is suitable for preparing the anode material.
The embodiment of the invention provides an aluminum ion battery, which comprises a negative electrode, electrolyte and a positive electrode, wherein the positive electrode is prepared from the organic positive electrode of the aluminum ion battery, the aluminum ion battery has low working voltage, and can realize quick charge and discharge and good cycle performance.
In some embodiments, the process of preparing the positive electrode comprises: the preparation method comprises the steps of preparing materials according to the composition of the organic anode of the aluminum ion battery, mixing and dissolving to obtain a material to be coated, coating the material to be coated on a conductive current collector, and drying. The solvent used in the dissolving process may be, but is not limited to, N-methylpyrrolidone, and the material of the conductive current collector may be, but is not limited to, molybdenum foil. The drying process can be vacuum drying at 50-120 deg.C for 5-15h, and then punching the dried pole piece into positive pole with required size. Specifically, the drying temperature can be 50 deg.C, 70 deg.C, 90 deg.C, 110 deg.C, 120 deg.C, etc.; the drying time can be 5h, 10h, 15h and the like.
In some embodiments, the negative electrode is a surface treated aluminum metal material (e.g., a commercially available high purity aluminum such as aluminum foil) having a thickness of 20 μm to 500 μm (e.g., 20 μm, 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, etc.). And cutting the aluminum foil after surface treatment into a negative electrode with a proper size, separating the positive electrode and the negative electrode by using a glass fiber diaphragm, and injecting the prepared ionic liquid electrolyte to obtain the organic aluminum ion secondary battery. The coating amount of the material to be coated on the aluminum foil is 2-5mg/cm 2 E.g. 2 mg-cm 2 、3mg/cm 2 、4mg/cm 2 、5mg/cm 2 And so on.
Further, the surface treatment method may be a treatment method in the prior art, and is not limited herein. For example, at least one of mechanical polishing, chemical erosion, ion liquid soaking or surface coating of artificial solid electrolyte interface film can be adopted, and the treatment can be carried out in any one or combination of ways. The preparation process of the artificial solid electrolyte interface film comprises the following steps: mixing aluminum cation substituted montmorillonite (Al-MMT) with a binder, and coating the mixture on a metal aluminum material to form the aluminum alloy; the thickness of the artificial solid electrolyte interface film is 1 μm to 10 μm (e.g., 1 μm, 3 μm, 5 μm, 7 μm, 10 μm, etc.). Specifically, the aluminum cation substituted montmorillonite can be a commercially available raw material and can also be prepared independently, and the preparation method comprises the following steps: treating montmorillonite by cation exchange, dispersing 2g montmorillonite and 0.5g aluminum chloride into 100ml water by stirring, stirring at 60 deg.C for 1 hr, centrifuging, collecting, and oven drying at 95 deg.C to obtain cation-exchanged montmorillonite.
In some embodiments, the electrolyte is an anhydrous aluminum chloride-based ionic liquid; the preparation process of the anhydrous aluminum chloride-based ionic liquid comprises the following steps: the anhydrous aluminum chloride and the ligand are mixed according to the proportion of 1-1.5; the ligand is at least one selected from 1-ethyl-3-methylimidazolium chloride, urea and acetamide, and can be any one or more of the above. The ratio of anhydrous aluminum chloride to ligand can be 1, 1.1, 1.2.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides an aluminum ion battery, which is prepared by the following steps:
60mg of poly-3-vinyl-N-methylphenoxazine, 30mg of acetylene black and 10mg of polyvinylidene fluoride were uniformly dispersed in 0.5mL of N-methylpyrrolidone and uniformly coated on the molybdenum foil (area coating amount: 4 mg/cm) 2 The same as below), then placing the anode plate in a 70 ℃ oven for vacuum drying for 10 hours, and blanking to prepare the anode plate. In a glove box filled with argon, the prepared positive pole piece is put into a glove boxThe aluminum-ion battery comprises a glass fiber diaphragm, an aluminum cathode coated with an artificial SEI film on the surface, and an anhydrous aluminum chloride-1-ethyl-3 methylimidazolium chloride ionic liquid electrolyte with the molar ratio of 1.3.
Electrochemical performance tests were performed on the aluminum ion batteries prepared in the examples, as shown in fig. 1. It can be seen that in the scan range of 0.1-2.0V, s is measured at 0.2mV -1 The cyclic voltammogram of the aluminum ion cell of example 1 was tested and two pairs of distinct redox peaks were present.
FIG. 2 shows the cell of example 1 at 200mA g -1 The current density of (A) shows more than 130mAh g in a constant current charge-discharge curve under an electrochemical window of 0.1-2.0V -1 The discharge capacity of (2). Increase the current density to 5 ag -1 The cell of example 1 showed no significant capacity fade after 14000 cycles (as shown in figure 3).
Example 2
This example provides an aluminum ion battery, which is prepared as follows:
uniformly dispersing 60mg of phenothiazine, 30mg of acetylene black and 10mg of polyvinylidene fluoride in 0.5mL of N-methyl pyrrolidone, uniformly coating the phenothiazine, the acetylene black and the polyvinylidene fluoride on a molybdenum foil, then placing the molybdenum foil on a 70 ℃ oven for vacuum drying for 10 hours, and blanking to prepare a positive pole piece; in a glove box filled with argon, the prepared positive electrode piece and the prepared glass fiber diaphragm are immersed in an ionic liquid (same as the electrolyte) for 24 hours to form an aluminum negative electrode, and the aluminum negative electrode is prepared from anhydrous aluminum chloride-1-ethyl-3-methylimidazolium chloride ionic liquid electrolyte with the molar ratio of 1.3.
And (3) performance testing: the charge and discharge test was performed in a voltage range of 0.1 to 2.0V, as shown in fig. 4.
Example 3
This example provides an aluminum ion battery, which is prepared as follows:
60mg of 5, 10-diphenyl-5, 10-dihydrophenazine, 30mg of acetylene black and 10mg of polyvinylidene fluoride are uniformly dispersed in 0.5mL of N-methylpyrrolidone, uniformly coated on a molybdenum foil, then placed in a 70 ℃ oven for vacuum drying for 10 hours, and blanked to prepare a positive pole piece; and (2) in a glove box filled with argon, assembling the prepared positive pole piece and the glass fiber diaphragm into an aluminum negative pole which is soaked in ionic liquid for 24 hours, and anhydrous aluminum chloride-urea ionic liquid electrolyte with the molar ratio of 1.3.
And (3) performance testing: the charge and discharge test was performed in a voltage range of 0.1 to 2.0V, as shown in fig. 5.
Example 4
The embodiment provides an aluminum ion battery, which is prepared by the following steps:
uniformly dispersing 60mg of thianthrene, 30mg of acetylene black and 10mg of polyvinylidene fluoride in 0.5mL of N-methyl pyrrolidone, uniformly coating the mixture on a molybdenum foil, then placing the molybdenum foil on a 70 ℃ oven for vacuum drying for 10 hours, and blanking to prepare a positive pole piece; and (3) assembling the prepared positive pole piece, the glass fiber diaphragm, the aluminum cathode with polished surface and the anhydrous aluminum chloride-urea ionic liquid electrolyte with the molar ratio of 1.3 into the aluminum ion battery in a glove box filled with argon gas.
And (3) performance testing: the charge and discharge test was performed in a voltage range of 0.1 to 2.0V as shown in fig. 6.
Example 5
This example provides an aluminum ion battery, which is prepared as follows:
uniformly dispersing 60mg of N-phenylthiophene, 30mg of acetylene black and 10mg of polyvinylidene fluoride in 0.5mL of N-methylpyrrolidone, uniformly coating the molybdenum foil with the mixture, then placing the molybdenum foil in an oven at 70 ℃ for vacuum drying for 10 hours, and blanking to prepare a positive pole piece; and (3) in a glove box filled with argon, the prepared positive pole piece and the glass fiber diaphragm are immersed in an ionic liquid for 24 hours to form an aluminum-ion battery, and the molar ratio of the aluminum-urea anhydrous ionic liquid electrolyte to the aluminum-ion battery is 1.3.
And (3) performance testing: the charge and discharge test was performed in a voltage range of 0.4 to 1.9V as shown in fig. 7.
Example 6
The embodiment provides an aluminum ion battery, which is prepared by the following steps:
uniformly dispersing 60mg of poly-N-propylphenothiazine, 30mg of acetylene black and 10mg of polyvinylidene fluoride in 0.5mL of N-methylpyrrolidone, uniformly coating the mixture on a molybdenum foil, then placing the molybdenum foil on a 70 ℃ drying oven for vacuum drying for 10 hours, and blanking to prepare a positive pole piece; and (2) in a glove box filled with argon, the prepared positive pole piece and the glass fiber diaphragm are immersed in an ionic liquid for 24 hours to form an aluminum negative pole, and the aluminum chloride-1-ethyl-3 methylimidazolium chloride ionic liquid electrolyte with the molar ratio of 1.3.
And (3) performance testing: the charge and discharge test was performed in a voltage range of 0.1 to 2.0V, as shown in fig. 8.
Example 7
The only difference from example 1 is: the formulation of the positive electrode was 80mg of poly-3-vinyl-N-methylphenoxazine, 10mg of acetylene black and 10mg of polyvinylidene fluoride.
Example 8
The only difference from example 1 is: the formulation of the positive electrode was 70mg of poly-3-vinyl-N-methylphenoxazine, 20mg of acetylene black and 10mg of polyvinylidene fluoride.
Example 9
The only difference from example 1 is that: the formulation of the positive electrode was 50mg of poly-3-vinyl-N-methylphenoxazine, 40mg of acetylene black and 10mg of polyvinylidene fluoride.
Example 10
The only difference from example 1 is: the formulation of the positive electrode was 40mg of poly-3-vinyl-N-methylphenoxazine, 50mg of acetylene black and 10mg of polyvinylidene fluoride.
The batteries of examples 1 and 7 to 10 were measured for specific discharge capacity at a current density of 200mA/g in a voltage range of 0.1 to 2.0V and the energy density thereof was recorded (mass is the total mass of the positive electrode); then taking the ratio of the discharge specific capacity tested by the current density of 2A/g to 200mA/g as the capacity retention rate; and tested for cycle performance at a current density of 2A/g, the results of which are shown in Table 1.
Table 1: energy Density, 2A/g Capacity Retention, and cycling stability of examples 1 and 7 to 10
As can be seen from table 1: compared with examples 7, 8 and 1, the energy density, rate capability and cycle performance of the battery are obviously improved with the increase of the using amount of the conductive agent, because the electron conductivity of the p-type organic compound is poor, a large amount of conductive agent is required to be used for improving the electron conductivity, and the capacity and rate capability of the battery are further improved. Compared with examples 1, 9 and 10, the energy density begins to decrease instead with the further increase of the dosage of the conductive agent, and the rate capability and the capacity retention rate are not improved, which is mainly because the conductive agent has no electrochemical activity, and the energy density of the battery is reduced when the dosage is excessive; and the nanometer conductive agent increases the difficulty in mixing materials, the slurry is easy to agglomerate, and the effect of the conductive agent in the battery is reduced. In summary, 60wt% of p-type organic active material, 30wt% of conductive agent and 10wt% of binder are the most preferable positive electrode formulation.
Comparative example 1
The present comparative example provides an aluminum ion battery, which is prepared as follows:
uniformly dispersing 60mg of anthraquinone (N-type organic compound), 30mg of acetylene black and 10mg of polyvinylidene fluoride in 0.5mL of N-methylpyrrolidone, uniformly coating the mixture on a molybdenum foil, then placing the molybdenum foil on a 70 ℃ oven for vacuum drying for 10 hours, and blanking to prepare a positive pole piece; and assembling the prepared anode plate, a glass fiber diaphragm, an aluminum cathode coated with a surface artificial SEI film and an anhydrous aluminum chloride-1-ethyl-3 methylimidazolium chloride ionic liquid electrolyte with the molar ratio of 1.3.
It should be added that comparative example 1 differs from example 1 only in that: the poly 3-vinyl-N-methylphenoxazine was replaced with an equal amount of anthraquinone.
And (3) performance testing: the charge and discharge test was performed in a voltage range of 0.2 to 1.6V as shown in fig. 9. The voltage plateau of the n-type organic compound as the anode of the aluminum ion battery is below 1V and is obviously lower than that of the p-type organic anode.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. An organic positive electrode of an aluminum ion battery is characterized by comprising 40-80 parts of organic active substances, 10-50 parts of conductive agents and 8-12 parts of binders in parts by mass;
wherein the organic active substance is a p-type organic compound or a polymer obtained by reacting the p-type organic compound.
2. The aluminum ion battery organic positive electrode according to claim 1, wherein the organic active material is 50 to 70 parts, the conductive agent is 20 to 40 parts, and the binder is 8 to 12 parts.
3. The aluminum ion battery organic positive electrode according to claim 1 or 2, wherein the p-type organic compound is a heterocyclic compound containing an element of N, S, or O or a derivative thereof;
preferably, the p-type organic compound is selected from at least one of phenothiazine, phenoxazine, thianthrene, thiophene, piperazine, promethazine, flavin, and pteridine.
4. The organic positive electrode of the aluminum-ion battery according to claim 3, wherein the polymer is obtained by grafting the p-type organic compound on a stable polymer chain or reacting with other organic compounds;
wherein the stable polymer chain is selected from at least one of organic polynorbornene, polyvinylbenzyl chloride, and polyethylene.
5. The aluminum-ion battery organic positive electrode according to claim 1 or 2, characterized in that the organic active substance is at least one selected from the group consisting of poly-3-vinyl-N-methylphenoxazine, phenothiazine, 5, 10-dihydro-5, 10-diphenylphenazine, thianthrene, benzothiophene, and poly-N-propylphenothiazine.
6. The aluminum-ion battery organic positive electrode according to claim 1 or 2, wherein the conductive agent is at least one selected from acetylene black, conductive carbon black, ketjen black, graphene, and carbon nanotubes;
the binder is at least one selected from polyvinylidene fluoride, sodium carboxymethylcellulose, sodium alginate, sodium polyacrylate and styrene butadiene rubber.
7. An aluminum ion battery, which is characterized by comprising a negative electrode, an electrolyte and a positive electrode, wherein the positive electrode is prepared from the organic positive electrode of the aluminum ion battery as claimed in any one of claims 1 to 6.
8. The aluminum-ion battery of claim 7, wherein the positive electrode is prepared by a process comprising: preparing materials according to the composition of the organic anode of the aluminum ion battery, mixing and dissolving to obtain a material to be coated, coating the material to be coated on a conductive current collector, and drying;
preferably, the drying is vacuum drying at 50-120 deg.C for 5-15h;
preferably, the solvent used in the dissolving process is N-methyl pyrrolidone;
preferably, the conductive current collector is made of molybdenum foil;
preferably, the method further comprises the step of punching the dried pole piece into a positive pole with a required size.
9. The aluminum-ion battery of claim 7, wherein the negative electrode is a surface-treated metallic aluminum material, and the organic positive electrode and the negative electrode of the aluminum-ion battery are separated by a glass fiber separator;
preferably, the surface treatment is selected from at least one of mechanical polishing, chemical etching, ionic liquid soaking or surface coating of an artificial solid electrolyte interfacial film; the thickness of the metal aluminum material is 20-500 μm;
more preferably, the process for preparing the artificial solid electrolyte interface membrane comprises: mixing the montmorillonite substituted by aluminum cations with a binder, and coating the mixture on a metal aluminum material to form the aluminum-based composite material;
the thickness of the artificial solid electrolyte interface film is 1-10 μm.
10. The aluminum-ion battery of claim 7, wherein the electrolyte is an anhydrous aluminum chloride-based ionic liquid;
preferably, the preparation process of the anhydrous aluminum chloride-based ionic liquid comprises the following steps: the anhydrous aluminum chloride and the ligand are mixed according to the proportion of 1-1.5; the ligand is selected from at least one of 1-ethyl-3-methylimidazolium chloride salt, urea and acetamide.
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