CN115411272B - Corrosion-resistant carbon-coated aluminum foil for lithium battery - Google Patents
Corrosion-resistant carbon-coated aluminum foil for lithium battery Download PDFInfo
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- CN115411272B CN115411272B CN202211155708.5A CN202211155708A CN115411272B CN 115411272 B CN115411272 B CN 115411272B CN 202211155708 A CN202211155708 A CN 202211155708A CN 115411272 B CN115411272 B CN 115411272B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 95
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 85
- 239000011888 foil Substances 0.000 title claims abstract description 85
- 238000005260 corrosion Methods 0.000 title claims abstract description 71
- 230000007797 corrosion Effects 0.000 title claims abstract description 71
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 38
- 239000011248 coating agent Substances 0.000 claims abstract description 41
- 238000000576 coating method Methods 0.000 claims abstract description 41
- 239000002033 PVDF binder Substances 0.000 claims abstract description 17
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims description 65
- 238000010992 reflux Methods 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 238000001291 vacuum drying Methods 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000007795 chemical reaction product Substances 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000012153 distilled water Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 239000012065 filter cake Substances 0.000 claims description 21
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 9
- 229930192474 thiophene Natural products 0.000 claims description 9
- DUDAKCCDHRNMDJ-UHFFFAOYSA-N thiophen-3-ylmethanamine Chemical compound NCC=1C=CSC=1 DUDAKCCDHRNMDJ-UHFFFAOYSA-N 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 6
- 229920000123 polythiophene Polymers 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 150000001263 acyl chlorides Chemical group 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000013543 active substance Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Classifications
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- 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
- H01M10/052—Li-accumulators
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the field of lithium batteries, and is used for solving the problems that the carbon-coated aluminum foil of the existing lithium battery is easy to be corroded by electrolyte, and a large amount of heat is emitted when the battery works, so that attachments on the carbon-coated aluminum foil of the lithium battery are easy to fall off due to oxidization of the carbon-coated aluminum foil of the lithium battery, and finally the normal working of the lithium battery is influenced and even potential safety hazards exist; the corrosion-resistant carbon-coated aluminum foil for the lithium battery can effectively improve corrosion resistance by forming the corrosion-resistant coating on the surface of the aluminum foil, wherein a large number of C-F bonds are contained in a molecular chain of polyvinylidene fluoride in the corrosion-resistant coating, and good chemical resistance and high temperature resistance are provided for the aluminum foil, so that the aluminum foil is not easy to be corroded by electrolyte, the aluminum foil is effectively protected, the modified conductive graphite powder in the corrosion-resistant coating has good conductivity, and the aluminum foil can still maintain high electrochemical performance after the corrosion-resistant coating is formed.
Description
Technical Field
The invention relates to the field of lithium batteries, in particular to a corrosion-resistant carbon-coated aluminum foil for a lithium battery.
Background
The lithium ion battery is widely applied to different fields such as digital products, power, energy storage and the like due to the advantages of high energy density, high voltage, wide working temperature range, no memory effect, good cycle performance, long service life and the like. However, the lithium battery has the problems of poor conductivity, low rate capability and poor heat dissipation performance, which affects the further popularization and application.
The lithium ion battery generally uses aluminum foil or carbon-coated aluminum foil as a carrier of a positive electrode material, and the conductive carbon layer is coated on the surface of the aluminum foil to inhibit polarization of the battery, reduce thermal effect, improve rate capability of the battery, improve adhesiveness between active substances and the aluminum foil and reduce consumption of a binder. The lithium battery adopting the carbon-coated aluminum foil has good conductivity, multiplying power performance and heat dissipation performance.
However, the existing carbon-coated aluminum foil of the lithium battery is easy to be corroded by electrolyte, and a large amount of heat is emitted during the operation of the battery, so that the carbon-coated aluminum foil of the lithium battery is easy to oxidize to cause the attachment on the carbon-coated aluminum foil to fall off, and finally the normal operation of the lithium battery is influenced and even potential safety hazards exist.
Therefore, in order to solve the above problems, there is a need for a corrosion-resistant carbon-coated aluminum foil for lithium batteries.
Disclosure of Invention
In order to overcome the technical problems, the invention aims to provide a corrosion-resistant carbon-coated aluminum foil for a lithium battery: the modified conductive graphite powder, the polyvinylidene fluoride and the N-methyl pyrrolidone are added into a mixer for stirring and mixing to obtain the corrosion-resistant coating, the aluminum foil is placed into absolute ethyl alcohol for ultrasonic cleaning, then is taken out for washing with distilled water, and then is dried to obtain the pretreated aluminum foil, the corrosion-resistant coating is coated on the pretreated aluminum foil, and then is dried to enable the corrosion-resistant coating to be solidified to form a corrosion-resistant coating, so that the corrosion-resistant carbon-coated aluminum foil for the lithium battery is obtained.
The aim of the invention can be achieved by the following technical scheme:
the corrosion-resistant carbon-coated aluminum foil for the lithium battery comprises an aluminum foil and a corrosion-resistant coating on the surface of the aluminum foil, wherein the corrosion-resistant coating contains modified conductive graphite powder;
the corrosion-resistant carbon-coated aluminum foil for the lithium battery is prepared by the following steps:
step one: weighing 3-15 parts of modified conductive graphite powder, 12-24 parts of polyvinylidene fluoride and 280-360 parts of N-methylpyrrolidone according to parts by weight for standby;
Step two: adding modified conductive graphite powder, polyvinylidene fluoride and N-methyl pyrrolidone into a mixer, and stirring and mixing for 4-5 hours under the conditions that the temperature is 35-45 ℃ and the stirring speed is 800-1200r/min to obtain a corrosion-resistant coating;
Step three: placing the aluminum foil in absolute ethyl alcohol, ultrasonically cleaning for 20-30min under the condition that the ultrasonic frequency is 45-55kHz, then taking out, washing for 3-5 times by distilled water, then placing in a vacuum drying oven, and drying for 3-4h under the condition that the temperature is 65-70 ℃ to obtain the pretreated aluminum foil;
step four: and (3) coating the corrosion-resistant coating on the pretreated aluminum foil, then placing the pretreated aluminum foil in a vacuum drying oven, drying for 1-2 hours at the temperature of 65-70 ℃, and then heating to 100-120 ℃ and drying for 2-3 hours, wherein the corrosion-resistant coating is cured to form a corrosion-resistant coating, so that the corrosion-resistant carbon-coated aluminum foil for the lithium battery is obtained.
As a further scheme of the invention: the modified conductive graphite powder is prepared by the following steps:
A1: adding conductive graphite powder and hydrogen peroxide solution into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirring and reacting for 8-12h at the temperature of 90-100 ℃ and the stirring speed of 500-600r/min, cooling the reaction product to room temperature after the reaction is finished, vacuum filtering, washing a filter cake with distilled water for 3-5 times, then placing in a vacuum drying oven, and drying for 6-8h at the temperature of 65-70 ℃ to obtain an intermediate 1;
The reaction principle is as follows:
a2: adding the intermediate 1, thionyl chloride, triethylamine and chloroform into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirring for 0.5-1h under the condition of 20-25 ℃ and stirring speed of 500-600r/min, heating to reflux, continuing stirring for 4-6h, vacuum filtering a reaction product after the reaction is finished, placing a filter cake into a vacuum drying oven, and drying for 3-5h under the condition of 65-70 ℃ to obtain an intermediate 2;
The reaction principle is as follows:
A3: adding the dispersion liquid of the intermediate 2 and 3-thiophenemethylamine into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirring for 0.5-1h at the temperature of 20-25 ℃ and the stirring speed of 500-600r/min, heating to reflux, controlling the heating speed to be 1-3 ℃/min, continuing stirring for 30-40h, filtering the reaction product while the reaction is hot, washing a filter cake with distilled water for 2-3 times, placing in a vacuum drying oven, and drying for 4-5h at the temperature of 65-70 ℃ to obtain an intermediate 3;
The reaction principle is as follows:
A4: adding the intermediate 3, anhydrous ferric trichloride and N, N-dimethylformamide into a four-neck flask provided with a stirrer, a thermometer, a constant-pressure dropping funnel and a reflux condenser, stirring for 0.5-1h under the condition of the temperature of 20-25 ℃ and the stirring rate of 500-600r/min, dropwise adding thiophene while stirring, controlling the dripping rate to be 1-2 drops/s, heating to reflux after the dripping, controlling the heating rate to be 1-3 ℃/min, continuing stirring for reaction for 10-15h, pouring the reaction product into anhydrous methanol after the reaction is finished, standing for 4-5h, vacuum-filtering, washing a filter cake with anhydrous methanol and distilled water for 3-5 times sequentially, and then placing in a vacuum drying box, and drying for 6-7h under the condition of the temperature of 65-70 ℃ to obtain the modified conductive graphite powder.
The reaction principle is as follows:
As a further scheme of the invention: the dosage ratio of the conductive graphite powder to the hydrogen peroxide solution in the step A1 is 1g:20-30mL, wherein the mass fraction of the hydrogen peroxide solution is 30-40%.
As a further scheme of the invention: the dosage ratio of the intermediate 1, thionyl chloride, triethylamine and chloroform in the step A2 is 10g:3.0-4.5g:0.1-0.15g:80-100mL.
As a further scheme of the invention: the dosage ratio of the intermediate 2 dispersion liquid and the 3-thiophenemethanamine in the step A3 is 100mL:3.5-9.5g of said intermediate 2 dispersion is prepared according to 1g of intermediate 2: adding 10mL into absolute ethanol, and performing ultrasonic dispersion for 30-50min under the condition of ultrasonic frequency of 50-60 kHz.
As a further scheme of the invention: the dosage ratio of the intermediate 3, anhydrous ferric trichloride, N-dimethylformamide and thiophene in the step A4 is 1g:0.85-1.2g:40-50mL:0.5-2.5g.
The invention has the beneficial effects that:
according to the corrosion-resistant carbon-coated aluminum foil for the lithium battery, the modified conductive graphite powder, the polyvinylidene fluoride and the N-methyl pyrrolidone are added into a mixer to be stirred and mixed to obtain the corrosion-resistant coating, the aluminum foil is placed into absolute ethyl alcohol to be ultrasonically cleaned, then the aluminum foil is taken out to be washed by distilled water, and then the aluminum foil is dried to obtain a pretreated aluminum foil, the corrosion-resistant coating is coated on the pretreated aluminum foil, and then the aluminum foil is dried to enable the corrosion-resistant coating to be solidified to form a corrosion-resistant coating, so that the corrosion-resistant carbon-coated aluminum foil for the lithium battery is obtained; the corrosion-resistant carbon-coated aluminum foil for the lithium battery can effectively improve corrosion resistance by forming the corrosion-resistant coating on the surface of the aluminum foil, wherein a large number of C-F bonds are contained in a molecular chain of polyvinylidene fluoride in the corrosion-resistant coating, so that the aluminum foil is not easy to corrode by electrolyte, the aluminum foil is effectively protected, and the modified conductive graphite powder in the corrosion-resistant coating has good conductivity, so that the aluminum foil can still maintain high electrochemical performance after the corrosion-resistant coating is formed, and therefore, the prepared corrosion-resistant carbon-coated aluminum foil for the lithium battery has good high-temperature oxidation resistance, corrosion resistance and good electrochemical performance;
In the process of preparing the corrosion-resistant carbon-coated aluminum foil for the lithium battery, firstly, preparing modified conductive graphite powder, firstly, oxidizing the conductive graphite powder by using hydrogen peroxide as an oxidant, introducing a large amount of carboxyl groups on the surface of the conductive graphite powder to obtain an intermediate 1, then, performing acyl chlorination on the carboxyl groups on the intermediate 1 by using thionyl chloride, introducing a large amount of acyl chloride groups to improve the reaction activity of the intermediate 1, obtaining an intermediate 2, performing nucleophilic substitution reaction on the acyl chloride groups on the intermediate 2 and amino groups on 3-thiophene methylamine, thereby introducing thiophene rings into the intermediate 2, obtaining an intermediate 3, performing reaction between the intermediate 3 and thiophene, polymerizing the thiophene rings on the intermediate 3 and thiophene to form polythiophene, and wrapping the conductive graphite powder to obtain the modified conductive graphite powder; the modified conductive graphite powder is a core-shell structure formed by conductive graphite powder and polythiophene, the conductive graphite powder has good conductive performance, the dispersibility of the conductive graphite powder is improved after the conductive graphite powder is wrapped by the polythiophene, the conductive graphite powder is prevented from agglomerating, the conductive graphite powder can be uniformly attached to the surface of an aluminum foil, the conductivity of the aluminum foil is improved, the polythiophene is a polymer with high conductive performance, the conductive graphite powder is wrapped by the conductive graphite powder, the conductive performance of the conductive graphite powder is not reduced, the conductive graphite powder is improved, and the corrosion resistance of electrolyte to the conductive graphite powder is improved after the conductive graphite powder is wrapped by the conductive graphite powder.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
The embodiment is a preparation method of modified conductive graphite powder, which comprises the following steps:
A1: adding 1g of conductive graphite powder and 20mL of 30% hydrogen peroxide solution in mass fraction into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirring at 90 ℃ and stirring speed of 500r/min for reaction for 8h, cooling the reaction product to room temperature after the reaction is finished, vacuum filtering, washing a filter cake with distilled water for 3 times, and then placing in a vacuum drying box, and drying at 65 ℃ for 6h to obtain an intermediate 1;
A2: 10g of intermediate 1, 3.0g of thionyl chloride, 0.1g of triethylamine and 80mL of chloroform are added into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, and are stirred for 0.5h under the condition that the temperature is 20 ℃ and the stirring rate is 500r/min, then the mixture is heated to reflux, stirring reaction is continued for 4h, after the reaction is finished, the reaction product is filtered in vacuum, a filter cake is placed in a vacuum drying oven, and is dried for 3h under the condition that the temperature is 65 ℃ to obtain intermediate 2;
A3: 100mL of intermediate 2 was taken at 1g: adding 10mL of the mixture into absolute ethyl alcohol, then adding 3.5g of 3-thiophenemethanamine and 3.5g of intermediate 2 dispersion liquid obtained by ultrasonic dispersion for 30min under the condition of ultrasonic frequency of 50kHz into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirring for 0.5h under the condition of temperature of 20 ℃ and stirring rate of 500r/min, then heating to reflux, controlling the heating rate to be 1 ℃/min, continuing stirring for 30h, filtering the reaction product while the reaction product is hot, washing a filter cake with distilled water for 2 times, then placing in a vacuum drying box, and drying for 4h under the condition of temperature of 65 ℃ to obtain intermediate 3;
A4: adding 1g of intermediate 3, 0.85g of anhydrous ferric trichloride and 40mLN, N-dimethylformamide into a four-neck flask provided with a stirrer, a thermometer, a constant pressure dropping funnel and a reflux condenser, stirring for 0.5h under the condition that the temperature is 20 ℃ and the stirring rate is 500r/min, dropwise adding 0.5g of thiophene while stirring, controlling the dropping rate to be 1 drop/s, heating to reflux after the dropping, controlling the heating rate to be 1 ℃/min, continuing stirring for reaction for 10h, pouring the reaction product into anhydrous methanol after the reaction is finished, standing for 4h, vacuum filtering, washing a filter cake with anhydrous methanol and distilled water for 3 times in sequence, and then placing in a vacuum drying box, and drying for 6h under the condition that the temperature is 65 ℃ to obtain the modified conductive graphite powder.
Example 2:
The embodiment is a preparation method of modified conductive graphite powder, which comprises the following steps:
A1: adding 1g of conductive graphite powder and 25mL of hydrogen peroxide solution with the mass fraction of 35% into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirring and reacting for 10 hours at the temperature of 95 ℃ and the stirring speed of 550r/min, cooling the reaction product to room temperature after the reaction is finished, carrying out vacuum suction filtration, washing a filter cake with distilled water for 4 times, and then placing in a vacuum drying box, and drying for 7 hours at the temperature of 68 ℃ to obtain an intermediate 1;
A2: 10g of intermediate 1, 3.8g of thionyl chloride, 0.12g of triethylamine and 90mL of chloroform are added into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, the mixture is stirred for 0.8h under the condition that the temperature is 22 ℃ and the stirring rate is 550r/min, then the mixture is heated to reflux, the mixture is continuously stirred for 5h, the reaction product is filtered in vacuum after the reaction is finished, a filter cake is placed in a vacuum drying oven, and the mixture is dried for 4h under the condition that the temperature is 68 ℃ to obtain intermediate 2;
A3: 100mL of intermediate 2 was taken at 1g: adding 10mL of the mixture into absolute ethyl alcohol, then adding an intermediate 2 dispersion liquid obtained by ultrasonic dispersion for 40min under the condition of ultrasonic frequency of 55kHz and 6.5g of 3-thiophene methylamine into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirring for 0.8h under the condition of temperature of 22 ℃ and stirring rate of 550r/min, then heating to reflux, controlling the heating rate to be 2 ℃/min, continuing stirring for 35h, filtering a reaction product while the reaction product is hot, washing a filter cake with distilled water for 2 times, then placing in a vacuum drying oven, and drying for 4.5h under the condition of temperature of 68 ℃ to obtain an intermediate 3;
A4: 1g of intermediate 3, 1.0g of anhydrous ferric trichloride and 45mLN, N-dimethylformamide are added into a four-neck flask provided with a stirrer, a thermometer, a constant pressure dropping funnel and a reflux condenser, stirred for 0.8h under the condition that the temperature is 22 ℃ and the stirring rate is 550r/min, 1.5g of thiophene is added dropwise while stirring, the dropping rate is controlled to be 1 drop/s, the temperature is raised to reflux after the dropping, the heating rate is controlled to be 2 ℃/min, then stirring is continued for 12h, the reaction product is poured into anhydrous methanol after the reaction is finished, then the reaction product is kept for 4.5h, then vacuum suction filtration is carried out, a filter cake is washed for 4 times by anhydrous methanol and distilled water in sequence, and then the filter cake is placed into a vacuum drying box and dried for 6.5h under the condition that the temperature is 68 ℃ to obtain the modified conductive graphite powder.
Example 3:
The embodiment is a preparation method of modified conductive graphite powder, which comprises the following steps:
A1: adding 1g of conductive graphite powder and 30mL of 40% hydrogen peroxide solution in mass fraction into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirring at a temperature of 100 ℃ and a stirring rate of 600r/min for reaction for 12h, cooling the reaction product to room temperature after the reaction is finished, carrying out vacuum suction filtration, washing a filter cake with distilled water for 5 times, and then placing in a vacuum drying box, and drying at a temperature of 70 ℃ for 8h to obtain an intermediate 1;
A2: 10g of intermediate 1, 4.5g of thionyl chloride, 0.15g of triethylamine and 100mL of chloroform are added into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, and are stirred for 1h under the condition that the temperature is 25 ℃ and the stirring rate is 600r/min, then the mixture is heated to reflux and is continuously stirred for 6h, after the reaction is finished, the reaction product is filtered in vacuum, and a filter cake is placed in a vacuum drying box and is dried for 5h under the condition that the temperature is 70 ℃ to obtain intermediate 2;
A3: 100mL of intermediate 2 was taken at 1g: adding 10mL of the mixture into absolute ethyl alcohol, then adding an intermediate 2 dispersion liquid obtained by ultrasonic dispersion for 50min under the condition of ultrasonic frequency of 60kHz and 9.5g of 3-thiophene methylamine into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirring for 1h under the condition of 25 ℃ and stirring rate of 600r/min, heating to reflux, controlling the heating rate to be 3 ℃/min, continuing stirring for 40h, filtering a reaction product while the reaction product is hot, washing a filter cake with distilled water for 3 times, then placing in a vacuum drying oven, and drying for 5h under the condition of 70 ℃ to obtain an intermediate 3;
A4: adding 1g of intermediate 3, 1.2g of anhydrous ferric trichloride and 50mLN, N-dimethylformamide into a four-neck flask provided with a stirrer, a thermometer, a constant pressure dropping funnel and a reflux condenser, stirring for 1h at the temperature of 25 ℃, dropwise adding 2.5g of thiophene while stirring at the stirring speed of 600r/min, controlling the dropping speed to be 2 drops/s, heating to reflux after the dropping, controlling the heating speed to be 3 ℃/min, continuing stirring for 15h, pouring the reaction product into anhydrous methanol after the reaction is finished, standing for 5h, vacuum filtering, washing a filter cake with anhydrous methanol and distilled water for 5 times sequentially, then placing in a vacuum drying box, and drying for 7h at the temperature of 70 ℃ to obtain the modified conductive graphite powder.
Example 4:
the embodiment is a preparation method of corrosion-resistant carbon-coated aluminum foil for a lithium battery, which comprises the following steps:
Step one: weighing 3 parts of modified conductive graphite powder, 12 parts of polyvinylidene fluoride and 280 parts of N-methylpyrrolidone in part by weight from example 1 for later use;
Step two: adding the modified conductive graphite powder, polyvinylidene fluoride and N-methyl pyrrolidone into a mixer, and stirring and mixing for 4 hours under the conditions that the temperature is 35 ℃ and the stirring speed is 800r/min to obtain the corrosion-resistant coating;
Step three: placing the aluminum foil in absolute ethyl alcohol, ultrasonically cleaning for 20min under the condition that the ultrasonic frequency is 45kHz, taking out, washing for 3 times by using distilled water, placing in a vacuum drying oven, and drying for 3h under the condition that the temperature is 65 ℃ to obtain pretreated aluminum foil;
Step four: and (3) coating the corrosion-resistant coating on the pretreated aluminum foil, then placing the pretreated aluminum foil in a vacuum drying oven, drying for 1h at the temperature of 65 ℃, and then drying for 2h at the temperature of 100 ℃ to obtain the corrosion-resistant carbon-coated aluminum foil for the lithium battery.
Example 5:
the embodiment is a preparation method of corrosion-resistant carbon-coated aluminum foil for a lithium battery, which comprises the following steps:
Step one: 9 parts of modified conductive graphite powder, 18 parts of polyvinylidene fluoride and 320 parts of N-methyl pyrrolidone from the example 2 are weighed according to parts by weight for standby;
Step two: adding the modified conductive graphite powder, polyvinylidene fluoride and N-methyl pyrrolidone into a mixer, and stirring and mixing for 4.5 hours under the conditions that the temperature is 40 ℃ and the stirring speed is 1000r/min to obtain the corrosion-resistant coating;
step three: placing the aluminum foil in absolute ethyl alcohol, ultrasonically cleaning for 25min under the condition that the ultrasonic frequency is 50kHz, taking out, washing for 3-5 times by distilled water, placing in a vacuum drying oven, and drying for 3.5h under the condition that the temperature is 68 ℃ to obtain the pretreated aluminum foil;
step four: and (3) coating the corrosion-resistant coating on the pretreated aluminum foil, then placing the pretreated aluminum foil in a vacuum drying oven, drying for 1.5 hours at the temperature of 68 ℃, and then drying for 2.5 hours at the temperature of 110 ℃ to obtain the corrosion-resistant carbon-coated aluminum foil for the lithium battery.
Example 6:
the embodiment is a preparation method of corrosion-resistant carbon-coated aluminum foil for a lithium battery, which comprises the following steps:
step one: 15 parts of modified conductive graphite powder, 24 parts of polyvinylidene fluoride and 360 parts of N-methyl pyrrolidone from the example 3 are weighed according to parts by weight for standby;
Step two: adding the modified conductive graphite powder, polyvinylidene fluoride and N-methyl pyrrolidone into a mixer, and stirring and mixing for 5 hours under the conditions that the temperature is 45 ℃ and the stirring speed is 1200r/min to obtain the corrosion-resistant coating;
Step three: placing the aluminum foil in absolute ethyl alcohol, ultrasonically cleaning for 30min under the condition that the ultrasonic frequency is 55kHz, taking out, washing for 5 times by distilled water, placing in a vacuum drying oven, and drying for 4h under the condition that the temperature is 70 ℃ to obtain pretreated aluminum foil;
Step four: and (3) coating the corrosion-resistant coating on the pretreated aluminum foil, then placing the pretreated aluminum foil in a vacuum drying oven, drying for 2 hours at the temperature of 70 ℃, and then drying for 3 hours at the temperature of 120 ℃ after heating, wherein the corrosion-resistant coating is solidified to form a corrosion-resistant coating, so that the corrosion-resistant carbon-coated aluminum foil for the lithium battery is obtained.
Comparative example 1:
Comparative example 1 is different from example 6 in that a conductive graphite powder is used instead of the modified conductive graphite powder.
Comparative example 2:
comparative example 2 differs from example 6 in that carboxymethyl cellulose was used instead of polyvinylidene fluoride.
Comparative example 3:
comparative example 3 is different from example 6 in that conductive graphite powder was used instead of modified conductive graphite powder and carboxymethyl cellulose was used instead of polyvinylidene fluoride.
| Sample of | Electrolyte corrosion resistance of aluminum foil | Electrode sheet impedance, Ω | Internal resistance of battery, mΩ |
| Example 4 | Good quality | 1.7 | 0.26 |
| Example 5 | Good quality | 1.5 | 0.25 |
| Example 6 | Good quality | 1.4 | 0.25 |
| Comparative example 1 | Good quality | 2.2 | 0.52 |
| Comparative example 2 | In general | 1.7 | 0.29 |
| Comparative example 3 | Poor quality | 2.4 | 0.28 |
Referring to the data in the table, according to the comparison between the embodiment 6 and the comparative examples 1-3, it can be known that the addition of the modified conductive graphite powder and polyvinylidene fluoride can effectively improve the corrosion resistance of the corrosion-resistant carbon-coated aluminum foil, reduce the internal resistance of the battery and improve the conductivity of the battery.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (5)
1. The corrosion-resistant carbon-coated aluminum foil for the lithium battery is characterized by comprising an aluminum foil and a corrosion-resistant coating on the surface of the aluminum foil, wherein the corrosion-resistant coating contains modified conductive graphite powder;
the corrosion-resistant carbon-coated aluminum foil for the lithium battery is prepared by the following steps:
step one: weighing 3-15 parts of modified conductive graphite powder, 12-24 parts of polyvinylidene fluoride and 280-360 parts of N-methylpyrrolidone according to parts by weight for standby;
Step two: adding modified conductive graphite powder, polyvinylidene fluoride and N-methyl pyrrolidone into a mixer, and stirring and mixing for 4-5 hours under the conditions that the temperature is 35-45 ℃ and the stirring speed is 800-1200r/min to obtain a corrosion-resistant coating;
Step three: placing the aluminum foil in absolute ethyl alcohol, ultrasonically cleaning for 20-30min under the condition that the ultrasonic frequency is 45-55kHz, then taking out, washing for 3-5 times by distilled water, then placing in a vacuum drying oven, and drying for 3-4h under the condition that the temperature is 65-70 ℃ to obtain the pretreated aluminum foil;
step four: coating the corrosion-resistant coating on the pretreated aluminum foil, then placing the pretreated aluminum foil in a vacuum drying oven, drying for 1-2 hours at the temperature of 65-70 ℃, then heating to 100-120 ℃ and drying for 2-3 hours, and curing the corrosion-resistant coating to form a corrosion-resistant coating, thus obtaining the corrosion-resistant carbon-coated aluminum foil for the lithium battery;
The modified conductive graphite powder is prepared by the following steps:
A1: adding conductive graphite powder and hydrogen peroxide solution into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirring and reacting for 8-12h at the temperature of 90-100 ℃ and the stirring speed of 500-600r/min, cooling the reaction product to room temperature after the reaction is finished, vacuum filtering, washing a filter cake with distilled water for 3-5 times, then placing in a vacuum drying oven, and drying for 6-8h at the temperature of 65-70 ℃ to obtain an intermediate 1;
a2: adding the intermediate 1, thionyl chloride, triethylamine and chloroform into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirring for 0.5-1h under the condition of 20-25 ℃ and stirring speed of 500-600r/min, heating to reflux, continuing stirring for 4-6h, vacuum filtering a reaction product after the reaction is finished, placing a filter cake into a vacuum drying oven, and drying for 3-5h under the condition of 65-70 ℃ to obtain an intermediate 2;
A3: adding the dispersion liquid of the intermediate 2 and 3-thiophenemethylamine into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirring for 0.5-1h at the temperature of 20-25 ℃ and the stirring speed of 500-600r/min, heating to reflux, controlling the heating speed to be 1-3 ℃/min, continuing stirring for 30-40h, filtering the reaction product while the reaction is hot, washing a filter cake with distilled water for 2-3 times, placing in a vacuum drying oven, and drying for 4-5h at the temperature of 65-70 ℃ to obtain an intermediate 3;
A4: adding the intermediate 3, anhydrous ferric trichloride and N, N-dimethylformamide into a four-neck flask provided with a stirrer, a thermometer, a constant-pressure dropping funnel and a reflux condenser, stirring for 0.5-1h under the condition of the temperature of 20-25 ℃ and the stirring rate of 500-600r/min, dropwise adding thiophene while stirring, controlling the dripping rate to be 1-2 drops/s, heating to reflux after the dripping, controlling the heating rate to be 1-3 ℃/min, continuing stirring for reaction for 10-15h, pouring the reaction product into anhydrous methanol after the reaction is finished, standing for 4-5h, vacuum-filtering, washing a filter cake with anhydrous methanol and distilled water for 3-5 times sequentially, and then placing in a vacuum drying box, and drying for 6-7h under the condition of the temperature of 65-70 ℃ to obtain the modified conductive graphite powder.
2. The corrosion-resistant carbon-coated aluminum foil for lithium batteries according to claim 1, wherein the ratio of the conductive graphite powder to the hydrogen peroxide solution in step A1 is 1g:20-30mL, wherein the mass fraction of the hydrogen peroxide solution is 30-40%.
3. The corrosion-resistant carbon-coated aluminum foil for lithium batteries according to claim 1, wherein the intermediate 1, thionyl chloride, triethylamine and chloroform in step A2 are used in an amount ratio of 10g:3.0-4.5g:0.1-0.15g:80-100mL.
4. The corrosion resistant carbon coated aluminum foil for lithium batteries according to claim 1, wherein the intermediate 2 dispersion, 3-thiophenemethanamine in step A3 is used in an amount ratio of 100mL:3.5-9.5g of said intermediate 2 dispersion is prepared according to 1g of intermediate 2: adding 10mL into absolute ethanol, and performing ultrasonic dispersion for 30-50min under the condition of ultrasonic frequency of 50-60 kHz.
5. The corrosion-resistant carbon-coated aluminum foil for lithium batteries according to claim 1, wherein the intermediate 3, anhydrous ferric trichloride, N-dimethylformamide and thiophene in step A4 are used in an amount ratio of 1g:0.85-1.2g:40-50mL:0.5-2.5g.
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| CN101386406A (en) * | 2008-10-24 | 2009-03-18 | 南开大学 | Composite hybridization material of mono-layer graphite and Fullerenes, preparation method and application thereof |
| CN110676462A (en) * | 2019-10-14 | 2020-01-10 | 福建巨电新能源股份有限公司 | Carbon-coated aluminum foil for lithium battery and preparation method thereof |
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| CN101386406A (en) * | 2008-10-24 | 2009-03-18 | 南开大学 | Composite hybridization material of mono-layer graphite and Fullerenes, preparation method and application thereof |
| CN110676462A (en) * | 2019-10-14 | 2020-01-10 | 福建巨电新能源股份有限公司 | Carbon-coated aluminum foil for lithium battery and preparation method thereof |
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| LiFePO_4正极材料的包覆层与集流体双改性研究;刘小月;李林峰;杨觉明;葛桂贤;;绵阳师范学院学报;20181115(第11期);全文 * |
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