CN112133882A - Solvent-free preparation method of electrode for electrochemical energy storage device - Google Patents
Solvent-free preparation method of electrode for electrochemical energy storage device Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0421—Methods of deposition of the material involving vapour deposition
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- 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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
A solvent-free preparation method of an electrode for an electrochemical energy storage device comprises the steps of placing polymer binder powder in an electric polarization device, and performing electric polarization treatment on the polymer binder to obtain an electric polarization polymer binder; placing the polymer binder subjected to electret polarization, the electrode active substance and the conductive agent in mixing equipment to be uniformly mixed to obtain electrode master batch; placing the electrode master batch into a briquetting machine, placing the electrode master batch into a plunger type extruder after briquetting, and extruding an electrode master batch sample strip; rolling the electrode master batch sample strip in a calender to form an electrode master batch membrane; and placing the electrode master batch membrane in vapor deposition equipment, and depositing a layer of metal collector with the thickness of 10 nm-5 mu m on the surface of the electrode master batch. The electrode master batch has good dispersibility, the manufactured electrode diaphragm has good uniformity, high density and mechanical strength, and easy processing and forming, and the formed electrode has good electrochemical stability, solvent resistance and mechanical property, and has good cycle service life and specific capacitance.
Description
Technical Field
The invention belongs to the field of electrode preparation, and particularly relates to a solvent-free preparation method of an electrode for an electrochemical energy storage device.
Background
The electrode provides a place for charge storage/release, and becomes a key core component of electrochemical energy storage devices such as lithium ion batteries, super capacitors and lithium ion capacitors. The preparation method of the electrode can be divided into a wet method and a dry method. The wet method is to mix electrode active material, conductive agent, binder and the like in water or organic solvent to obtain viscous slurry; then compounding with a metal collector by using methods such as roller coating, blade coating, spraying and the like; and finally, removing the solvent through the processes of rolling, drying, finishing and the like to obtain the electrode. The wet method for preparing the electrode has the advantages of uniform mixing of electrode components, simple technical process, strong continuity and the like, but also has the defects of more water/solvent residues, blockage of a charge channel by a binder, low volume ratio energy storage density and the like. The dry electrode preparation process comprises the steps of obtaining uniformly mixed electrode master batch by mixing electrode active substances, a conductive agent and a binder through mixing equipment; then, the adhesive is fiberized through fiberizing equipment to form a three-dimensional net structure, so that the granular inorganic particles form an electrode master batch membrane; and finally compounding the electrode master batch membrane with a metal collector through a conductive adhesive to obtain the electrode. The dry process has the advantages of no solvent residue, high utilization rate of electrode active substances, wide adjustable range of electrode thickness and the like, and becomes an advanced electrode preparation method.
CN 109755473A discloses a dry preparation method of lithium battery electrode, which is to mix and fine-crush the electrode material evenly, roll it in multiple passes at high temperature to form the electrode film belt, then compound it on the metal foil belt with adhesive coating by high temperature rolling, finally get the coiled electrode. CN 105225847A discloses a method for preparing a dry electrode for an electric double layer capacitor, which comprises uniformly mixing powder-state activated carbon, a binder polytetrafluoroethylene powder and a conductive agent by a high-speed airflow mixing technology; meanwhile, the active substance, the conductive agent and the binder are mixed by means of the deformation structure of the PTFE under the high-speed shearing condition, and the electrode plate for the super capacitor is obtained. The two methods adopt dry methods to manufacture the electrode, but the two methods adopt electrode master batch powder to directly roll to form an electrode diaphragm, and have the defects of poor uniformity, low density, small mechanical strength and the like of the electrode.
CN 102629681A discloses a preparation method of a dry electrode, which is to uniformly mix a powder active substance, a powder conductive agent and a powder binder through a three-dimensional powder mixer or a gravity-free powder mixer, then crush the mixture through a low-temperature crusher, then perform fiberization extrusion molding through a double-screw extruder or an internal mixer/open mill, then perform hot pressing through a calender to reach a target thickness, finally form the electrode by combining three layers with a current collector printed with conductive adhesive, and perform cold rolling to improve the compaction density. CN 101894676A discloses a preparation method of a membrane for an electrode plate of a super capacitor, which comprises extruding carbon black, linear low density polyethylene and activated carbon powder by a double screw to form a soft core blank with a paste-shaped blank shell, and then obtaining the electrode by processes of rolling, finish rolling, curling and the like. The two methods also adopt a dry method to manufacture the electrode, but the polymer binder agglomeration of the two methods can not be completely opened, so that the dispersion degree between electrode materials is low; the problems of difficult master batch conveying, easy material slipping, large equipment loss and the like in the screw extrusion processing process are caused by the fact that a polymer binder has large molecular weight, high viscosity and high content of electrode active powder in the screw extrusion processing process, and due to frictional heat generation, powder can be adhered to a screw or a machine barrel, so that feeding is more difficult and unstable; the conductive adhesive connecting the electrode master batch membrane and the collector has insufficient electrochemical stability, solvent resistance and mechanical property, can influence the cycle service life of an electrochemical device, belongs to a non-electrode active substance, and can reduce the specific capacitance of the electrochemical energy storage device.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a solvent-free preparation method of an electrode for an electrochemical energy storage device, the dispersibility of an electrode master batch is good, a prepared electrode membrane has good uniformity, large density and high mechanical strength, is easy to machine and form, and the formed electrode has good electrochemical stability, solvent resistance and mechanical property, and has good cycle service life and specific capacitance.
The technical scheme of the invention is as follows:
a solvent-free preparation method of an electrode for an electrochemical energy storage device comprises the following specific steps:
(1) polymer binder electro-electret
Placing the polymer binder powder in an electric polarization device, and performing electric polarization treatment on the polymer binder to obtain an electric polarization polymer binder;
(2) preparation of electrode masterbatch
Placing the polymer binder subjected to electret polarization, the electrode active substance and the conductive agent in mixing equipment to be uniformly mixed to obtain electrode master batch;
(3) preparation of electrode master batch membrane
Placing the electrode master batch into a briquetting machine, placing the electrode master batch into a plunger type extruder after briquetting, and extruding an electrode master batch sample strip; rolling the electrode master batch sample strip into an electrode master batch membrane with the thickness of 50 mu m-5 mm and the width of 100 mm-1000 mm in a rolling mill;
(4) electrode prepared by depositing metal on electrode master batch membrane
And (3) placing the electrode master batch membrane in vapor deposition equipment, and depositing a layer of metal collector with the thickness of 10 nm-5 mu m on the surface of the electrode master batch at the deposition temperature of 80-200 ℃.
Furthermore, the number average molecular weight of the polymer binder is 200-1000 ten thousand, and the particle size is 20 nm-50 μm.
Further, the polymer binder is at least one of polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride and polytetrafluoroethylene-hexafluoropropylene copolymer.
Furthermore, when the electro-electret treatment is carried out, one mode of electrostatic spinning, corona discharge, triboelectrification, thermal polarization and low-energy electron beam bombardment is adopted for treatment.
Further, when electrostatic spinning electro-electret treatment is adopted, the spinning voltage is 15kV, the spinning distance is 10cm, and the spinning speed is 2.0 mL/h;
when adopting corona discharge electro-electret treatment, the voltage of a mesh grid is 10kV, the discharge interval is 1cm, and the treatment speed is 800cm2Min; when the thermal polarization and the electric polarization are adopted, the polymer adhesive is evenly paved on the surface of the copper plate to form a processing layer with the thickness of 1mm and the width of 100mm for heat treatment, the heat treatment temperature is 120 ℃, the intensity of the polarization electric field is 150MV/m, and the polarization speed is 600cm2/min。
Further, the mixing equipment is at least one of a high-speed stirrer, a V-shaped mixer, a gravity-free mixer, a three-dimensional mixer, a ball mill, an open mill, an internal mixer and an air flow mill; when mixing materials, the mixing temperature is 0-200 ℃, and the mixing time is 1-60 min.
Further, the electrode active substance is at least one of lithium salt, carbon-based porous material, graphite-based electrode material, metal oxide and the like, and the particle diameter D505-50 μm; the conductive agent is at least one of carbon aerogel, conductive carbon black, crystalline flake graphite, carbon nano tubes, graphene and ball graphite, and the mass ratio of the polymer binder to the electrode active substance to the conductive agent is 200:1700: 100.
Further, the green compact conditions are that the pressure is 1.0 MPa-10.0 MPa, the green compact speed is 5 mm/min-50 mm/min, the pressure maintaining time is 5 s-10 s, and the green compact temperature is 20-120 ℃;
the plunger type extruder is one of a vertical type, a horizontal type, a single column type, a double plunger type, a continuous type or an intermittent type, and the plunger type extrusion conditions are as follows: the extrusion speed is 10 mm/min-100 mm/min, the extrusion temperature is 30-310 ℃, the compression ratio (RR) is 50-500, the length-diameter ratio (L/D) is 5-50, the cone angle (alpha) is 10-90 degrees, and an extruded electrode master batch spline is one of a rod, a rectangle, a belt or a tube;
the calender is 2-5 rollers, the length-diameter ratio is 2.0-3.0, the calendering speed is 1-10 m/min, and the roller temperature is 20-200 ℃.
The vapor deposition equipment is one of magnetron sputtering equipment, evaporation deposition equipment, ion plating equipment, pulse deposition equipment and atomic layer deposition equipment; the material of the metal collector is one or more of copper, aluminum, silver, gold, platinum and the like.
When the metal aluminum collector is deposited by adopting a magnetron sputtering deposition mode, the purity of an aluminum target material is more than or equal to 99.99 percent, the temperature of a substrate is 200 ℃, and the argon pressure is 4 multiplied by 10-3Torr, bias voltage is-500V, deposition rate is 50nm/min, sputtering time is 60 min; when the metallic silver collector is deposited by adopting an evaporation deposition mode, the purity of a silver target material is more than or equal to 99.99 percent, the temperature of a base material is 120 ℃, the evaporation current is 500A, and the deposition thickness is 5 mu m;
when the metal copper collector is deposited by adopting an atomic layer deposition mode, bis (hexafluoroacetylacetone ketone) copper is used as a precursor, the deposition temperature is 120 ℃, the input power is 300W, the deposition rate is 0.1 nm/cycle, and the deposition thickness is 2 micrometers.
Firstly, obtaining an electret polymer binder by adopting an electric polarization method, and uniformly mixing the electret polymer binder with an electrode active substance, a conductive agent and the like to obtain an electrode master batch; secondly, preparing an electrode master batch sample strip by a plunger type extruder, and rolling the electrode master batch sample strip into an electrode master batch membrane; and finally, preparing the electrode by a vapor deposition metal collector method. The beneficial effects are as follows:
1. the dispersion uniformity among the electrode master batches is improved by performing electric electret treatment on the polymer binder. The polymer binder with the electret polarization has the same charge, so that the electrostatic repulsion can weaken the cohesion and the agglomeration degree among the molecular chains of the polymer binder, and further improve the dispersibility of the polymer binder; and the polymer binder of the electric polarization is easier to be adsorbed on the surfaces of electrode active materials and conductive agent particles, so that the mixing and dispersing uniformity among electrode materials is improved.
2. The solvent-free electrode master batch membrane is prepared in a plunger type extrusion mode, and has the advantages of simple process, strong controllability and good product quality. The blank making process of the electrode master batch is beneficial to removing gas among master batch particles and improving the contact among the particles and the density of an electrode master batch membrane; the plunger type extrusion process is beneficial to the extrusion processing of the solvent-free type electrode master batch with high viscosity, low fluidity and high inorganic particle content; the plunger type extrusion process can effectively control the fiberization degree of the polymer adhesive, is beneficial to the rolling forming processing of the electrode diaphragm and the improvement of the mechanical strength and the density of the electrode master batch diaphragm.
3. The electrode master batch membrane is used for depositing the metal collector, so that the electrode quality can be improved. The metal collector is deposited on the surface of the electrode master batch membrane by adopting a vapor deposition method, and the interface between the metal collector and the electrode active substance with high bonding strength can be obtained by utilizing the characteristics of high adhesive force of the metal deposition layer, high porosity, rough irregular surface of the electrode master batch membrane, fibrous network structure of polymer binder and the like, so that the cycle service life of the electrode is prolonged; the metal collector with the nanometer and micron thickness reduces the metal content without charge storage capacity, and is beneficial to improving the specific capacitance of the electrochemical energy storage device; the binding agent between the electrode diaphragm and the metal collector is not needed, so that the restriction of the binding agent on the electrochemical cycle stability can be removed, the mass ratio of electrode active substances in the electrode can be improved, and the improvement of the specific capacitance of the electrochemical energy storage device is facilitated.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a scanning electron microscope photograph of a polytetrafluoroethylene binder of the invention (corresponding to example 1) before and after electric polarization;
FIG. 3 is a scanning electron micrograph of an electrode masterbatch made of a polymer binder before and after electro-electret treatment according to the invention (corresponding to example 1);
FIG. 4 is a scanning electron microscope photograph of an electrode master batch direct calendered film and a ram extruder post-strip extrusion calender rolled film of the present invention (corresponding to example 1);
FIG. 5 optical photograph of electrode master batch membrane deposited metallic aluminum;
fig. 6 is a test curve of specific charge-discharge capacity retention ratio in cycles of example 1 and comparative example 1.
Detailed Description
Example 1
The process flow is shown in figure 1, and the specific preparation steps are as follows:
1. polytetrafluoroethylene binder electro-electret
The polytetrafluoroethylene binder particles (fig. 2a) were electro-electret by corona discharge. 400g of polytetrafluoroethylene binder particles with the particle size of 20nm and the molecular weight of 1000 ten thousand are uniformly spread to form a treatment layer with the thickness of 500 mu m and the width of 100 mm. Adopting corona discharge equipment, the voltage of a mesh grid is 10kV, the discharge distance is 1cm, and the processing speed is 800cm2Min, resulting in electret poled polytetrafluoroethylene binder particles (FIG. 2 b).
2. Preparation of active carbon electrode master batch
And preparing the electrode master batch by adopting three-dimensional mixing equipment. 200g of electret-polarized polytetrafluoroethylene, 100g of carbon aerogel and 1700g of activated carbon (D)5050 μm), placing in a three-dimensional mixing device, rotating at 72 rpm for 30min, and sieving with 100 mesh sieve to obtain activated carbon electrode master batch (fig. 3 b).
3. Preparation of active carbon electrode master batch membrane
And preparing the electrode master batch membrane by adopting a plunger extrusion sample strip calendaring method. After 1000g of electrode master batch is pressed: the pressure is 100.0MPa, the blank pressing speed is 50mm/min, the blank pressing temperature is 20 ℃, and the pressure maintaining time is 5s, so that the electrode master blank is obtained. The pressed electrode master batch was placed in a single ram extruder to extrude bars: the extrusion speed is 50mm/min, the extrusion temperature is 85 ℃, the compression ratio (RR) is 200, the length-diameter ratio (L/D) is 25, and the cone angle (alpha) is 40 degrees, so that an electrode master batch sample strip with the diameter of 10mm is prepared. The electrode master batch sample strip is placed in a double-roll calender, the length-diameter ratio is 2.0, the calendering speed is 1m/min, the roll temperature is 20 ℃, and an electrode master batch membrane with the thickness of 200 mu m and the width of 500mm is prepared (figure 4 b).
4. Active carbon electrode master batch membrane deposited metal collector
And depositing a metal aluminum collector on the surface of the electrode master batch membrane by adopting a magnetron sputtering method. Placing the electrode master batch membrane in a magnetron sputtering device, and obtaining an aluminum target material (the purity is more than or equal to 99.99 percent),Substrate temperature 200 ℃ and argon pressure 4X 10-3Torr, bias voltage-500V, deposition rate 50nm/min, sputtering time 60 min. And preparing the electrode for the supercapacitor with the activated carbon electrode master batch membrane deposited with the metal aluminum (figure 5 b).
5. Preparation of activated carbon electrode super capacitor
The method comprises the steps of taking metal aluminum deposited on an activated carbon electrode master batch membrane as an electrode for a super capacitor, taking Mitsubishi diaphragm paper (FPC3018) as an electrode diaphragm, taking an acetonitrile solution (1.0mol/L) of tetraethylammonium tetrafluoroborate as an electrolyte, and assembling the super capacitor in a glove box with the water oxygen content less than or equal to 10 ppm. The electrochemical data after 10000 times of charge and discharge under the conditions of constant current of 10.0A/g and working voltage of 2.7V are shown in Table 1.
FIG. 2 is a scanning electron micrograph of a polytetrafluoroethylene binder of the invention (corresponding to example 1) taken before and after electric polarization. The result shows that the diameter of the nano-sized polytetrafluoroethylene particles before electro-electret treatment is 20-30 nm, and the degree of agglomeration among the particles is large (figure 2 a); the diameter of the electrically-standing polarized polytetrafluoroethylene particles is slightly increased, and the agglomeration degree among the particles is reduced (FIG. 2 b). The electrically-standing polarized polytetrafluoroethylene can increase the molecular chain spacing and reduce the agglomeration among polytetrafluoroethylene nano particles due to the repulsion effect among the same charges.
Fig. 3 is a scanning electron micrograph of an electrode masterbatch made of a polymer binder before and after electro-electret treatment according to the invention (corresponding to example 1). The results show that the phase separation between the electrode master batch particles prepared by the polymer binder which is not electrically electret polarized is obvious, and the full uniform dispersion between the larger activated carbon particles and the polytetrafluoroethylene binder particles with smaller particle size is not realized (figure 3 a); in the electrode master batch prepared from the electrically-standing polarized polytetrafluoroethylene binder particles, the charged polytetrafluoroethylene binder particles with smaller particle size are uniformly adsorbed on the surfaces of the activated carbon particles with larger particle size (fig. 3 b).
FIG. 4 is a scanning electron microscope photograph of an electrode master batch direct calendered film sheet of the invention (corresponding to example 1) and a ram extruder post-strip extrusion calender rolled film sheet. The results show that the polytetrafluoroethylene fibrosis degree of the electrode master batch membrane directly rolled by the electrode master batch is low, and the binding type bonding forming effect on the electrode active material particles is poor (figure 4 a); the calendering membrane of the sample strip extruded by the electrode master batch plunger has high degree of fibrosis of the polytetrafluoroethylene binder, good binding type binding forming effect on electrode active material particles, and close contact among the particles (figure 4 b).
Fig. 5 is an optical photograph of an electrode master batch film of the present invention (corresponding to example 1) before and after deposition of a metal collector. The results show that the surface of the electrode master batch membrane before metal deposition exhibits a black surface possessed by activated carbon particles (fig. 5 a); after the metallic aluminum is electrodeposited, the surface of the electrode master batch membrane presents silvery white of the metallic aluminum, and obvious phenomena of cracks, delamination, peeling and the like do not appear, so that the combination of the metallic deposition layer and the electrode master batch membrane is good (fig. 5 b).
Fig. 6 is a cycle charge and discharge retention rate test curve of example 1 and comparative example 1. The results show that the capacity retention of the supercapacitor prepared in example 1 is much better than that of the supercapacitor in comparative example 1.
Example 2
1. Electro-electret of polypropylene electrode binder
The polypropylene adhesive is electrically polarized by a thermal polarization method. 300g of polypropylene binder particles with the molecular weight of 500 ten thousand and the particle size of 50 mu m are evenly paved on the surface of a copper plate to form a processing layer with the thickness of 1mm and the width of 100 mm. The heat treatment temperature is 120 ℃, the polarization electric field intensity is 150MV/m, and the polarization speed is 600cm2And/min, obtaining the electro-electret polypropylene binder.
2. Preparation of lithium ion battery anode master batch
And preparing the electrode master batch by adopting high-speed stirring equipment. 200g of electret polarized polypropylene, 100g of Keqin black and 1700g of lithium iron phosphate (D)505 mu m), placing the mixture into a high-speed stirring device, rotating at 2500 rpm for 3min, and sieving the mixture through a 100-mesh sieve to obtain the lithium ion battery cathode master batch.
3. Preparation of lithium ion battery anode master batch membrane
And preparing the electrode diaphragm by adopting a plunger extrusion sample strip tabletting method. Taking 1000g of electrode master batch pressed compact: the pressure is 10.0MPa, the green pressing speed is 20mm/min, the pressure maintaining time is 10s, and the green pressing temperature is 60 ℃. And (3) placing the pressed electrode mother blank in a double-plunger type extruder: the extrusion speed is 10mm/min, the extrusion temperature is 310 ℃, the compression ratio (RR) is 500, the length-diameter ratio (L/D) is 5, and the cone angle (alpha) is 90 degrees, so that a rectangular positive electrode master batch sample strip of 2cm multiplied by 5cm is obtained. And (3) placing the electrode master batch sample strip in a 5-roll calender, wherein the length-diameter ratio is 2.5, the calendering speed is 5m/min, and the roll temperature is 200 ℃, and preparing the lithium ion battery positive master batch membrane with the thickness of 5mm and the width of 1000 mm.
4. Aluminum collector deposited on master batch diaphragm of lithium ion battery anode
And depositing a metal aluminum collector on the surface of the electrode master batch by adopting an evaporation deposition method. And (3) placing the electrode master batch membrane in evaporation equipment, and obtaining the electrode for the lithium ion battery anode with the master batch membrane deposited with the metal silver collector, wherein the silver target material (the purity is more than or equal to 99.99%), the substrate temperature is 120 ℃, the evaporation current is 500A, and the deposition thickness is 5 mu m.
5. Preparation of lithium ion battery
The method comprises the steps of taking a master batch membrane deposited metal silver collector as an electrode, taking Celgard (2400) diaphragm paper as an electrode diaphragm, taking a scale graphite electrode as a negative electrode, taking a lithium hexafluorophosphate ethylene carbonate solution (1.0mol/L) as an electrolyte, and assembling the super capacitor in a glove box with the water oxygen content less than or equal to 10 ppm. Electrochemical data after 300 times of charge and discharge under the conditions of constant current of 10.0A/g and working voltage of 3.7V are shown in Table 1.
Example 3
1. Electroelectret of polyvinylidene fluoride binder
And (3) carrying out stationary polarization on the polyvinylidene fluoride binder by adopting a high-voltage electrostatic spinning method. 300g of polyvinylidene fluoride having a weight average molecular weight of 200 ten thousand and a particle size of 10 μm was taken and prepared into an electrospinning solution having a concentration of 15 wt.% in N, N' -dimethylformamide. Under the conditions of spinning voltage of 15kV, spinning distance of 10cm and spinning speed of 2.0mL/h, the electret polarized polyvinylidene fluoride electrostatic spinning fiber binder is obtained.
2. Preparation of lithium ion capacitor negative electrode master batch
And preparing the lithium ion capacitor negative electrode master batch by adopting gravity-free mixing equipment. 200g of electret polarized polyvinylidene fluoride, 100g of bead graphite and 1700g of a negative electrode material (the mass ratio of hard carbon to lithium titanate is 0.8:1.0) are placed in a gravity-free mixing device, the rotation number is 81 revolutions per minute, the filling coefficient is 0.6, and the processing time is 3min, so that the negative electrode master batch of the lithium ion capacitor is obtained.
3. Preparation of negative master batch membrane of lithium ion capacitor
And preparing the electrode diaphragm by adopting a plunger extrusion sample bar calendaring method. Taking 1000g of electrode master batch pressed compact: the pressure is 1.0MPa, the green pressing speed is 10mm/min, the pressure maintaining time is 7s, and the green pressing temperature is 120 ℃. The pressed electrode master batch was placed in a single ram extruder to extrude bars: the extrusion speed is 100mm/min, the extrusion temperature is 30 ℃, the compression ratio (RR) is 50, the length-diameter ratio (L/D) is 50, and the cone angle (alpha) is 10 degrees, so that an electrode master batch sample strip with the diameter of 10mm is prepared. And (3) placing the electrode master batch sample strip in a three-roll calender, wherein the length-diameter ratio is 3.0, the calendering speed is 10m/min, and the roll temperature is 60 ℃, and preparing the electrode master batch membrane with the thickness of 150 mu m and the width of 600 mm.
4. Deposition of metal copper on negative master batch membrane of lithium ion capacitor
And depositing metal copper on the surface of the electrode master batch collector by adopting an atomic layer deposition method. And (3) placing the electrode master batch membrane in atomic layer deposition equipment, taking bis (hexafluoroacetylacetone ketone) copper as a precursor, and preparing the electrode for the lithium ion capacitor with the master batch membrane deposited with the metal copper, wherein the deposition temperature is 120 ℃, the input power is 300W, the deposition rate is 0.1 nm/cycle, and the deposition thickness is 2 micrometers.
5. Preparation of lithium ion capacitor
The method comprises the steps of taking a master batch diaphragm deposited metal copper collector as an electrode, taking Celgard (2325) diaphragm paper as an electrode diaphragm, taking a lithium iron phosphate electrode as a positive electrode, taking a propylene carbonate solution (1.0mol/L) of lithium hexafluorophosphate as an electrolyte, and assembling the supercapacitor in a glove box with the water oxygen content of less than or equal to 10 ppm. Electrochemical data after 1000 times of charge and discharge under the conditions of constant current of 10.0A/g and working voltage of 3.2V are shown in Table 1.
Comparative example 1
1. Preparation of active carbon electrode master batch
And preparing the electrode master batch by adopting three-dimensional mixing equipment. 200g of polytetrafluoroethylene, 100g of carbon aerogel and 1700g of activated carbon are placed in a three-dimensional mixing device, the rotation speed is 72 revolutions per minute, and the processing time is 30 minutes, so that the electrode master batch is obtained. The scanning electron micrograph of the prepared electrode master batch is shown in figure 2 a.
3. Preparation of active carbon electrode master batch membrane
1000g of the electrode master batch was placed in a twin-roll calender: the length-diameter ratio is 2.0, the rolling speed is 1m/min, the roller temperature is 20 ℃, and the electrode master batch membrane with the thickness of 200 mu m and the width of 500mm is prepared.
Comparative example 2
1. Preparation of lithium ion battery anode master batch
And preparing the electrode master batch by adopting high-speed stirring equipment. 200g of polypropylene, 100g of Keqin black and 1700g of lithium iron phosphate (D)505 mu m), placing the mixture into a high-speed stirring device, rotating at 2500 rpm for 3min, and sieving the mixture through a 100-mesh sieve to obtain the lithium ion battery cathode master batch.
2. Preparation of lithium ion battery anode master batch membrane
The electrode diaphragm is prepared by a direct master batch calendering method. And (3) putting 1000g of the electrode master batch into a 5-roll calender, and preparing the lithium ion battery anode master batch membrane with the thickness of 5mm and the width of 1000mm at the length-diameter ratio of 2.5, the calendering speed of 5m/min and the roll temperature of 200 ℃.
3. Preparation of positive electrode of lithium ion battery
The lithium ion battery anode master batch membrane is adhered to a metal silver collector with the thickness of 200 mu m by conductive adhesive (Henkel EB102) to prepare the anode electrode.
4. Preparation of lithium ion battery
The anode of the lithium ion battery is assembled into the button type lithium ion battery in a glove box with the water oxygen content less than or equal to 10ppm, the size thickness of 5mm multiplied by the diameter of 20mm, Celgard (2400) diaphragm paper as an electrode diaphragm, a scale graphite electrode as a cathode, and a ethylene carbonate solution (1.0mol/L) of lithium hexafluorophosphate as an electrolyte. Electrochemical data after 300 times of charge and discharge under the conditions of a charge and discharge rate of 1C and an operating voltage of 3.7V are shown in table 1.
Comparative example 3
1. Preparation of lithium ion capacitor negative electrode master batch
And preparing the lithium ion capacitor negative electrode master batch by adopting gravity-free mixing equipment. 200g of polyvinylidene fluoride, 100g of bead graphite and 1700g of a negative electrode material (the mass ratio of hard carbon to lithium titanate is 0.8:1.0) are placed in a gravity-free mixing device, the rotation number is 81 revolutions per minute, the filling factor is 0.6, and the processing time is 3min, so that the negative electrode master batch of the lithium ion capacitor is obtained.
2. Preparation of negative master batch membrane of lithium ion capacitor
The electrode diaphragm is prepared by a direct master batch calendering method. 1000g of the electrode master batch is placed in a three-roll calender, the length-diameter ratio is 3.0, the calendering speed is 10m/min, the roll temperature is 60 ℃, and the electrode master batch membrane with the thickness of 150 mu m and the width of 600mm is prepared.
3. Preparation of negative electrode of lithium ion capacitor
And (3) adhering the lithium ion capacitor negative electrode master batch membrane to a metal copper collector with the thickness of 300 mu m by using conductive adhesive (Henkel EB102) to prepare the lithium ion capacitor negative electrode.
4. Preparation of lithium ion capacitor
A cathode electrode for a lithium ion capacitor is taken, the size of the cathode electrode is 200 mu m multiplied by 10mm multiplied by 27.5mm, Celgard (2325) diaphragm paper is taken as an electrode diaphragm, a lithium iron phosphate electrode is taken as an anode, a propylene carbonate solution (1.0mol/L) of lithium hexafluorophosphate is taken as an electrolyte, and the supercapacitor is assembled in a glove box with the water oxygen content less than or equal to 10 ppm. Electrochemical data after 1000 times of charge and discharge under the conditions of constant current of 10.0A/g and working voltage of 3.2V are shown in Table 1.
TABLE 1 electrochemical Performance of electrochemical energy storage devices in examples and comparative examples
As can be seen from table 1, the results of comparing the electrochemical data of example 1 with that of comparative example 1 show that the energy density of example 1 is higher than the capacity density of comparative example 1 (1.8 times) due to the omission of the conductive paste, good fiberization of the binder, thinning of the current collector, and the like; because of adopting methods such as the standing polarization of the conductive agent, the plunger extrusion processing and the like, the adhesive has high fiberization degree and uniform distribution, so that the contact between electrode active substances is tighter and firmer, and meanwhile, the collector electrode is directly compounded with the electrode active substance used as a substrate material through vapor deposition, thereby reducing the internal resistance of the capacitor (about 3.2 times), improving the charge-discharge efficiency (about 1.2 times) and increasing the maximum power density (about 1.2 times).
Comparing the electrochemical data of example 2 with that of comparative example 3, the results show that the energy density of example 2 is higher than that of comparative example 1 (1.3 times) due to the omission of conductive glue, good fiberization of binder, thinning of current collector, etc.; because of adopting methods such as the standing polarization of the conductive agent, the plunger extrusion processing and the like, the adhesive has high fiberization degree and uniform distribution, so that the contact between electrode active substances is tighter and firmer, and meanwhile, the collector electrode is directly compounded with the electrode active substance used as a substrate material through vapor deposition, so that the internal resistance of the capacitor is reduced (about 1.9 times), the charge-discharge efficiency is improved (about 1.2 times) and the maximum power density is increased (about 1.2 times).
Comparing the electrochemical data of example 3 with that of comparative example 3, the results show that the energy density of example 3 is higher than the capacity density of comparative example 3 (1.3 times) due to the omission of conductive glue, good fiberization of binder, thinning of current collector, etc.; because of adopting methods such as the standing polarization of the conductive agent, the plunger extrusion processing and the like, the adhesive has high fiberization degree and uniform distribution, so that the contact between electrode active substances is tighter and firmer, and meanwhile, the collector electrode is directly compounded with the electrode active substance used as a substrate material through vapor deposition, thereby reducing the internal resistance of the capacitor (about 1.9 times), improving the charge-discharge efficiency (about 1.2 times) and increasing the maximum power density (about 1.2 times).
The above description is only exemplary of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by 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. A solvent-free preparation method of an electrode for an electrochemical energy storage device is characterized by comprising the following steps:
the method comprises the following specific steps:
(1) polymer binder electro-electret
Placing the polymer binder powder in an electric polarization device, and performing electric polarization treatment on the polymer binder to obtain an electric polarization polymer binder;
(2) preparation of electrode masterbatch
Placing the polymer binder subjected to electret polarization, the electrode active substance and the conductive agent in mixing equipment to be uniformly mixed to obtain electrode master batch;
(3) preparation of electrode master batch membrane
Placing the electrode master batch into a briquetting machine, placing the electrode master batch into a plunger type extruder after briquetting, and extruding an electrode master batch sample strip; rolling the electrode master batch sample strip into an electrode master batch membrane with the thickness of 50 mu m-5 mm and the width of 100 mm-1000 mm in a rolling mill;
(4) electrode prepared by depositing metal on electrode master batch membrane
And (3) placing the electrode master batch membrane in vapor deposition equipment, and depositing a layer of metal collector with the thickness of 10 nm-5 mu m on the surface of the electrode master batch at the deposition temperature of 80-200 ℃.
2. A method of solventless preparation of an electrode for an electrochemical energy storage device as in claim 1, characterized by: the polymer binder has the number average molecular weight of 200-1000 ten thousand and the grain size of 20 nm-50 microns.
3. A method of solventless preparation of an electrode for an electrochemical energy storage device as in claim 1, characterized by: the polymer binder is at least one of polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride and polytetrafluoroethylene-hexafluoropropylene copolymer.
4. A method of solventless preparation of an electrode for an electrochemical energy storage device as in claim 1, characterized by: when the electro-electret treatment is carried out, one mode of electrostatic spinning, corona discharge, triboelectrification, thermal polarization and low-energy electron beam bombardment is adopted for treatment.
5. A method of solventless preparation of an electrode for an electrochemical energy storage device as in claim 1, characterized by: when electrostatic spinning electro-electret treatment is adopted, the spinning voltage is 15kV, the spinning distance is 10cm, and the spinning speed is 2.0 mL/h;
when adopting corona discharge electro-electret treatment, the voltage of a mesh grid is 10kV, the discharge interval is 1cm, and the treatment speed is 800cm2/min；
When the thermal polarization and the electric polarization are adopted, the polymer adhesive is evenly paved on the surface of the copper plate to form a processing layer with the thickness of 1mm and the width of 100mm for heat treatment, the heat treatment temperature is 120 ℃, the intensity of the polarization electric field is 150MV/m, and the polarization speed is 600cm2/min。
6. A method of solventless preparation of an electrode for an electrochemical energy storage device as in claim 1, characterized by: the mixing equipment is at least one of a high-speed stirrer, a V-shaped mixer, a gravity-free mixer, a three-dimensional mixer, a ball mill, an open mill, an internal mixer and an air flow mill; when mixing materials, the mixing temperature is 19-200 ℃, and the mixing time is 1-60 min.
7. A method of solventless preparation of an electrode for an electrochemical energy storage device as in claim 1, characterized by: the electrode active substance is at least one of lithium salt, carbon-based porous material, graphite-based electrode material, metal oxide and the like, and has a particle size D505-50 μm; the conductive agent is at least one of carbon aerogel, conductive carbon black, crystalline flake graphite, carbon nano tubes, graphene and ball graphite, and the mass ratio of the polymer binder to the electrode active substance to the conductive agent is 200:1700: 100.
8. A method of solventless preparation of an electrode for an electrochemical energy storage device as in claim 1, characterized by: the green compact conditions are that the pressure is 1.0 MPa-10.0 MPa, the green compact speed is 5 mm/min-50 mm/min, the pressure maintaining time is 5 s-10 s, and the green compact temperature is 20-120 ℃;
the plunger type extruder is one of a vertical type, a horizontal type, a single column type, a double plunger type, a continuous type or an intermittent type, and the plunger type extrusion conditions are as follows: the extrusion speed is 10 mm/min-100 mm/min, the extrusion temperature is 30-310 ℃, the compression ratio (RR) is 50-500, the length-diameter ratio (L/D) is 5-50, the cone angle (alpha) is 10-90 degrees, and an extruded electrode master batch spline is one of a rod, a rectangle, a belt or a tube;
the calender is 2-5 rollers, the length-diameter ratio is 2.0-3.0, the calendering speed is 1-10 m/min, and the roller temperature is 20-200 ℃.
9. A method of solventless preparation of an electrode for an electrochemical energy storage device as in claim 1, characterized by: the vapor deposition equipment is one of magnetron sputtering equipment, evaporation deposition equipment, ion plating equipment, pulse deposition equipment and atomic layer deposition equipment; the material of the metal collector is one or more of copper, aluminum, silver, gold, platinum and the like.
10. A method of solventless preparation of an electrode for an electrochemical energy storage device as in claim 1, characterized by: when the metal aluminum collector is deposited by adopting a magnetron sputtering deposition mode, the purity of an aluminum target material is more than or equal to 99.99 percent, the temperature of a substrate is 200 ℃, and the argon pressure is 4 multiplied by 10-3Torr, bias voltage is-500V, deposition rate is 50nm/min, sputtering time is 60 min;
when the metallic silver collector is deposited by adopting an evaporation deposition mode, the purity of a silver target material is more than or equal to 99.99 percent, the temperature of a base material is 120 ℃, the evaporation current is 500A, and the deposition thickness is 5 mu m;
when the metal copper collector is deposited by adopting an atomic layer deposition mode, bis (hexafluoroacetylacetone ketone) copper is used as a precursor, the deposition temperature is 120 ℃, the input power is 300W, the deposition rate is 0.1 nm/cycle, and the deposition thickness is 2 micrometers.
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