CN112635760A - Rechargeable fullerene-aluminum ion safety battery - Google Patents
Rechargeable fullerene-aluminum ion safety battery Download PDFInfo
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- CN112635760A CN112635760A CN202011530837.9A CN202011530837A CN112635760A CN 112635760 A CN112635760 A CN 112635760A CN 202011530837 A CN202011530837 A CN 202011530837A CN 112635760 A CN112635760 A CN 112635760A
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- fullerene
- rechargeable
- aluminum
- safety battery
- aluminum ion
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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 relates to a rechargeable fullerene-aluminum ion safety battery, which is a battery system mainly taking a fullerene material as an anode, aluminum metal as a cathode and ionic liquid as electrolyte, wherein ions participating in the reaction are chloroaluminate anions. The invention has the advantages that: according to the invention, fullerene is used as the anode material of the aluminum ion battery, during the discharge process, the aluminum storage potential of the fullerene is as high as 1.5V, a very long voltage platform appears, and the specific capacity of the fullerene is as high as 200mAh g‑1In addition, the battery exhibits good stability and safety during charging and discharging.
Description
Technical Field
The invention belongs to the technical field of aluminum ion batteries, and relates to a rechargeable fullerene-aluminum ion safety battery.
Background
With the current social development and technical progress, in the existing secondary battery system, alkali metal cannot stably exist in air and the electrolyte has flammability, so that the safety problems of spontaneous combustion and the like can be caused. Aluminum ion batteries, as a new type of secondary energy storage batteries, have been attracting much attention and research since 2015 due to the characteristics of low price and stability in air of aluminum metal negative electrodes.
Currently, the common cathode materials for aluminum ion batteries are mainly carbon materials (graphene, natural graphite, pyrolytic graphite, porous carbon and the like), metal oxides, sulfides, phosphides and the like, among which, metal materials mainly store aluminum ions through conversion reaction, but the aluminum ions carry three charges and have larger ionic radius, so that the materials have poor cycle stability and lower reversible capacity in the aluminum storage process. For carbon materials, chloroaluminate anions in the electrolyte are mainly used as energy storage ions in the aluminum storage process. In this class of materials, at 100mA g-1The specific capacity of the graphene is 150mAh g at the highest current density-1This capacity still cannot meet the current energy demand, and therefore, a new high-capacity aluminum ion battery needs to be found and developed.
For example, chinese patent CN110492078A discloses an aluminum ion battery positive electrode material, an aluminum ion battery and applications thereof, wherein a composite electrode material is prepared by ball-milling and mixing polythiophene and graphite to obtain a polythiophene/graphite mixture material, adding carbon black, polyvinylidene fluoride and 1-methyl-2-pyrrolidone to obtain a slurry, coating the slurry on a current collector and drying to obtain the positive electrode material, similar to the aluminum ion battery using general graphene as the positive electrode material, and the specific capacity of the aluminum ion battery prepared by the patent can only reach about 150mAh g-1Still relatively low.
Disclosure of Invention
The invention aims to provide a rechargeable fullerene-aluminum ion safety battery, which takes fullerene as the positive electrode material of an aluminum ion battery, the aluminum storage potential of the fullerene is as high as 1.5V in the discharging process, a very long voltage platform is formed, and the specific capacity of the fullerene is as high as 200mAh g-1。
The purpose of the invention can be realized by the following technical scheme:
a rechargeable fullerene-aluminum ion safety battery is characterized in that a positive electrode is made of fullerene materials, aluminum metal is used as a negative electrode, and ionic liquid is used as electrolyte.
Further, the preparation process of the positive electrode comprises the following steps:
(1) dispersing the fullerene material, the conductive agent and the binder in a solvent to prepare slurry with viscosity;
(2) and coating the slurry on a current collector, and drying to obtain the anode.
Furthermore, the mass ratio of the fullerene material to the conductive agent to the binder is (50-80): (10-30): (10-20).
Further, the fullerene material is C60、C70、C76、C78、C80Or C84One kind of (1).
Furthermore, the conductive agent is one or more of acetylene black, single-arm or multi-arm carbon nanotubes, graphene or Ketjen black.
Furthermore, the binder is one or more of polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethylcellulose or styrene butadiene rubber.
Furthermore, the solvent is one of deionized water, ethanol or nitrogen methyl pyrrolidone.
Furthermore, the current collector adopts inert metal molybdenum, tantalum or titanium and the like, and the thickness of the current collector is preferably 0.01-0.1 mm.
Furthermore, the thickness of the aluminum metal is 0.01-0.5mm, and micropores with the pore diameter of 0.5-2um are densely distributed. The aluminum metal is provided with micropores, the function of the micropores is mainly to inhibit the growth of aluminum dendrites, and meanwhile, the aluminum metal serves as a negative electrode to provide aluminum ions in the charging and discharging processes.
Further, the diaphragm is one of glass fiber, polyethylene microporous diaphragm or polypropylene microporous diaphragm. The function of the ion-conducting membrane is mainly to separate the anode and the cathode, prevent short circuit and enable ions to pass through smoothly in the charging and discharging process.
Further, the electrolyte is prepared from anhydrous aluminum chloride and one of imidazole, pyridine, pyrrole or quaternary ammonium ionic liquids according to a molar ratio (1.1-1.6): 1 is configured. Preferably, the imidazole ionic liquid is 1-ethyl-3-methylimidazole chloride and the like.
Further, the long plateau and high voltage result from intercalation of chloroaluminate anions into the interstices of the fullerene material. Preferably, the fullerene material is C with a body-centered cubic structure60。
Compared with the prior art, the invention provides a novel rechargeable fullerene-aluminum ion battery with high capacity, high stability and safety, and simultaneously provides a positive electrode material with high voltage, long platform and high specific capacity. The novel aluminum ion battery provided by the invention has the aluminum storage potential as high as 1.5V, a long voltage platform and a specific capacity as high as 300mAh g-1Among the current carbon cathode materials, the capacity is highest.
Drawings
FIG. 1 is a schematic diagram of the crystal structure of a fullerenic material of example 1;
fig. 2 is a charging performance test curve of the rechargeable aluminum-ion battery of example 1;
fig. 3 is a rate performance graph of the rechargeable aluminum-ion battery of example 2;
fig. 4 is a charge-discharge curve of the expanded graphite of comparative example 1.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, ionic liquids such as 1-ethyl-3-methylimidazolium chloride and C60The fullerene materials are purchased from Shanghai Chengjie chemical Co., Ltd. and Xiamen New Material science and technology Co., Ltd.
The assembly technology of the battery is conventional in the field, and specifically can be as follows: (1) the shell is a button battery shell made of stainless steel and different in thickness, and a layer of molybdenum foil is fixed inside the negative electrode shell to inhibit the electrolyte from corroding the battery shell; (2) in the process of battery assembly, the components are placed in the following order, the anode is placed at one end of the cathode shell, then the diaphragm is placed, a certain amount of electrolyte is dripped, the cathode aluminum metal is placed at one end of the anode shell, the molybdenum foil is placed to avoid the corrosion of the electrolyte to the battery shell, then the gasket is placed, finally the battery is packaged, and the whole process is carried out in the glove box.
In addition, the rest of the material or processing technology, if not specifically stated, indicates that it is the conventional commercial material or conventional processing technology in this field.
Example 1:
with C60(crystal structure shown in FIG. 1) as positive electrode active material, adding C60Acetylene black and PTFE in a mass ratio of 50: 30: 20, uniformly mixing, then dripping 1mL of absolute ethyl alcohol, and mixing in a slurry stirring machine for 10min to obtain slurry with certain viscosity; coating the slurry on a current collector molybdenum foil, and heating and drying for 12 hours in a vacuum drying oven at the temperature of 80 ℃; and then cutting the electrode plate into a circular plate with the diameter of 8mm, namely the positive plate. The positive plate is placed on the side of the negative electrode shell with the molybdenum foil adhered, then the glass fiber is placed as a diaphragm, and 50 mu L of ionic liquid electrolyte (prepared by anhydrous aluminum chloride and 1-ethyl-3-methylimidazole chloride according to the molar ratio of 1.2: 1) is dripped in. Then, aluminum foil, molybdenum foil, gaskets and positive electrode shells with the thickness of 0.1mm are placed in the battery, the battery is packaged, and then the battery is placed still for 12 hours to test various electrochemical performances.
FIG. 2 shows a charging performance test curve of the rechargeable aluminum-ion battery, as shown in FIG. 2, C60After the anode and the metallic aluminum cathode are assembled into the battery according to the method, the reversible discharge specific mass capacity of the battery is 195 mAmp per gram at the current density of 200 milliampere per gram, and a longer voltage platform exists at 1.56 volts, which indicates that C60The aluminum ion battery cathode material has excellent electrochemical performance.
Example 2:
with C70As a positive electrode material, C70Acetylene black and PTFE in a mass ratio of 5: 3: 2, uniformly mixing, then dripping 1mL of absolute ethyl alcohol, and mixing in a slurry stirring machine for 10min to obtain slurry with certain viscosity; coating the slurry on a current collector molybdenum foil, and heating and drying for 12 hours in a vacuum drying oven at the temperature of 80 ℃; and then cutting the electrode plate into a circular plate with the diameter of 8mm, namely the positive plate. The positive plate is placed on the side of the negative electrode shell with the molybdenum foil adhered, then the glass fiber is placed as a diaphragm, and 50 mu L of ionic liquid electrolyte (prepared by anhydrous aluminum chloride and 1-ethyl-3-methylimidazole chloride according to the molar ratio of 1.2: 1) is dripped in. Then, aluminum foil, molybdenum foil, gaskets and positive electrode shells with the thickness of 0.1mm are placed in the battery, the battery is packaged, and then the battery is placed still for 12 hours to test various electrochemical performances.
Fig. 3 shows a rate performance graph of the rechargeable aluminum-ion battery. As shown in FIG. 3, C70After assembly into a battery for the positive electrode and the metallic aluminum negative electrode as described above, the battery exhibited reversible discharge specific mass capacities at 320, 195, 140, 104, 55, and 370 milliamp-hours per gram at current densities of 200, 500, 1000, 1500, 2000, and 4000 milliamps per gram, respectively, indicating C70The aluminum ion battery cathode material has excellent electrochemical performance.
Comparative example 1:
compared to example 1, most of them are the same except that the fullerene is changed to expanded graphite of equal mass. FIG. 4 shows the charge-discharge curve of the expanded graphite at 500mA g as shown in FIG. 4-1The specific discharge capacity of the material is 63mAh g under the current density-1And a long voltage platform does not exist, which shows that the energy storage mechanism of the chloroaluminate anions in the fullerene material is different from that in the graphite material.
Example 3:
compared with example 1, the method is mostly the same, except that the molar ratio of the anhydrous aluminum chloride to the 1-ethyl-3-methylimidazolium chloride is 1.1: 1, preparation.
Example 4:
compared with example 1, most of the components are the same, except that the molar ratio of the anhydrous aluminum chloride to the 1-ethyl-3-methylimidazolium chloride is 1.6: 1, preparation.
Example 5:
compared with example 1, the pore diameter of the aluminum foil was changed to 0.5 μm, which is the most common.
Example 6:
compared with example 1, the same is mostly true except that the pore size of the aluminum foil is changed to 1.0 μm.
Example 7-example 10:
compared with example 1, most of them are the same except for fullerene C60Are respectively replaced by C76、C78、C80Or C84。
Example 11:
compared with example 1, most of them are the same except that the mass ratio of the fullerene material, the conductive agent and the binder is adjusted to 80: 10: 10.
example 12:
compared with example 1, most of them are the same except that the mass ratio of the fullerene material, the conductive agent and the binder is adjusted to 75: 20: 15.
example 13-example 15:
compared with the embodiment 1, the conductive agent acetylene black is mostly the same except that the conductive agent acetylene black is replaced by equal mass of carbon nanotubes, graphene or ketjen black.
Example 16-example 18:
compared with example 1, the binder PTFE is mostly the same except that the binder PTFE is replaced by polyvinylidene fluoride, sodium carboxymethyl cellulose or styrene-butadiene rubber with equal mass respectively.
Example 19-example 20:
compared with example 1, most of them are the same except that the absolute ethanol is replaced by deionized water or nitrogen methyl pyrrolidone with equal mass respectively.
The separator in the aluminum-ion battery of each of the above embodiments may also be replaced with a polyethylene microporous separator or a polypropylene microporous separator.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A rechargeable fullerene-aluminum ion safety battery is characterized in that a positive electrode is made of fullerene materials, aluminum metal is used as a negative electrode, and ionic liquid is used as electrolyte.
2. The rechargeable fullerene-aluminum ion safety battery as claimed in claim 1, wherein the positive electrode is prepared by the following steps:
(1) dispersing the fullerene material, the conductive agent and the binder in a solvent to prepare slurry with viscosity;
(2) and coating the slurry on a current collector, and drying to obtain the anode.
3. A rechargeable fullerene-aluminium ion safety battery according to claim 2, wherein the mass ratio of fullerene material, conductive agent and binder is (50-80): (10-30): (10-20).
4. A rechargeable fullerene-aluminium ion safety battery according to claim 2, characterised in that the fullerene-like material is C60、C70、C76、C78、C80Or C84One kind of (1).
5. The rechargeable fullerene-aluminum ion safety battery according to claim 2, wherein the conductive agent is one or more of acetylene black, single-arm or multi-arm carbon nanotubes, graphene or Kejin black.
6. The rechargeable fullerene-aluminum ion safety battery as claimed in claim 2, wherein the binder is one or more of polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethylcellulose or styrene butadiene rubber.
7. A rechargeable fullerene-aluminium ion safety cell according to claim 2, wherein the solvent is one of de-ionized water, ethanol or nitrogen methyl pyrrolidone.
8. A rechargeable fullerene-aluminium ion safety battery according to claim 1, wherein the aluminium metal has a thickness of 0.01-0.5mm and is densely packed with micropores having a pore size of 0.5-2 um.
9. The rechargeable fullerene-aluminum ion safety battery according to claim 1, wherein the separator is one of glass fiber, polyethylene microporous separator or polypropylene microporous separator.
10. The rechargeable fullerene-aluminum ion safety battery according to claim 1, wherein the electrolyte is prepared from anhydrous aluminum chloride and one of imidazole, pyridine, pyrrole or quaternary ammonium ionic liquids according to a molar ratio (1.1-1.6): 1 is configured.
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| CN202011530837.9A CN112635760A (en) | 2020-12-22 | 2020-12-22 | Rechargeable fullerene-aluminum ion safety battery |
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| CN202011530837.9A CN112635760A (en) | 2020-12-22 | 2020-12-22 | Rechargeable fullerene-aluminum ion safety battery |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101641809A (en) * | 2006-12-12 | 2010-02-03 | 联邦科学及工业研究组织 | Improved energy storage device |
| CN103825045A (en) * | 2014-03-26 | 2014-05-28 | 北京科技大学 | Aluminium ion battery and preparation method thereof |
| CN104241596A (en) * | 2014-08-22 | 2014-12-24 | 北京科技大学 | Rechargeable aluminum ion cell and preparation method thereof |
| CN105977526A (en) * | 2016-06-15 | 2016-09-28 | 昆明理工大学 | Rechargeable aluminum carbon battery and preparation method thereof |
-
2020
- 2020-12-22 CN CN202011530837.9A patent/CN112635760A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101641809A (en) * | 2006-12-12 | 2010-02-03 | 联邦科学及工业研究组织 | Improved energy storage device |
| CN103825045A (en) * | 2014-03-26 | 2014-05-28 | 北京科技大学 | Aluminium ion battery and preparation method thereof |
| CN104241596A (en) * | 2014-08-22 | 2014-12-24 | 北京科技大学 | Rechargeable aluminum ion cell and preparation method thereof |
| CN105977526A (en) * | 2016-06-15 | 2016-09-28 | 昆明理工大学 | Rechargeable aluminum carbon battery and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 尉海军，何世满: "铝离子电池研究进展", 《北京工业大学学报》 * |
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