CN112473501B - Dry mixing device for preparing energy storage electrode and preparation method of energy storage electrode - Google Patents

Dry mixing device for preparing energy storage electrode and preparation method of energy storage electrode Download PDF

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CN112473501B
CN112473501B CN202011154317.2A CN202011154317A CN112473501B CN 112473501 B CN112473501 B CN 112473501B CN 202011154317 A CN202011154317 A CN 202011154317A CN 112473501 B CN112473501 B CN 112473501B
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energy storage
electrode
storage electrode
kettle body
pressure air
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CN112473501A (en
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阮殿波
屠建飞
方志梅
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Ningbo University
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Ningbo University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
    • B01F33/40—Mixers using gas or liquid agitation, e.g. with air supply tubes
    • B01F33/409—Parts, e.g. diffusion elements; Accessories
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
    • B01F33/70—Mixers specially adapted for working at sub- or super-atmospheric pressure, e.g. combined with de-foaming
    • B01F33/71—Mixers specially adapted for working at sub- or super-atmospheric pressure, e.g. combined with de-foaming working at super-atmospheric pressure, e.g. in pressurised vessels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
    • B01F35/181—Preventing generation of dust or dirt; Sieves; Filters
    • B01F35/187—Preventing generation of dust or dirt; Sieves; Filters using filters in mixers, e.g. during venting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
    • B01F35/50—Mixing receptacles
    • B01F35/51—Mixing receptacles characterised by their material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
    • B01F35/60—Safety arrangements
    • 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
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0435—Rolling or calendering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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

Abstract

The invention relates to a dry mixing device for preparing an energy storage electrode and a preparation method of the energy storage electrode. The invention provides a dry-type mixing device for preparing an energy storage electrode, which comprises a dispersion kettle, wherein the dispersion kettle comprises a kettle body and a flange positioned at an opening at the upper end of the kettle body, an air outlet is formed in the middle of the flange, and a gas filtering hole is formed in the air outlet; the kettle body cross section is circular, kettle body middle part is equipped with a plurality of high-pressure air cock along kettle body periphery in the same altitude plane, the axis of high-pressure air cock forms angle phi with the radial line of kettle body cross section, the jet-propelled direction of high-pressure air cock is anticlockwise. The invention utilizes the high-pressure expansion of compressed gas and the fiberization principle of gas phase convolution traction binder, and prepares the high-density electrode supporting membrane with adjustable thickness by dry mixing under the action of ultrahigh pressure gas, the preparation method is simple, the cost is low, the swelling rate of the obtained energy storage electrode is low, and the electrochemical performance is good.

Description

Dry mixing device for preparing energy storage electrode and preparation method of energy storage electrode
Technical Field
The invention belongs to the technical field of energy storage devices, and particularly relates to a dry mixing device for preparing an energy storage electrode and a preparation method of the energy storage electrode.
Background
With the development of pure electric vehicles, the energy storage technology is more and more emphasized. In recent years, the united states Maxwell company is purchased by the united states tesla company, and the technology of dry-type preparation of energy storage devices is vigorously developed to obtain energy storage devices with high energy density. The conventional electrodes of lithium ion batteries and supercapacitors are usually prepared by a wet method, but the method needs to consume a large amount of energy and a certain drying technology to remove the solvent, so that the solvent residue in the electrodes is easily caused, the service life of the electrodes is reduced, and the binder dissolved on the surface of an active material can increase the resistivity of the battery and reduce the energy density and the power density. Moreover, the wet preparation method of slurry coating is adopted, the problems of cracking, delamination, poor flexibility and the like of the electrode are easy to occur, and the ionic conductivity is poor along with the increase of the thickness or density of the electrode film, so that the electrochemical performance and the reliability are reduced. Compared with the wet preparation which is time-consuming and high in cost, the dry preparation method directly mixes the binder and the electrode active material and then presses the mixture into the electrode film, which is beneficial to improving the energy density and the cycle life of the electrode. Chinese patent application publication No. CN111436199A, for example, provides a method for manufacturing a dry electrode film for an energy storage device that produces a cell with an energy density of up to 250Wh/L.
The core of the dry-type energy storage device is a dry-type energy storage material and binder dry powder mixing mode, so that the binder is subjected to nano-fibrosis, the effect of uniform mixing is achieved, and the preparation of a high-density electrode is realized, so that the traditional wet-method mixing method can be replaced, the use of a solvent is avoided, and the durability of the energy storage device is improved. However, there is still little research on dry fabrication techniques for electrodes in energy storage devices. Fibrillation of the binder component in the electrode film is typically achieved by mechanical treatment, such as a blender or jet mill, to manipulate the binder component into fibrils by applying strong shear forces on the binder component. However, the application of high shear to the binder tends to cause the active material components of the electrode-membrane mixture to be destroyed, thereby degrading the electrochemical performance of the electrode. To avoid the impact of mechanical treatment on the performance of the dry electrode, chinese patent application CN109923698A discloses an apparatus for forming an energy storage device electrode film mixture, which comprises a first source containing a polymer dispersion, a second source containing an energy storage device electrode film mixture, and a fluidized bed coating apparatus, but it provides a dry polymer by heating air to evaporate liquid in the polymer dispersion, thereby reducing the drying step in the wet-process electrode film preparation process, i.e. the mixing and drying processes are simultaneously realized, but the raw material of the first component used in this method is still a polymer dispersion containing a liquid phase, and the way of heating to evaporate the liquid is energy-consuming. Chinese patent CN106104858B, on the other hand, provides a negatively charged fibrillatable binder component, the fibrillation of which is achieved by applying an electric field, so that the shear forces on the electrode film component are significantly reduced in the electrostatic field fibrillation process, maintaining the physical and electrochemical integrity of the electrode film active material. However, fibrillation by applying an electrostatic field requires high equipment requirements, the mixing vessel needs to have an affinity material that can provide electrons to the binder component, the electric field generator is also needed, the cost is high, and the polymer in the binder component has a higher dielectric constant, which limits the choice of binders and does not have universality.
Disclosure of Invention
The invention aims to solve the technical problems and provides a dry mixing device for preparing an energy storage electrode and a preparation method of the energy storage electrode, so that a high-density electrode with adjustable thickness can be obtained.
The above object of the present invention is achieved by the following technical solutions:
the dry type mixing device for preparing the energy storage electrode comprises a dispersion kettle, wherein the dispersion kettle comprises a kettle body and a flange positioned at an opening at the upper end of the kettle body; the cross section of the kettle body is circular, a plurality of high-pressure air nozzles in the same horizontal plane are radially arranged on the outer side wall of the middle part of the kettle body, and an angle phi is formed between the axis of each high-pressure air nozzle and the radial line of the cross section of the kettle body.
The dry-type mixing device is characterized in that a plurality of high-pressure air nozzles are radially arranged on the outer side wall of the middle part of the dispersing kettle body, and the axes of the high-pressure air nozzles form a certain angle with the radial line of the cross section of the kettle body, so that gas can enter the dispersing kettle through the high-pressure air nozzles, compressed gas generates high-pressure expansion in the dispersing kettle and rotates anticlockwise along the inner side wall of the dispersing kettle, thereby generating a rotating traction effect on mixed materials in the dispersing kettle, and realizing dry-type mixing of different materials under the action of ultrahigh-pressure gas. Meanwhile, the filter plate is arranged in the air outlet pipe of the flange, and the filter plate is provided with the gas filter hole, so that the gas in the dispersion kettle can be smoothly discharged through the gas filter hole, and the particles of the dispersion material are prevented from being brought out.
Preferably, the axis of the high-pressure air nozzle forms an angle phi =5-10 degrees with the radial line of the cross section of the kettle body.
Preferably, the inner diameter of the dispersion kettle is 50-100cm, the diameter of the high-pressure air nozzle is 1-3cm, and the length of the high-pressure air nozzle is 8-10cm.
Preferably, the body of the dispersion kettle is made of two layers of different materials, the outer side wall is made of a metal material, and the inner side wall is made of a corundum material.
Preferably, the total thickness of the kettle body of the dispersion kettle is 3-5cm, and the thickness of the inner side wall is 1-3mm.
Further preferably, the metal material may be iron and its alloy, copper and its alloy, aluminum and its alloy.
Preferably, the gas filtering holes of the invention are metal nets with 1000 meshes to 5000 meshes, and the metal nets are made of iron and alloys thereof, copper and alloys thereof, aluminum and alloys thereof or other metal materials.
The dispersion kettle body is made of corundum materials and metal materials, and has good wear resistance and high pressure resistance. And the axis of the high-pressure air nozzle and the radial line of the cross section of the kettle body form an angle fixation, and meanwhile, the reasonable design of the size of the dispersion kettle and the size of the high-pressure air nozzle are mutually matched, so that the realization of the function of compressed gas convolution traction and the realization of the dispersion mixing function are facilitated.
The invention also provides a dry preparation method of the energy storage device electrode, which comprises the following steps:
adding an energy storage material and dry adhesive powder into a dispersion kettle of a dry mixing device, locking a flange, opening a high-pressure air nozzle to admit air, wherein the pressure of the high-pressure air nozzle is 0.5-2Mpa, and dispersing to obtain mixed dry powder, wherein the adhesive forms a fiberized adhesive in the dispersion process;
and pressing the mixed dry powder into an electrode supporting film, and pressing the electrode supporting film on a current collector to obtain the energy storage electrode.
The dry electrode film only consists of energy storage materials and binder dry powder, and reduces the use of additives or other inactive materials, thereby reducing impurity interference, reducing resistivity and further improving energy density and power density. In addition, the method can avoid the influence of wet preparation on the electrode performance, can better control the thickness and the uniformity of the electrode, does not need a complicated process of drying and removing the solvent after coating the slurry, greatly simplifies the process and reduces the production cost.
The invention utilizes the high-pressure expansion of compressed gas and the fiberization principle of vapor phase convolution traction binder to realize the dry mixing of the energy storage material and the binder under the action of ultrahigh pressure gas, thereby preparing the high-density electrode. In the existing dry preparation technology, mechanical treatment methods such as a stirrer or a jet mill are mostly adopted to fibrillate the binder component in the dry electrode film, but the application of high shearing force to the binder easily causes the active material component of the electrode film mixture to be damaged, and the electrochemical performance of the electrode is reduced. The dry mixing device of the invention only utilizes the convolution traction action of the ultrahigh pressure gas to fibrillate the binder, selects a proper material of the dispersion kettle, reasonably designs the size, the angle and the like of the dispersion kettle and the high pressure air nozzle, and ensures the effectiveness and the safety of dry mixing. The method can avoid the exposure of electrode components to high shearing force, avoid the damage and loss of active materials, help to maintain the integrity of the electrode materials and further improve the electrochemical performance.
Preferably, the mass ratio of the energy storage material to the binder dry powder is (6-10): 1.
preferably, the air inlet speed of the high-pressure air nozzle is 360-450m/s.
Further preferably, the gas entering the kettle body from the high-pressure gas nozzle can be air, nitrogen, argon and the like.
Preferably, the dispersion time of the present invention is 1 to 10 hours.
Preferably, the electrode support film according to the present invention is prepared by placing the mixed dry powder on a vertical roller mill and applying a pressure of 10 to 50 tons.
The invention also provides an energy storage electrode which is prepared by the preparation method, and the fiber diameter of the fiberization binder in the energy storage electrode is 10-50nm.
Preferably, the swelling ratio of the energy storage electrode measured by soaking the energy storage electrode in the electrolyte for 24 hours is not more than 5%.
Generally, the firmness of adhesion between the electrode material of the energy storage electrode and the current collector affects both the cycle performance and the internal resistance of the energy storage device. The higher the swelling ratio of the electrode is, the easier the electrode film is to separate from the current collector, namely the lower the peeling strength is, the serious powder falling phenomenon of the electrode can occur, and the electrochemical performance of the energy storage device is reduced. The invention utilizes the high-pressure expansion of compressed gas and gas phase convolution to fibrillate the binder to prepare uniform and stable mixed dry powder, thereby ensuring that the energy storage electrode has lower swelling rate and being difficult to fall off and fall off.
Preferably, the thickness of the electrode supporting film of the energy storage electrode is 30-200 μm, and the density is 0.65-1.1g/cm 3 。
The density of the electrode prepared by the traditional method can only reach 0.45-0.47 g/cm 3 The electrode density of the energy storage device obtained by the dry preparation method can be improved by about 20%, the thickness of the electrode can be adjusted by controlling the pressure of the vertical rolling machine, and the larger the pressure is, the larger the pressure isThe thinner the obtained dry type energy storage electrode is, the production requirements of different types of energy storage devices can be met.
Preferably, the energy storage material of the present invention includes, but is not limited to, one or more of activated carbon, carbon aerogel, graphene, silicon-carbon composite material, soft carbon, hard carbon, lithium iron phosphate, ternary material, lithium titanate.
Preferably, the binder dry powder of the present invention includes, but is not limited to, a composite binder of one or more of Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), sodium carboxymethylcellulose (CMC), polyethylene oxide (PEO).
Preferably, the current collector of the present invention is a metal foil, including but not limited to nickel foam, aluminum foil, etched aluminum foil, porous aluminum foil, copper foil, porous copper foil.
Preferably, the electrolyte used for testing the electrode of the energy storage device is LiPF 6 、LiClO 4 、LiBF 4 、LiAsF 6 、TEABF 4 、TEMABF 4 、SBPBF 4 Or a solution of another salt in a solvent such as a cyclic carbonate, a chain carbonate, or a carboxylic ester.
The cyclic carbonate used may be Polycarbonate (PC), ethylene Carbonate (EC), etc.; the chain carbonate may be diethyl carbonate (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), or the like; the carboxylic acid ester may be Methyl Formate (MF), methyl Acetate (MA), ethyl Acetate (EA), methyl Butyrate (MB), ethyl Butyrate (EB), etc.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the dry-wet mixing device provided by the invention, the plurality of high-pressure air nozzles are radially arranged on the outer side wall of the kettle body of the dispersion kettle, and the axes of the high-pressure air nozzles form a certain angle with the radial line of the cross section of the kettle body, so that ultrahigh-pressure gas can make rotary motion in the dispersion kettle, a rotary traction effect is generated on mixed materials in the dispersion kettle, and the effectiveness and the safety of dry mixing are ensured through reasonable material and size design.
2. According to the invention, the filter plate is arranged in the gas outlet pipe of the top flange of the dispersion kettle, and the filter plate is provided with the gas filter hole, so that gas in the dispersion kettle can be smoothly discharged through the filter hole, and meanwhile, dispersed material particles are prevented from being brought out.
3. The invention utilizes the high-pressure expansion of compressed gas and the fiberization principle of vapor phase rotary traction binder, realizes the dry mixing of the energy storage material and the binder under the action of ultrahigh pressure gas and high-speed airflow, and prepares the high-density electrode support membrane by vertical rolling.
4. The dry preparation method of the electrode avoids the influence of the traditional wet preparation on the electrochemical performance and reliability of the electrode, improves the density of the electrode by about 20 percent, simplifies the production process, reduces the production cost, can adjust the thickness of the electrode supporting film according to the requirements of different energy storage devices, has low swelling rate of the electrode supporting film, and can ensure effective ionic conductivity and effective adhesion between the electrode supporting film and a current collector.
5. The energy storage device electrode prepared by the invention only consists of the active energy storage material and the binder, and no solvent or other inactive materials are added, so that the internal resistance of the electrode is greatly reduced, the energy density and the power density of the electrode are improved, and the energy storage device electrode can be used for preparing energy storage devices with higher performance.
Drawings
FIG. 1 is a longitudinal sectional view of a dispersion tank of a dry mixing apparatus in example 1;
FIG. 2 is a cross-sectional view of a dispersion tank of the dry mixing device in example 1;
in the drawings, 1: kettle body, 11: cauldron body inside wall, 12: cauldron body lateral wall, 2: flange, 21: outlet duct, 22: filter plate, 3: high-pressure air tap, 4: binder, 5: an energy storage material.
Detailed Description
The technical solution of the present invention is further described and illustrated by the following specific examples. The raw materials used in the examples of the present invention are all those commonly used in the art, and the methods used in the examples are all those conventionally used in the art, unless otherwise specified. It should be understood that the specific embodiments described herein are merely to aid in the understanding of the invention and are not intended to limit the invention specifically.
Example 1
Embodiment 1 provides a dry mixing device for preparing an energy storage electrode, which comprises a dispersion kettle, wherein the dispersion kettle comprises a kettle body 1 and a flange 2 positioned at the upper end opening of the kettle body, an air outlet pipe 21 is arranged in the middle of the flange, a filter plate 22 is arranged in the air outlet pipe, and a gas filtering hole (not shown in the figure) is formed in the filter plate 22; the cross section of the kettle body is circular, a plurality of high-pressure air nozzles 3 which are positioned on the same horizontal plane are radially arranged on the outer side wall 12 in the middle of the kettle body 1, and an angle phi is formed between the axis of each high-pressure air nozzle 3 and the radial line of the cross section of the kettle body.
Wherein the total wall thickness of the dispersion kettle is 4cm, the thickness of the inner side wall is 2mm, the inner diameter is 50cm, and a steel metal mesh with 2000 meshes is arranged in a gas filtering hole in a flange at the upper end of the kettle body of the dispersion kettle; the diameter of the high-pressure air nozzle is 2cm, and the length of the high-pressure air nozzle is 9cm; the axial line of the high-pressure air nozzle 3 forms an angle phi =6 degrees with the radial line of the cross section of the kettle body 1.
In this embodiment, the outer side wall 12 of the dispersion kettle body is made of alloy steel material, and the inner side wall 11 of the kettle body is made of corundum material.
Example 2
Example 2 provides a dry-hybrid device for energy storage electrode preparation which differs from example 1 only in that: the total wall thickness of the dispersion kettle is 5cm, the thickness of the inner side wall is 2mm, the inner diameter is 80cm, and a steel metal mesh with 3000 meshes is arranged in a gas filtering hole 22 in the flange 2 at the upper end of the kettle body of the dispersion kettle; the diameter of the high-pressure air nozzle 3 is 1cm, and the length of the high-pressure air nozzle is 8cm; the axial line of the high-pressure air nozzle 3 and the radial line of the cross section of the kettle body 1 form an angle phi =8 deg.
Example 3
Example 3 provides a dry-hybrid device for energy storage electrode preparation which differs from example 1 only in that: the total wall thickness of the dispersion kettle is 4cm, the thickness of the inner side wall is 2mm, the inner diameter is 60cm, and the gas filtering holes 22 in the flange 2 at the upper end of the dispersion kettle body are steel metal meshes of 4000 meshes; the diameter of the high-pressure air nozzle 3 is 1.5cm, and the length is 9.3cm; the axial line of the high-pressure air nozzle 3 and the radial line of the cross section of the kettle body 1 form an angle phi =10 deg.
Example 4
Example 4 provides a dry hybrid device for energy storage electrode preparation which differs from example 1 only in that: the total wall thickness of the dispersion kettle is 4cm, the thickness of the inner side wall is 2mm, the inner diameter is 50cm, and a gas filtering hole 22 in a flange 2 at the upper end of the kettle body of the dispersion kettle is a 1500-mesh steel metal net; the diameter of the high-pressure air nozzle 3 is 2cm, and the length of the high-pressure air nozzle is 9cm; the axial line of the high-pressure air nozzle 3 forms an angle phi =5 degrees with the radial line of the cross section of the kettle body 1.
Example 5
Embodiment 5 provides a dry-type preparation method of an energy storage electrode, including the following steps:
(1) Mixing soft carbon 5 and polytetrafluoroethylene 4 according to a mass ratio of 7:1, adding the mixture into a steel dispersion kettle of the embodiment 1, and locking a flange;
(2) Opening a high-pressure air nozzle to admit air, introducing the air at the pressure of 0.5MPa, wherein the air admission speed is 380m/s, the dispersion time is 5h, and the binder is fiberized into fibers with the diameter of 25nm to obtain mixed dry powder;
(3) The mixed dry powder was put on a vertical roller mill and a pressure of 20 tons was applied to prepare an electrode supporting film having a density of 0.75g/cm 3 The thickness of the electrode supporting film is 120 mu m;
(4) And pressing the electrode supporting film on the aluminum foil to prepare the electrode of the energy storage device.
The electrode of the energy storage device prepared in the embodiment is placed in 1mol/L TEMABF 4 The electrode was immersed in the PC electrolyte for 24 hours, and taken out, and the swelling ratio of the electrode was found to be 4.2%.
Example 6
Embodiment 6 provides a dry-type preparation method of an energy storage electrode, including the following steps:
(1) Mixing active carbon 5 and polyvinylidene fluoride 4 according to a mass ratio of 9:1, adding the mixture into a steel dispersion kettle of the embodiment 2, and locking a flange;
(2) Opening a high-pressure air nozzle to admit air, introducing the air at the pressure of 2MPa, wherein the air admission speed is 420m/s, the dispersion time is 7h, and the binder is fiberized into fibers with the diameter of 45nm to obtain mixed dry powder;
(3) The mixed dry powder was placed on a vertical roller mill and a pressure of 15 tons was appliedPreparing an electrode supporting film having a density of 0.65g/cm 3 The thickness of the electrode supporting film is 180 mu m;
(4) And pressing the electrode supporting film on the aluminum foil to prepare the electrode of the energy storage device.
The electrode of the energy storage device prepared in the embodiment is placed in 1mol/L LiBF 4 The DEC electrolyte is soaked for 24 hours and taken out, and the swelling ratio of the electrode is measured to be 3.5 percent.
Example 7
Embodiment 7 provides a dry-type preparation method of an energy storage electrode, including the steps of:
(1) Mixing a silicon-carbon composite material 5 and sodium carboxymethyl cellulose 4 according to a mass ratio of 6:1, adding the mixture into a steel dispersion kettle, and locking a flange;
(2) Opening a high-pressure air nozzle to admit air, introducing the air at the pressure of 1.5MPa, wherein the air admission speed is 370m/s, the dispersion time is 10h, and the binder is fiberized into fibers with the diameter of 15nm to obtain mixed dry powder;
(3) The mixed dry powder was put on a vertical roller mill, and a pressure of 50 tons was applied to prepare an electrode supporting film having a density of 1.06g/cm 3 The thickness of the electrode supporting film is 150 μm;
(4) And pressing the electrode supporting film on the aluminum foil to prepare the electrode of the energy storage device.
The electrode of the energy storage device prepared in the embodiment is placed in 1mol/L LiAsF 6 The MP electrolyte is soaked for 24 hours and taken out, and the swelling ratio of the electrode is measured to be 2.4 percent.
Example 8
Embodiment 8 provides a dry fabrication method of an energy storage electrode, comprising the steps of:
(1) Lithium titanate 5 and a polyvinylidene fluoride/polyethylene oxide composite binder 4 are mixed according to a mass ratio of 8:1, adding the mixture into a steel dispersion kettle, and locking a flange;
(2) Opening a high-pressure air nozzle to admit air, introducing the air at the pressure of 1.5MPa, wherein the air admission speed is 390m/s, the dispersion time is 5h, and the binder is fiberized into fibers with the diameter of 35nm to obtain mixed dry powder;
(3) Mixing the dry powders, and grinding in a vertical roller millApplying a pressure of 40 tons to form an electrode supporting film, wherein the density of the electrode supporting film is 1.1g/cm 3 The thickness of the electrode supporting film is 45 mu m;
(4) And pressing the electrode supporting film on the aluminum foil to prepare the electrode of the energy storage device.
The electrode of the energy storage device prepared in the embodiment is placed in 1mol/L LiPF 6 The EC electrolyte is soaked for 24 hours and taken out, and the swelling ratio of the electrode is measured to be 1.2 percent.
Comparative example 1
The comparative example 1 provides an energy storage device electrode prepared by a conventional wet method, and the energy storage material, the binder and the conductive agent are mixed with water, stirred to form uniform slurry, coated on a current collector and dried to obtain the energy storage device electrode; the energy storage material, binder and current collector used were the same as in example 5.
The electrode obtained in this comparative example had a density of 0.58g/cm 3 The thickness of the electrode supporting film was 250 μm, and the swelling ratio was measured by the method of example 1 to be 8.7%.
Comparative example 2
Comparative example 2 provides a conventional wet-laid energy storage device electrode prepared in the same manner as in comparative example 1, using the same energy storage material, binder and current collector as in example 6.
The electrode obtained in this comparative example had a density of 0.61g/cm 3 The thickness of the electrode-supporting film was 223 μm, and the swelling ratio was 7.5% by the method of example 1.
Comparative example 3
Comparative example 3 provides an electrode for a conventional wet-laid energy storage device prepared in the same manner as in comparative example 1, using the same energy storage material, binder and current collector as in example 7.
The electrode obtained in this comparative example had a density of 0.62g/cm 3 The thickness of the electrode-supporting film was 235 μm, and the swelling ratio was 6.9% by the method of example 1.
Comparative example 4
Comparative example 4 provides an electrode for a conventional wet-laid energy storage device prepared in the same manner as in comparative example 1, using the same energy storage material, binder and current collector as in example 8.
The electrode obtained in this comparative example had a density of 0.63g/cm 3 The thickness of the electrode-supporting film was 110 μm, and the swelling ratio was 4.3% by the method of example 1.
Comparative example 5
Comparative example 5 provides a dry fabrication method of an energy storage electrode, which is different from example 5 only in that the pressure of air input from a high pressure air nozzle is 0.45Mpa, the speed of air input from the high pressure air nozzle is 350m/s, and the remaining materials and process conditions are the same as those of example 5.
The electrode obtained in this comparative example had a density of 0.61g/cm 3 The thickness of the electrode supporting film was 175 μm, and the swelling ratio was measured by the method of example 1 to be 5.8%.
The above embodiments are not exhaustive of the range of parameters of the claimed technical solutions of the present invention and the new technical solutions formed by equivalent replacement of single or multiple technical features in the technical solutions of the embodiments are also within the scope of the claimed technical solutions of the present invention, and if no specific description is given for all the parameters involved in the technical solutions of the present invention, there is no unique combination of the parameters with each other that is not replaceable.
The specific embodiments described herein are merely illustrative of the spirit of the invention and do not limit the scope of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.

Claims (7)

1. The preparation method of the energy storage electrode is characterized by comprising the following steps of: adding an energy storage material and dry adhesive powder into a dispersion kettle of a dry mixing device, locking a flange, opening a high-pressure air nozzle to admit air, wherein the pressure of the high-pressure air nozzle is 0.5-2Mpa, and dispersing to obtain mixed dry powder, wherein the adhesive forms a fiberized adhesive in the dispersion process; pressing the mixed dry powder into an electrode support film, and pressing the electrode support film on a current collector to obtain an energy storage electrode;
the dry type mixing device for preparing the energy storage electrode comprises a dispersion kettle, wherein the dispersion kettle comprises a kettle body and a flange positioned at an opening at the upper end of the kettle body, an air outlet pipe is arranged in the middle of the flange, a filter plate is arranged in the air outlet pipe, and a gas filtering hole is formed in the filter plate; the cross section of the kettle body is circular, a plurality of high-pressure air nozzles in the same horizontal plane are radially arranged on the outer side wall of the middle part of the kettle body, and an angle phi is formed between the axis of each high-pressure air nozzle and the radial line of the cross section of the kettle body;
the angle phi formed by the axis of the high-pressure air nozzle and the radial line of the cross section of the kettle body is 5-10 degrees;
the inner diameter of the dispersion kettle is 50-100cm, the diameter of the high-pressure air nozzle is 1-3cm, and the length of the high-pressure air nozzle is 8-10cm.
2. The preparation method of the energy storage electrode according to claim 1, wherein the mass ratio of the energy storage material to the binder dry powder is (6 to 10): 1.
3. a method of forming a storage electrode according to claim 1 wherein the high pressure nozzle is supplied at a rate of 360 to 450m/s.
4. The method of claim 1, wherein the dispersion time is 1-10 hours.
5. A storage electrode produced by the production method according to claim 1, wherein the fibrous binder in the storage electrode has a fiber diameter of 10 to 50nm.
6. The energy storage electrode of claim 5, wherein the swelling ratio of the energy storage electrode measured by soaking the energy storage electrode in an electrolyte for 24 hours is not more than 5%.
7. The energy storage electrode of claim 5, wherein the electrode support film of the energy storage electrode has a thickness of 30 to 200 μm and a density of 0.65 to 1.1g/cm 3 。
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