WO2017054297A1 - 电化学电源用电极及其制造方法 - Google Patents

电化学电源用电极及其制造方法 Download PDF

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Publication number
WO2017054297A1
WO2017054297A1 PCT/CN2015/094158 CN2015094158W WO2017054297A1 WO 2017054297 A1 WO2017054297 A1 WO 2017054297A1 CN 2015094158 W CN2015094158 W CN 2015094158W WO 2017054297 A1 WO2017054297 A1 WO 2017054297A1
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Prior art keywords
electrode
current collector
electrochemical power
power supply
granulation
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PCT/CN2015/094158
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English (en)
French (fr)
Inventor
薛龙均
阿龙·埃里
刘凤丹
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薛龙均
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Priority claimed from CN201510641082.2A external-priority patent/CN105336913B/zh
Application filed by 薛龙均 filed Critical 薛龙均
Publication of WO2017054297A1 publication Critical patent/WO2017054297A1/zh

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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
    • 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
    • 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
    • H01M4/0419—Methods of deposition of the material involving spraying
    • 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

Definitions

  • the present invention relates to the field of electrochemistry, and in particular to an electrode for electrochemical power supply and a method of manufacturing the same, and an electrode manufactured by the method, the electrode can be applied to various electrochemical power sources, including a supercapacitor, a lithium ion battery , fuel cells, hybrid capacitors and lithium ion capacitors.
  • Electrochemical power supply is an environmentally-friendly energy storage and release device that converts energy through physical or chemical means, provides energy for various electrical facilities, involves many aspects of social life, and is portable and easy to use. Sex, widely used in electronic products, power tools, wind energy, solar energy, automotive, aviation and other fields.
  • electrochemical power sources include supercapacitors, lithium ion batteries, fuel cells, hybrid capacitors, and lithium ion capacitors.
  • the electrode is the core component of the electrochemical power source.
  • the electrode manufacturing method determines the electrode quality and is a key factor affecting the performance of the electrochemical power source.
  • the electrode material is generally composed of an active material, a conductive agent, and a binder.
  • the electrode material and the current collector are combined to form an electrode.
  • the active material is the main material of the electrode, providing capacity; the conductive agent is used to improve the electrical conductivity of the electrode; the binder is used to bond the electrode material and the current collector together, and the current collector is used to support the electrode material and provide an electron migration channel.
  • the electrode manufacturing method mainly includes two kinds of coating processes and solventless processes.
  • the coating process is to first mix the active material, the conductive agent and the binder with a large amount of solvent to prepare a slurry having a certain solid content, then apply the slurry to the current collector, and then dry to remove the solvent.
  • this process has a series of problems. Firstly, due to the difference in the physical structure of various electrode materials, especially the particle size of some materials is small, only micron or even nanometer level, difficult to disperse, and difficult to process later, so even after long time stirring, it is still difficult to be in the slurry. In the material, the mixing is uniform, which affects the performance of the electrode and causes batch difference between the electrode level and the power supply performance.
  • the power supply string parallel combination application requires high consistency of the single power supply, otherwise it will affect the performance. And the service life; secondly, the method of introducing a large amount of solvent and then drying and removing it in the manufacturing process is cumbersome, consumes energy, increases manufacturing time and cost, and organic solvent has great harm to the environment and the human body.
  • the electrode fabricated by this process, the adhesion between the electrode material and the current collector is also easily deteriorated as the charge and discharge cycle progresses, causing the electrode material to fall off, the electrochemical power source to fail, and affecting the life.
  • Another method for manufacturing an electrode is a solventless process, that is, a large amount of solvent is not used in the manufacturing process, but the active material, the conductive agent and the binder are directly mixed, the fibrillated binder is formed, and then compacted to form a self-supporting The functional membrane is then pressed against the current collector to form an electrode.
  • this process avoids a series of problems caused by the use of a large amount of solvent in the coating process, but the manufacturing process of the process is complicated, and the parameters such as accuracy, pressure, tension and the like of the device are relatively high in the manufacturing process. Moreover, there is still a certain error in the electrode thickness.
  • the technical solution adopted by the present invention is a method for manufacturing an electrode for an electrochemical power source, which comprises the following steps:
  • the granulating material is electrostatically sprayed to form a charged high-speed particle stream, and the deposition is adsorbed on the oppositely charged current collector to form an electrode coating;
  • the mass ratio of the active material, the conductive agent and the binder is from 80 to 97:0.1 to 15:1 to 15; preferably from 80 to 97:0.1 to 10:1 to 10.
  • the active material includes one or more of activated carbon, carbon nanotubes, graphene, carbon aerogel, activated carbon fiber, graphite, silicon, metal oxide, and lithium-containing compound.
  • the conductive agent includes one or more of graphite, carbon black, acetylene black, carbon nanotubes, carbon fibers, and metal fibers.
  • the binder includes one or more of a fluoropolymer, an olefin polymer, a polycarbonate, an acrylic resin, styrene butadiene rubber, and carboxymethyl cellulose.
  • the active material, the conductive agent and the binder are preferably powder particles.
  • the step 1) granulation process is achieved by the collision and aggregation forces of the particles.
  • the meshing number is 10 to 200 mesh.
  • the drying temperature is 20 to 200 °C.
  • the granulating material has a particle diameter of 5 to 90 um.
  • a bridging liquid can be added to the granulation process.
  • the bridging liquid can be one or a mixture of water, organic solvent.
  • the ratio of the mass of the bridging liquid to the total mass of the active material, the conductive agent and the binder is 0.1 to 30%.
  • the voltage of the step 2) electrostatic spraying is 30 to 90 kV.
  • the carrier gas of the high velocity particle stream is a compressed gas.
  • the compressed gas can be air or an inert gas.
  • the pressure of the compressed gas is 0.6 to 0.8 MPa.
  • the step 2) current collector comprises aluminum foil, copper foil, nickel foil, stainless steel, aluminum mesh, copper mesh, nickel mesh or stainless steel mesh; the current collector can be pretreated before spraying; the pretreatment can be pre-concentrated on the current collector Painted with an intermediate transition layer. Further, the current collector may be used as it is without pretreatment.
  • the number of lamination of the step 3) is 1 to 5 times.
  • the thickness reduction of the electrode coating is 5 to 30% per time.
  • the method of the present invention is applied to an electrode for an electrochemical power source and an electrochemical power source including the electrode.
  • the electrochemical power source may be a super capacitor, a lithium ion battery, a fuel cell, a hybrid capacitor, a lithium ion capacitor, or the like.
  • the electrode material is uniformly mixed, and it is easy to be successively processed and processed continuously, and the electrode batch consistency is good, and the performance is excellent.
  • the manufacturing process does not use a large amount of solvent, save energy, reduce environmental pollution, short manufacturing time and high production efficiency.
  • the granulated materials in the manufacturing process can be recycled and reused, with high material utilization rate and low manufacturing cost.
  • the adhesion can be increased by the charge attraction and the laminating step, so that the amount of the required binder can be minimized, which is advantageous for reducing the internal resistance of the electrode. Increase the power density of the electrochemical power source.
  • the electrode coating thickness control is simple and precise, and the consistency is high; the method provided by the invention mainly realizes electrode coating deposition by granulating material and current collector charge attraction, and can simply adjust the working parameters during electrostatic spraying. The charge charge is changed to obtain the electrode coating of the desired thickness, and the consistency is strictly ensured, and its simplicity and precision are unmatched by other electrode manufacturing processes.
  • the electrode compaction density is large.
  • the static density can increase the bulk density of the granulating material on the current collector, and it can also pass Subsequent multiple lamination steps increase the electrode compaction density and increase the energy density of the electrochemical power source.
  • the electrode compaction density is consistent.
  • the method provided by the invention is that the granulated charge and the collector charge are attracted to each other, and the granulated material is piled up to form an electrode coating. As the electrode coating is thickened, the charge attraction is weakened, and the granulated material accumulated on the surface of the electrode coating is accumulated. Looser than the internal, the electrode coating compactness decreases with the distance from the current collector. In the lamination, the roll pressure first acts on the surface of the electrode coating, and the granulated material having a relatively loose surface is compacted and laminated a plurality of times to finally obtain an electrode having a good internal and external compact density.
  • Electrodes fabricated by other processes will cause the surface density of the electrode to be larger than the internal density during lamination, which is not conducive to the penetration of the electrolyte into the interior of the electrode, affecting the performance and life of the electrode.
  • the method of the present invention effectively solves this problem.
  • the method has a wider range of selection of current collectors.
  • mesh current collectors are also suitable.
  • the mesh current collector is lighter in mass than the conventional current collector, has a larger contact area with the electrode coating, and can accommodate more active materials, thereby greatly reducing the quality of the electrochemical power source, increasing the capacity and energy density.
  • the current collector is squeezed between the plurality of coating rolls and brought into contact with the doctor blade, and it is likely to destroy the structure of the current collector to some extent, so the use of the mesh current collector exists. Restrictions affect power supply performance.
  • the method of the present invention does not have such problems.
  • the invention provides an electrode for electrochemical power supply.
  • the electrode manufactured by the method is applied to an electrochemical power source, so that the electrochemical power source has a substantial improvement in overall performance compared with the product obtained by the prior art.
  • FIG. 1 is a schematic view showing a manufacturing process of an electrode for an electrochemical power source.
  • Figure 2 is a schematic view of the state of the granulation process.
  • Figure 3 is a schematic flow chart of the equipment of the electrostatic spraying step.
  • Figure 4 is a schematic view of the working principle of the electrostatic spraying device.
  • Fig. 5 is a view showing the electrode topography of the first embodiment of the present invention.
  • Fig. 6 is a view showing the electrode topography of the second embodiment of the present invention.
  • Figure 7 (a) is a schematic structural view of an electrochemical power supply electrode.
  • Figure 7 (b) is a schematic illustration of the density of an electrode fabricated using the method of the present invention.
  • Fig. 7(c) is a schematic view showing the density of an electrode fabricated by the method.
  • Figure 8 is a schematic view showing the structure of the positive and negative electrodes of an electrochemical power source.
  • 21 is the active material
  • 22 is the conductive agent
  • 23 is the binder
  • 24 is the nuclear particle
  • 25 is the aggregate
  • 26 is the granulation particle
  • 31 is the air compressor
  • 32 is the compressed gas storage tank
  • 33 is the cold Dry machine
  • 34 is granulated storage tank
  • 35 is spray booth
  • 36 is spray equipment
  • 37 is electrostatic generator
  • 38 is dust removal equipment
  • 39 is induced draft fan
  • 41 discharge electrode
  • 42 is negative charge
  • 43 is set
  • the fluid, 44 is a granulation material
  • 45 is a compressed gas stream
  • 46 is a particle stream
  • 71 is an electrode coating.
  • 81 is a positive electrode coating layer
  • 82 is a positive electrode current collector
  • 83 is a negative electrode coating layer
  • 84 is a negative electrode current collector
  • 85 is a separator.
  • the electrode produced by the method has the characteristics of good consistency, high energy density and power density, long service life and high material utilization rate.
  • the method for manufacturing an electrode provided by the present invention mainly comprises three steps of granulation, electrostatic spraying and lamination.
  • the granulating material is electrostatically sprayed to form a charged high-speed particle stream, and the deposition is adsorbed on the oppositely charged current collector to form an electrode coating;
  • FIG. 1 is a schematic view showing a manufacturing process of an electrode for an electrochemical power source. A method of manufacturing an electrode for an electrochemical power source will be described in detail below with reference to the flowchart:
  • the active material, the conductive agent and the binder may be separately sieved, dried, and then pre-mixed to form a premix.
  • the animal material can be rolled and mixed by stirring or container rotation.
  • the mesh used for the screening is 10 to 200 mesh.
  • the drying temperature range is 20 to 200 °C. Drying can be vacuum drying.
  • the active material is a main material of the electrode material, and is preferably a powder particle, and examples thereof include graphite, activated carbon, carbon nanotubes, graphene, carbon aerogel, metal oxide, and a lithium-containing compound.
  • Metal oxides include nickel oxide, cobalt oxide, oxidized granules, vanadium oxide, manganese oxide, iron oxide, and the like.
  • the lithium-containing compound includes lithium titanate, lithium cobaltate, lithium manganate, lithium iron phosphate, and the like.
  • the conductive agent is a substance having electron conductivity, and is preferably powder particles, and examples thereof include graphite, carbon black, acetylene black, carbon nanotubes, carbon fibers, metal fibers, and the like.
  • the binder is a substance for bonding, preferably powder particles, and examples thereof include fluoropolymers such as polyvinylidene fluoride and polytetrafluoroethylene, and olefin polymers such as polyethylene, polypropylene, and acrylic acid. Resin, styrene butadiene rubber and sodium carboxymethyl cellulose.
  • the particles in the present invention include various forms such as granular, flake, fibrous, and block.
  • the meaning of "including” in the present invention includes but is not limited to.
  • the particle size of the active material, the conductive agent and the binder particles are generally on the order of micrometers or nanometers.
  • the premix is granulated in the next step.
  • the granulation process is achieved by collision and aggregation of various electrode material particles.
  • a granulator including a disc type, a cylinder type, a double cone type, a stirring type, or the like can be mentioned.
  • FIG. 2 is a schematic view of the state of the granulation process.
  • the small particles of the active material 21, the conductive agent 22 and the binder 23 first rapidly aggregate to form the core particles 24, and then the subsequent impact.
  • the incoming particles continue to aggregate around the core particles, forming an aggregate 25, which undergoes a snowball growth and is densed during further impact, eventually becoming a granulated particle 26 that is uniformly mixed, has good fluidity, and is easily processed.
  • the granulated granules are classified and classified to meet the particle size requirements, which is the final granulated material.
  • the particle size of the granulating material is preferably from 5 to 90 um.
  • the particle size is too large, it can be pulverized and then sieved.
  • the granulation time is determined depending on factors such as the amount of the material, the specific material properties, and the type of equipment, and is preferably from 5 to 120 minutes, more preferably from 10 to 60 minutes.
  • the invention provides a method for granulating, which can process small particle size particles into granules with large particle size and good free-flowing property while mixing several electrode materials uniformly, so as to facilitate subsequent processing and continuous production.
  • a small amount of bridging liquid can be added to increase the adhesion between the particles.
  • the bridging liquid is present in an amount of from 0.1 to 30%, more preferably from 5 to 20%, based on the total mass of the electrode material.
  • the bridging liquid can be water-based, organically soluble
  • One or a mixture of the agents may, for example, be water, alcohols, ketones, hydrocarbons or the like.
  • the content of each component is preferably such that the mass of the active material accounts for 60 to 97%, more preferably 80 to 97%, based on the total mass of the electrode material.
  • the amount of the conductive agent accounts for 0.1 to 20%, more preferably 0.1 to 10%, based on the total mass of the electrode material.
  • the binder mass is from 1 to 20%, more preferably from 1 to 10%, based on the total mass of the electrode material.
  • the electrostatic spraying process is entered.
  • the air compressor 31 is sequentially connected to the compressed gas storage tank 32 and the cold drying machine 33, and the compressed air after the cold-drying treatment is supplied to the granulating material storage tank 34 to push the granulated material into the spraying equipment 36.
  • the electrostatic generator 37 is coupled to the spray equipment 36 to provide a high voltage power supply.
  • the spray equipment can be a spray gun.
  • the electrostatic generator 37 can be mounted inside or outside the spray gun. The spraying process takes place in the spray booth 35.
  • the inner wall of the spray booth 35 is made of an insulating material such as a polypropylene plate, a stainless steel plate, a plexiglass plate or the like.
  • the dust removing device 38 is connected to the induced draft fan 39.
  • the granulated material that is not adsorbed onto the current collector is recovered by the dust removing device 38.
  • the dust removing device may use one or more of a cyclone separator or a bag filter. After the dust removal and purification treatment and screening, the recycled materials can enter the granulation process with a certain proportion of the new electrode materials or enter the spraying process with a certain proportion of the new granulation materials.
  • Working principle of electrostatic spraying equipment Referring to Fig.
  • the discharge of the electrostatic generator 37 generates a high voltage acting on the discharge electrode 41 of the port of the spraying device 36, generating a negative charge 42 at the port, and the current collector 43 is grounded, and is brought under the action of the induced electric field.
  • the charge; the granulating material 44 is negatively charged through the nozzle under the rapid pushing action of the compressed gas stream 45 and becomes a charged high-speed particle stream 46, which is impacted and adsorbed in the set under the dual force of airflow pushing and charge attraction.
  • An electrode coating is formed on the fluid 43.
  • the nozzles can be designed in multiple side-by-side arrangements.
  • the thickness of the electrode coating is preferably from 30 to 200 um. More specifically, it is preferably 50 to 150 um.
  • an electrode coating can be formed on one or both sides of the current collector.
  • the voltage of the electrostatic generator is preferably 30 to 90 kV. More specifically, the voltage of the electrostatic generator is preferably 40 to 50 kV.
  • the compressed gas can be compressed air or an inert gas. The pressure of the compressed gas is preferably 0.6 to 0.8 MPa.
  • the current collector deposited with the electrode coating enters the lamination apparatus.
  • the laminating apparatus can be a roller press.
  • the number of laminations is preferably from 1 to 5 times, depending on the final desired electrode thickness and compaction density, and the amount of reduction in lamination thickness per time is preferably from 5 to 30%.
  • a dense electrode is obtained by gradually reducing the amount of compression per lamination.
  • Current collectors include aluminum foil, copper foil, nickel foil, stainless steel, aluminum mesh, copper mesh, stainless steel mesh, and various deformations and pretreatments of the above materials.
  • the thickness of the current collector is preferably from 5 to 100 um, more specifically, preferably from 8 to 50 um.
  • the current collector can be pretreated prior to spraying.
  • the form of the pretreatment may, for example, pre-coat the intermediate transition layer on the surface of the current collector.
  • the intermediate transition layer is mainly composed of a conductive material and a binder.
  • the intermediate transition layer can increase the bond strength of the current collector to the electrode coating and reduce the internal resistance.
  • the thickness of the intermediate transition layer is preferably from 1 to 15 um, more specifically from 3 to 10 um.
  • the current collector can also be used directly without pretreatment.
  • the method for manufacturing an electrode of the present invention has a wider selection range of current collectors, and is particularly suitable for a mesh current collector.
  • the mesh current collector is lighter in mass than the conventional current collector, has a larger contact area with the electrode coating, and can accommodate more active materials, thereby greatly reducing the quality of the electrochemical power source, increasing the capacity and energy density.
  • the current collector is squeezed between the plurality of coating rolls and brought into contact with the doctor blade, and it is likely to destroy the structure of the current collector to some extent, and the method of the present invention does not exist. problem.
  • Activated carbon, carbon black and polyethylene are separately sieved, dried and premixed for 50 minutes according to the mass ratio of 80:10:10.
  • Ethanol having a total mass of the electrode material of 0.1% by mass was added, granulated for 30 minutes, and classified by sieving to obtain a granulated material.
  • the electrostatic generator voltage was set to 55 KV
  • the compressed air pressure was set to 0.6 MPa
  • the granulated material was sprayed onto a 20 um thick aluminum foil to form an electrode coating having a thickness of 110 um.
  • an electrode coating was also sprayed and laminated by a roll press to obtain a 200 um thick electrode.
  • Fig. 5 is a topographical view of the electrode obtained in the present embodiment.
  • Activated carbon, carbon black and polytetrafluoroethylene were sieved, dried and pre-mixed for 50 minutes according to the mass ratio of 95:4:1.
  • the total mass of the electrode material was 30% by mass of ethanol, granulated for 20 minutes, and classified. Sieve to obtain granulated material.
  • the electrostatic generator voltage was set to 50 kV, the compressed air pressure was set to 0.6 MPa, and the granulated material was sprayed onto a 30 um thick aluminum foil to form an electrode coating having a thickness of 120 um. An electrode coating was also sprayed on the other side of the aluminum foil. After lamination by a roller press, a 230 um thick electrode was obtained.
  • Fig. 6 is a topographical view of the electrode obtained in the present embodiment.
  • the carbon aerogel, carbon fiber and polytetrafluoroethylene were respectively sieved according to the mass ratio of 97:0.1:2.9, dried, premixed for 100 minutes, and acetone was added in an amount of 10% by mass of the total mass of the electrode material, and granulation was carried out for 20 minutes.
  • the sieve is classified and granulated.
  • the electrostatic generator voltage was set to 50 kV, the compressed air pressure was set to 0.65 MPa, and the granulated material was sprayed onto a 20 um thick nickel mesh to form an electrode coating having a thickness of 150 um.
  • the laminate was laminated four times through a roll press to obtain an electrode having a thickness of 120 ⁇ m.
  • Graphene, graphite and polyurethane are separately sieved according to the mass ratio of 80:15:5, dried, premixed for 100 minutes, and acetone is added in an amount of 10% by mass of the total mass of the electrode material, granulated for 20 minutes, and sieved to obtain Granulation material.
  • the electrostatic generator voltage was set to 50 kV
  • the compressed air pressure was set to 0.65 MPa
  • the granulated material was sprayed onto the 20 um thick aluminum mesh side precoated with the intermediate transition layer to form an electrode coating having a thickness of 150 um.
  • the laminate was laminated five times by a roll press to obtain an electrode having a thickness of 110 ⁇ m.
  • Graphene, graphite, styrene-butadiene rubber, carboxymethyl cellulose are separately sieved according to the mass ratio of 85:10:4:1, dried, pre-mixed for 100 minutes, and added with water having a total mass of 10% by mass of the electrode material. Granulation was carried out for 40 minutes, and classified by sieving to obtain a granulated material.
  • the electrostatic generator voltage was set to 45 kV
  • the compressed air pressure was set to 0.6 MPa
  • the granulated material was sprayed onto a 20 um thick stainless steel precoated with an intermediate transition layer to form an electrode coating having a thickness of 150 um.
  • the electrode coating was also sprayed on the other side of the stainless steel.
  • the laminate was laminated three times by a roll press to obtain an electrode having a thickness of 280 um.
  • the cerium oxide, carbon black and polyurethane are respectively sieved according to the mass ratio of 80:5:15, dried, pre-mixed for 100 minutes, and acetone is added in an amount of 10% by mass of the total mass of the electrode material, granulated for 20 minutes, and sieved by grading. A granulated material is obtained.
  • the electrostatic generator voltage was set to 50 kV, the compressed air pressure was set to 0.8 MPa, and the granulated material was sprayed onto a 30 um thick stainless steel mesh to form an electrode coating having a thickness of 100 um.
  • the electrode coating was also sprayed on the other side of the stainless steel mesh.
  • the laminate was laminated three times by a roll press to obtain an electrode having a thickness of 190 um.
  • the carbon nanotubes, the metal aluminum fibers and the polycarbonate are respectively sieved according to a mass ratio of 95:1:4, dried, pre-mixed for 100 minutes, and acetone is added in an amount of 10% by mass of the total mass of the electrode material, and granulated for 20 minutes.
  • the sieve is classified and granulated.
  • the electrostatic generator voltage was set to 50 KV
  • the compressed air pressure was set to 0.8 MPa
  • the granulated material was sprayed onto a 30 um thick nickel foil to form an electrode coating having a thickness of 150 um.
  • An electrode coating was also sprayed on the other side of the nickel foil. Laminated three times by a roller press, An electrode having a thickness of 280 um was obtained.
  • Nickel oxide, acetylene black and acrylic resin were separately sieved according to the mass ratio of 95:1:4, dried, premixed for 100 minutes, and acetone was added in an amount of 10% by mass of the total mass of the electrode material, granulated for 20 minutes, and sieved by grading. , to obtain granulated materials.
  • the electrostatic generator voltage was set to 50 kV, the compressed air pressure was set to 0.8 MPa, and the granulated material was sprayed onto the 30 um thick aluminum foil side to form an electrode coating having a thickness of 150 um.
  • the laminate was laminated three times by a roll press to obtain an electrode having a thickness of 120 ⁇ m.
  • Lithium titanate, graphite, and polyvinylidene fluoride are separately sieved, dried, premixed for 50 minutes according to the ratio of parts by mass ratio of 93:3:4, and acetone is added in an amount of 20% by mass of the total mass of the electrode material, and granulation is carried out for 30 minutes.
  • the sieve is classified and granulated.
  • the electrostatic generator voltage was 60 KV
  • the compressed air pressure was 0.7 MPa
  • the granulated material was sprayed onto a 10 um copper foil precoated with an intermediate transition layer to form an electrode coating having a thickness of 80 um.
  • An electrode coating was also sprayed on the other side of the copper foil. It was laminated twice by a roll press to obtain an electrode having a thickness of 110 ⁇ m.
  • Graphite, acetylene black and polyvinylidene fluoride are separately sieved according to the mass ratio of 85:10:5, dried, pre-mixed for 100 minutes, and acetone is added in an amount of 20% by mass of the total mass of the electrode material, granulated for 30 minutes, and classified. Sieve to obtain granulated material.
  • the electrostatic generator voltage was 60KV
  • the compressed air pressure was 0.7MPa
  • the granulated material was sprayed onto a 10um copper mesh to form an electrode coating with a thickness of 100um.
  • the laminate was laminated at a time by a roll press to obtain an electrode having a thickness of 80 ⁇ m.
  • Lithium cobaltate, activated carbon, acetylene black, polystyrene are separately sieved according to the mass ratio of 20:70:5:5, dried, premixed for 50 minutes, and added to the total mass of the electrode material by 20% by mass of water, granulation After 20 minutes, the sieve was classified to obtain a granulated material.
  • the electrostatic generator voltage was 60 KV
  • the compressed air pressure was 0.7 MPa
  • the granulated material was sprayed onto a 10 um aluminum foil to form an electrode coating having a thickness of 120 um.
  • the laminate was laminated at a time by a roll press to obtain an electrode having a thickness of 90 ⁇ m.
  • Graphite, silicon, acetylene black, polyvinylidene fluoride are separately sieved according to the mass ratio of 80:10:7:3, dried, pre-mixed for 100 minutes, and added to the total mass of the electrode material by 20% by mass of propanol, granulated After 30 minutes, the sieve was classified to obtain a granulated material.
  • the electrostatic generator voltage was 60KV
  • the compressed air pressure was 0.7MPa
  • the granulated material was sprayed onto a 10um copper mesh to form an electrode coating with a thickness of 100um.
  • the electrode coating was also sprayed on the other side of the copper mesh. It was laminated twice by a roll press to obtain an electrode having a thickness of 150 ⁇ m.
  • Fig. 7(a) is a schematic view showing the structure of an electrode of an electrochemical power source, wherein 38 is a current collector and 71 is an electrode coating.
  • Figure 7 (b) is a schematic view of the electrode density produced by the method of the present invention. Among them, the curve b1 is the electrode density before lamination, and the curve b2 is the electrode density after lamination.
  • the electrode is fabricated by the method provided by the present invention, and the granulating material and the current collector form an electrode coating by anisotropic charge attraction.
  • the charge repellency of the sprayed granules is enhanced, and the adsorbable granules are reduced, resulting in a looser and more porous electrode coating from the current collector.
  • the looser coating surface is directly in contact with the roller press, and the force is the largest, and the denser coating has less internal force, so the inner and outer density of the electrode coating after lamination is substantially the same.
  • the electrode density produced by other methods is as shown in Fig. 7(c), wherein the curve c1 is the electrode density before lamination, and the curve c2 is the electrode density after lamination.
  • the inner and outer densities of the pole coating are basically the same, and the surface of the coating is also subjected to a force greater than the internal force during lamination, resulting in a surface density of the electrode after lamination is greater than the internal density.
  • Such an electrode is not conducive to the penetration of the electrolyte during the injection, and affects the performance of the electrode.
  • the method of the present invention has a good consistency of electrode compaction density and solves this problem.
  • FIG 8 is a schematic view showing the structure of the positive and negative electrodes of an electrochemical power source.
  • the positive electrode current collector 82 is coated with an electrode coating 81, which is a positive electrode of the power source.
  • the negative electrode current collector 84 is coated with a negative electrode coating 83 as a negative electrode of the power source.
  • the positive electrode and the negative electrode are placed opposite each other through the separator 85 to form a battery core, and after being assembled into the shell, an electrolyte is injected to form an electrochemical power source.
  • the battery cells can be in a variety of forms such as laminated, wound, and the like.
  • the same or different types of electrode combinations can constitute a variety of electrochemical power sources.
  • an activated carbon electrode can be used for both the positive and negative electrodes to constitute a supercapacitor.
  • a positive electrode uses an activated carbon electrode
  • a negative electrode uses a lithium titanate electrode to constitute a hybrid capacitor.

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Abstract

一种电化学电源用电极及其制造方法，该制造方法包括以下步骤：1)、造粒：活性物质、导电剂和粘结剂分别筛分、干燥后进行预混合，然后造粒，得到造粒料；2)、静电喷涂：造粒料经静电喷涂，形成带有电荷的高速粒子流，沉积吸附在带有相反电荷的集流体上，形成电极涂层；3)、层压：对附有电极涂层的集流体进行层压。该制造方法应用于电化学电源用电极和包含有电极的电化学电源。采用该方法制得的电极性能优异，一致性好，材料利用率高，制造成本低，使得电化学电源在综合性能上比原有工艺制得的产品有了大幅度的提高。电化学电源可以是超级电容器、锂离子电池、燃料电池、混合电容器和锂离子电容器等。

Description

电化学电源用电极及其制造方法 技术领域
本发明涉及电化学领域，具体地，本发明涉及一种电化学电源用电极及制造方法，以及由该方法制造的电极，该电极可应用于多种电化学电源，包括超级电容器、锂离子电池、燃料电池、混合电容器和锂离子电容器。
背景技术
电化学电源是一种环保的能量存储和释放装置，它通过物理或化学的方式进行能量的转化，为各种用电设施提供能源动力，涉及社会生活的多个方面，具有便携性和使用方便性，广泛应用于电子产品、电动工具、风能、太阳能、汽车、航空等领域。这种电化学电源包括超级电容器、锂离子电池、燃料电池、混合电容器和锂离子电容器等。
电极是电化学电源的核心元件，电极的制造方法决定了电极质量，是影响电化学电源性能的关键因素。电极材料一般由活性物质、导电剂和粘结剂组成。电极材料与集流体复合构成电极。活性物质是电极的主材料，提供容量；导电剂用于改善电极的导电性能；粘结剂用于把电极材料及集流体粘结在一起，集流体用于支撑电极材料并提供电子迁移通道。
目前电极的制造方法主要有涂覆工艺和无溶剂工艺两种。涂覆工艺，即先把活性物质、导电剂和粘结剂与大量溶剂混合，制成具有一定固含量的浆料，然后把浆料涂覆在集流体上，再烘干去除溶剂。然而这种工艺存在一系列问题。首先由于各种电极材料物理结构上存在差异性，尤其是有的材料颗粒粒径很小，仅为微米甚至纳米级别，难于分散，后续加工处理困难，因此即使经过长时间搅拌，仍然难以在浆料中实现混合均匀，从而影响电极性能和导致电极水平和电源性能存在批次性差异，而在某些应用领域电源串并联组合应用时对单体电源的一致性要求很高，否则会影响性能和使用寿命；其次制造过程中采用先引入大量溶剂然后再烘干去除的方法，步骤繁琐，耗费能源，增加了制造时间和成本，并且有机溶剂对环境和人体有较大危害。采用这种工艺制造的电极，电极材料与集流体间的粘结性也容易随着充放电循环的进行而变差，导致电极材料脱落，电化学电源失效，影响寿命。
另外一种电极的制造方法是无溶剂工艺，即制造过程中不使用大量溶剂，而是直接把活性物质、导电剂和粘结剂混合，纤丝化粘结剂，然后压实形成具有自支撑功能的膜，再把膜与集流体压合，形成电极。相对而言，这种工艺避免了涂覆工艺使用大量溶剂带来的一系列问题，但这种工艺制造过程较为复杂，而且制造过程中对设备的精度、压力、张力等参数控制要求较高，而且电极厚度仍存在一定误差。
发明内容
基于此，有必要提供一种新的电极制造方法，解决以上问题。本发明采用的技术方案是：电化学电源用电极的制造方法，其包括以下步骤：
1)、造粒。活性物质、导电剂和粘结剂分别筛分、干燥后进行预混合，然后造粒，得到造粒料；
2)、静电喷涂。造粒料经静电喷涂，形成带有电荷的高速粒子流，沉积吸附在带有相反电荷的集流体上，形成电极涂层；
3)、层压。对附有电极涂层的集流体进行层压。
本发明中，所述活性物质、导电剂和粘结剂的质量份数比为80～97：0.1～15：1～15；优选为80～97：0.1～10：1～10。
其中，所述活性物质包括活性炭、碳纳米管、石墨烯、碳气凝胶、活性炭纤维、石墨、硅、金属氧化物、含锂化合物中的一种或几种。
所述导电剂包括石墨、碳黑、乙炔黑、碳纳米管、碳纤维、金属纤维中的一种或几种。
所述粘结剂包括含氟聚合物、烯烃聚合物、聚碳酸酯、丙烯酸树脂、丁苯橡胶和羧甲基纤维素中的一种或几种。
所述活性物质、导电剂和粘结剂优选为粉体颗粒。
所述步骤1)造粒过程是通过颗粒的碰撞、聚集作用力实现。造粒步骤所述筛分目数是10～200目。所述干燥温度是20～200℃。所述造粒料的粒径是5～90um。造粒过程可以加入桥连液体。桥连液体可以是水、有机溶剂中的一种或混合物。桥连液体的质量占活性物质、导电剂和粘结剂总质量的比例是0.1～30％。
所述步骤2)静电喷涂的电压是30～90KV。所述高速粒子流的载气是压缩气体。压缩气体可以是空气或惰性气体。压缩气体的压力是0.6～0.8MPa。
所述步骤2)集流体包括铝箔、铜箔、镍箔、不锈钢、铝网、铜网、镍网或不锈钢网等；集流体在喷涂前可以进行预处理；预处理可以是在集流体上预涂有中间过渡层。另外，集流体也可以不进行预处理而直接使用。
所述步骤3)层压次数是1～5次。每次电极涂层厚度减少量是5～30％。
本发明的方法应用于一种电化学电源用电极和一种包含有电极的电化学电源。
本发明中，所述电化学电源可以是超级电容器、锂离子电池、燃料电池、混合电容器和锂离子电容器等。
本发明提供的电化学电源用电极的制造方法，优势在于：
1、通过采用造粒的方法，保证电极材料混合均匀，易于后续连续生产加工，电极批次一致性好，且性能优异。
2、制造过程没有使用大量溶剂，节约能源，减少环境污染，制造时间短，生产效率高。
3、制造过程中的造粒料可回收再使用，材料利用率高，制造成本低。
4、除了原材料现有的粘结剂外，还可以依靠电荷吸引作用和层压步骤增加粘结力，从而可以使得需要的粘结剂的量几乎降到最低，有利于减小电极内阻，提高电化学电源的功率密度。
5、电极涂层厚度控制简单精确，且一致性高；本发明提供的方法，主要是是通过造粒料和集流体电荷吸引实现电极涂层沉积，可以简单地通过调节静电喷涂时的工作参数改变电荷电量以得到期望厚度的电极涂层，并严格保证其一致性，其简便性和精确性是其他电极制造工艺所不可比拟的。
6、电极压实密度大。通过静电控制可以提高造粒料在集流体上的堆积密度，还可以通过 后续多次层压步骤，增加电极压实密度，提高电化学电源的能量密度。
7、电极压实密度一致性高。本发明提供的方法，是通过造粒料电荷与集流体电荷相互吸引，造粒料堆积形成电极涂层，随着电极涂层增厚，电荷吸引作用减弱，电极涂层表面堆积的造粒料比内部要疏松，造成电极涂层致密性随距离集流体越远而呈减小趋势。而在层压时，轧辊压力首先作用在电极涂层表面，把表面较为疏松的造粒料压实，并经多次层压，最终得到内外部压实密度一致性良好的电极。而其他工艺制造的电极，在层压时都会导致电极表面密度比内部密度大，不利于电解液向电极内部的渗透，影响电极性能和寿命。本发明的方法有效解决了这一问题。
8、该方法对集流体的选择范围更加广泛，除普通集流体外，网状集流体也较为适用。网状集流体与普通的集流体相比，质量轻，与电极涂层的接触面积更大，可容纳的活性物质更多，从而在减轻电化学电源质量、提高容量和能量密度方面有较大优势。然而若采用其他如涂覆工艺制造电极时，集流体在多个涂覆辊间挤压并与刮刀接触，很有可能在一定程度上破坏集流体的结构，因此对网状集流体的使用存在限制，影响电源性能提升。而本发明的方法不存在该类问题。
本发明提供的电化学电源用电极的制造方法该方法制造的电极应用于电化学电源，使得电化学电源在综合性能上比原有工艺制得的产品有了大幅度的提高。
附图说明
图1是电化学电源用电极的制造流程示意图。
图2是造粒过程状态示意图。
图3是静电喷涂步骤的设备流程示意图。
图4是静电喷涂设备的工作原理示意图。
图5是本发明实施例1的电极形貌图。
图6是本发明实施例2的电极形貌图。
图7(a)是一电化学电源电极的结构示意图。
图7(b)是采用本发明的方法制造的电极的密度示意图。
图7(c)是采用其方法制造的电极的密度示意图。
图8是一电化学电源的正负极结构示意图。
其中：21为活性物质，22为导电剂，23为粘结剂，24为核粒子，25为凝集体，26为造粒颗粒，31为空压机，32为压缩气体储罐，33为冷干机，34为造粒料储罐，35为喷涂室，36为喷涂设备，37为静电发生器，38为除尘设备，39为引风机，41为放电电极，42为负电荷，43为集流体，44为造粒料，45为压缩气体气流，46为粒子流，71为电极涂层。81为正极涂层，82为正极集流体，83为负极涂层，84为负极集流体，85为隔膜。
具体实施方式
下面结合附图和具体实施方式对发明内容提供详细说明。然而应当理解，本发明可以以各种形式体现。因此，此处公开的具体细节不应理解成限制性的，而应仅受限于所附的权利 要求。
本发明的目的，在于提供一种电极的制造方法。该方法制造的电极具有一致性好、能量密度和功率密度高、寿命长、材料利用率高等特点。
本发明提供的电极的制造方法，主要包括造粒、静电喷涂和层压三个步骤。
1)、造粒。活性物质、导电剂和粘结剂分别筛分、干燥后进行预混合，然后造粒，得到造粒料；
2)、静电喷涂。造粒料经静电喷涂，形成带有电荷的高速粒子流，沉积吸附在带有相反电荷的集流体上，形成电极涂层；
3)、层压。对附有电极涂层的集流体进行层压。
图1是电化学电源用电极的制造流程示意图。下面将参考该流程图详细描述电化学电源用电极的制造方法：
在造粒前，可以先对活性物质、导电剂和粘结剂分别进行筛分、干燥处理，然后预混合，形成预混料。具体混合方式，可以举例如通过搅拌或容器转动带动物料滚动使其混合。其中筛分所用筛网的目数是10～200目。其中干燥的温度范围是20～200℃。干燥可以是真空干燥。活性物质是电极材料的主材，优选为粉体颗粒，可以举例如石墨、活性炭、碳纳米管、石墨烯、碳气凝胶、金属氧化物、含锂化合物等。金属氧化物包括氧化镍、氧化钴、氧化辽、氧化钒、氧化锰、氧化铁等。含锂化合物包括钛酸锂、钴酸锂、锰酸锂、磷酸铁锂等。导电剂是具有电子传导性的物质，优选为粉体颗粒，可以举例如石墨、碳黑、乙炔黑、碳纳米管、碳纤维、金属纤维等。粘结剂是起粘合作用的物质，优选为粉体颗粒，可以举例如含氟聚合物，如聚偏氟乙烯和聚四氟乙烯，还有烯烃聚合物，如聚乙烯、聚丙烯以及丙烯酸树脂、丁苯橡胶和羧甲基纤维素钠等。需要说明的是，本发明中所述颗粒，包括粒状、片状、纤维状、块状等多种形式。另外，本发明中所述“包括”，是包括但不限于的意思。活性物质、导电剂和粘结剂颗粒粒径一般都在微米或者纳米级别。
下一步对预混料进行造粒。造粒过程是通过各种电极材料颗粒的碰撞、聚集作用实现。只要能够提供以上作用力的设备都可以用作造粒设备，具体地，可以举例如造粒机，包括圆盘式、圆筒式、双锥式、搅拌式等多种形式。
图2是造粒过程状态示意图，造粒开始时，随造粒设备或搅拌桨不断转动，活性物质21、导电剂22和粘结剂23的小颗粒首先快速聚集形成核粒子24，然后后续撞击过来的颗粒在核粒子周围继续聚集，形成凝集体25，凝集体经过滚雪球式增长，并在进一步撞击过程中得以密实，最终成为混合均匀、流动性良好、易于后续加工的造粒颗粒26。对造粒颗粒筛分分级，满足粒径要求的，即为最终的造粒料。造粒料的粒径优选在5～90um。粒径过大的，可以进行粉碎后再筛分。造粒的时间根据料量、具体材料性质和设备类型等因素确定，优选5～120分钟，更优选地是10～60分钟。本发明提供了造粒的方法，在把几种电极材料混合均匀的同时，把小粒径的颗粒加工成大粒径、自由流动性良好的造粒料，方便后续加工处理和连续生产。
在造粒过程中，可以添加少量桥连液体用于增加颗粒间的黏结力。优选地是，桥连液体的含量占电极材料总质量的0.1～30％，更优选地是5～20％。桥连液体可以是水系、有机溶 剂中的一种或混合物，可以举例如水、醇类、酮类、烃类等。
另外，上述电极材料中，各成分的含量，优选地是，活性物质质量占电极材料总质量的60～97％，更优选地是80～97％。导电剂质量占电极材料总质量的0.1～20％，更优选地是0.1～10％。粘结剂质量占电极材料总质量的1～20％，更优选地是1～10％。
造粒完成后，进入静电喷涂工序。如图3的静电喷涂步骤：空压机31与压缩气体储罐32以及冷干机33依次连接，经冷干处理后的压缩气体输入造粒料储罐34，推动造粒料进入喷涂设备36。静电发生器37与喷涂设备36相连，提供高压电源。喷涂设备可以是喷枪。静电发生器37可以安装在喷枪的内部或外部。喷涂过程在喷涂室35内进行。喷涂室35内壁由绝缘材料构成，如聚丙烯板、不锈钢板、有机玻璃板等。除尘设备38与引风机39相连接。未吸附到集流体上的造粒料由除尘设备38回收。除尘设备可以使用如旋风分离器、布袋过滤器中的一种或几种。回收料经除尘净化处理和筛选后，可以与新的电极材料按照一定比例进入造粒工序或与新的造粒料按照一定比例进入喷涂工序再利用。静电喷涂设备工作原理参考图4，静电发生器37放电产生高压作用在喷涂设备36端口的放电电极41上，在端口处产生负电荷42，而集流体43接地，在感应电场作用下带上正电荷；造粒料44在压缩气体气流45的快速推动作用下经过喷嘴喷出时带上负电荷并成为带电的高速粒子流46，在气流推动和电荷吸引的双重作用力下撞击并吸附在集流体43上形成电极涂层。为提高生产效率，喷嘴可以设计为多个并列排布。电极涂层的厚度优选在30～200um。更具体地，优选在50～150um。根据电化学电源的实际使用需要，可以在集流体的单面或双面制作有电极涂层。静电发生器的电压优选是30～90KV。更具体地，静电发生器的电压优选是40～50KV。压缩气体可以是压缩空气或惰性气体。压缩气体的压力优选是0.6～0.8MPa。
沉积有电极涂层的集流体进入层压设备。层压设备可以是辊压机。根据最终需要的电极厚度和压实密度，层压次数优选1～5次，每次的层压厚度减少量优选是5～30％。通过逐步减小每次层压的压缩量，得到致密的电极。
集流体包括铝箔、铜箔、镍箔、不锈钢、铝网、铜网、不锈钢网以及对上述材料的各种变形和预处理。集流体的厚度优选在5～100um，更具体地，优选8～50um。本发明中，可以在喷涂前对集流体进行预处理。预处理的形式可以举例如，在集流体表面预涂中间过渡层。中间过渡层主要由导电物质和粘结剂构成。中间过渡层可以增加集流体与电极涂层的粘结强度并减小内阻。中间过渡层的厚度优选在1～15um，更具体地，优选3～10um。另外，集流体也可以不经预处理直接使用。需要说明的是，本发明的电极的制造方法对集流体的选择范围更加广泛，尤其适用于网状集流体。网状集流体与普通的集流体相比，质量轻，与电极涂层的接触面积更大，可容纳的活性物质更多，从而在减轻电化学电源质量、提高容量和能量密度方面有较大优势。然而若采用其他如涂覆工艺制造电极时，集流体在多个涂覆辊间挤压并与刮刀接触，很有可能在一定程度上破坏集流体的结构，而本发明的方法不存在该类问题。
本发明不限于上述实施方式，而是可以在如权利要求所述的本发明的范围内进行各种改进。这些改进包含在本发明的范围之内。
实施例1
活性炭、炭黑和聚乙烯按照80：10：10的质量份数比分别筛分、干燥，预混合50分钟， 加入电极材料总质量0.1％质量比的乙醇，造粒30分钟，分级过筛，得到造粒料。静电发生器电压设置为55KV，压缩空气压力设置为0.6MPa，造粒料喷涂到20um厚的铝箔上，形成厚度110um的电极涂层。在铝箔的另一侧同样喷涂制作电极涂层，经过辊压机一次层压，得到200um厚的电极。图5为本实施例得到的电极形貌图。
实施例2
活性炭、炭黑和聚四氟乙烯按照95:4:1的质量份数比分别筛分、干燥，预混合50分钟，加入电极材料总质量30％质量比的乙醇，造粒20分钟，分级过筛，得到造粒料。静电发生器电压设置为50KV，压缩空气压力设置为0.6MPa，造粒料喷涂到30um厚的铝箔上，形成厚度120um的电极涂层。在铝箔的另一侧同样喷涂制作电极涂层。经过辊压机一次层压最终得到230um厚的电极。图6为本实施例得到的电极形貌图。
实施例3
碳气凝胶、碳纤维和聚四氟乙烯按照97：0.1：2.9的质量份数比分别筛分、干燥，预混合100分钟，加入电极材料总质量10％质量比的丙酮，造粒20分钟，分级过筛，得到造粒料。静电发生器电压设置为50KV，压缩空气压力设置为0.65MPa，造粒料喷涂到20um厚的镍网上，形成厚度150um的电极涂层。经过辊压机四次层压，得到厚度120um的电极。
实施例4
石墨烯、石墨、聚氨酯按照80:15:5的质量份数比分别筛分、干燥，预混合100分钟，加入电极材料总质量10％质量比的丙酮，造粒20分钟，分级过筛，得到造粒料。静电发生器电压设置为50KV，压缩空气压力设置为0.65MPa，造粒料喷涂到预涂有中间过渡层的20um厚的铝网一侧上，形成厚度150um的电极涂层。经辊压机五次层压，得到厚度110um的电极。
实施例5
石墨烯、石墨、丁苯橡胶、羧甲基纤维素按照85:10:4:1的质量份数比分别筛分、干燥，预混合100分钟，加入电极材料总质量10％质量比的水，造粒40分钟，分级过筛，得到造粒料。静电发生器电压设置为45KV，压缩空气压力设置为0.6MPa，造粒料喷涂到预涂有中间过渡层的20um厚的不锈钢上，形成厚度150um的电极涂层。在不锈钢另一侧同样喷涂制作电极涂层。经辊压机三次层压，得到厚度280um的电极。
实施例6
氧化钌、炭黑和聚氨酯按照80：5：15的质量份数比分别筛分、干燥，预混合100分钟，加入电极材料总质量10％质量比的丙酮，造粒20分钟，分级过筛，得到造粒料。静电发生器电压设置为50KV，压缩空气压力设置为0.8MPa，造粒料喷涂到30um厚的不锈钢网上，形成厚度100um的电极涂层。在不锈钢网另一侧同样喷涂制作电极涂层。经辊压机三次层压，得到厚度190um的电极。
实施例7
碳纳米管、金属铝纤维和聚碳酸酯按照95：1：4的质量份数比分别筛分、干燥，预混合100分钟，加入电极材料总质量10％质量比的丙酮，造粒20分钟，分级过筛，得到造粒料。静电发生器电压设置为50KV，压缩空气压力设置为0.8MPa，造粒料喷涂到30um厚的镍箔上，形成厚度150um的电极涂层。在镍箔另一侧同样喷涂制作电极涂层。经辊压机三次层压， 得到厚度280um的电极。
实施例8
氧化镍、乙炔黑和丙烯酸树脂按照95：1：4的质量份数比分别筛分、干燥，预混合100分钟，加入电极材料总质量10％质量比的丙酮，造粒20分钟，分级过筛，得到造粒料。静电发生器电压设置为50KV，压缩空气压力设置为0.8MPa，造粒料喷涂到30um厚的铝箔一侧上，形成厚度150um的电极涂层。经辊压机三次层压，得到厚度120um的电极。
实施例9
钛酸锂、石墨、聚偏氟乙烯按照93:3:4的比例质量份数比分别筛分、干燥，预混合50分钟，加入电极材料总质量20％质量比的丙酮，造粒30分钟，分级过筛，得到造粒料。静电发生器电压采用60KV，压缩空气压力采用0.7MPa，把造粒料喷涂到预涂有中间过渡层的10um的铜箔上，形成厚度80um的电极涂层。在铜箔另一侧同样喷涂制作电极涂层。经辊压机两次层压，得到厚度110um的电极。
实施例10
石墨、乙炔黑、聚偏氟乙烯按照85:10:5的质量份数比分别筛分、干燥，预混合100分钟，加入电极材料总质量20％质量比的丙酮，造粒30分钟，分级过筛，得到造粒料。静电发生器电压采用60KV，压缩空气压力采用0.7MPa，把造粒料喷涂到10um的铜网上，形成厚度100um的电极涂层。经辊压机一次层压，得到厚度80um的电极。
实施例11
钴酸锂、活性炭、乙炔黑、聚苯乙烯按照20:70:5:5的质量份数比分别筛分、干燥，预混合50分钟，加入电极材料总质量20％质量比的水，造粒20分钟，分级过筛，得到造粒料。静电发生器电压采用60KV，压缩空气压力采用0.7MPa，把造粒料喷涂到10um的铝箔上，形成厚度120um的电极涂层。经辊压机一次层压，得到厚度90um的电极。
实施例12
石墨、硅、乙炔黑、聚偏氟乙烯按照80:10:7:3的质量份数比分别筛分、干燥，预混合100分钟，加入电极材料总质量20％质量比的丙醇，造粒30分钟，分级过筛，得到造粒料。静电发生器电压采用60KV，压缩空气压力采用0.7MPa，把造粒料喷涂到10um的铜网上，形成厚度100um的电极涂层。在铜网另一侧同样喷涂制作电极涂层。经辊压机两次层压，得到厚度150um的电极。
本发明的方法制造的电极，压实密度一致性远远优于其他工艺制造的电极。图7(a)是一电化学电源的电极结构示意图，其中38为集流体，71为电极涂层。图7(b)是采用本发明的方法制造的电极密度示意图。其中，曲线b1为层压前的电极密度，曲线b2为层压后的电极密度。采用本发明提供的方法制造电极，造粒料与集流体通过异性电荷吸引作用形成电极涂层。随着沉积在集流体上的造粒料越来越多，对喷涂过来的造粒料的电荷排斥作用增强，可吸附的造粒料减少，导致电极涂层离集流体越远越疏松。而在层压时，较为疏松的涂层表面直接与辊压机接触，受力最大，较为致密的涂层内部受力较小，所以层压后的电极涂层内外部密度基本一致。而采用其他方法制造的电极密度，如图7(c)所示，其中，曲线c1为层压前的电极密度，曲线c2为层压后的电极密度。因不存在电荷吸引和排斥作用，层压前的电 极涂层内外部密度基本一致，层压时同样涂层表面受力大于内部受力，导致层压后电极表面密度大于内部密度。这样的电极在注液时不利于电解液的渗透，影响电极性能。而本发明的方法电极压实密度一致性良好，解决了这一问题。
使用不同的活性物质材料可以制作相应的电极，分别用于不同类型的电化学电源。图8是一电化学电源的正负极结构示意图。正极集流体82上涂有电极涂层81，为电源正极。负极集流体84上涂有负极涂层83，为电源负极。正极和负极经隔膜85相对放置组成电芯，装配入壳后，注入电解液，组成电化学电源。电芯可以是叠片式、卷绕式等多种形式。相同或不同类型的电极组合可以构成多种电化学电源。可以举例如正负极都使用活性炭电极，组成超级电容器。再例如，正极使用活性炭电极，负极使用钛酸锂电极，组成混合电容器。
本发明公开和提出的一种电化学电源用电极的制造方法，本领域技术人员可通过借鉴本文内容，适当改变条件路线等环节实现，尽管本发明的方法和制备技术已通过较佳实施例子进行了描述，相关技术人员明显能在不脱离本发明内容、精神和范围内对本文所述的方法和技术路线进行改动或重新组合，来实现最终的制备技术。特别需要指出的是，所有相类似的替换和改动对本领域技术人员来说是显而易见的，他们都被视为包括在本发明精神、范围和内容中。

Claims (10)

  1. 一种电化学电源用电极的制造方法，其特征是包括以下步骤：
    1)、造粒：将活性物质、导电剂和粘结剂分别筛分、干燥后进行预混合，然后造粒，得到造粒料；
    2)、静电喷涂：造粒料经静电喷涂，形成带有电荷的高速粒子流，沉积吸附在带有相反电荷的集流体上，形成电极涂层；
    3)、层压：对附有电极涂层的集流体进行层压。
  2. 如权利要求1所述的方法，其特征是所述活性物质、导电剂和粘结剂的质量份数比为80～97：0.1～15：1～15。
  3. 如权利要求1所述的方法，其特征是所述活性物质包括活性炭、碳纳米管、石墨烯、碳气凝胶、活性炭纤维、石墨、硅、金属氧化物、含锂化合物中的一种或几种。
  4. 如权利要求1所述的方法，其特征是所述导电剂包括石墨、碳黑、乙炔黑、碳纳米管、碳纤维、金属纤维中的一种或几种。
  5. 如权利要求1所述的方法，其特征是所述粘结剂包括含氟聚合物、烯烃聚合物、聚碳酸酯、丙烯酸树脂、丁苯橡胶和羧甲基纤维素中的一种或几种。
  6. 如权利要求1所述的方法，其特征是所述步骤1)造粒过程是：造粒筛分目数是10～200目；干燥温度是20～200℃；造粒料的粒径是5～90um。
  7. 如权利要求1所述的方法，其特征是所述造粒过程加入桥连液体；桥连液体是水、有机溶剂中的一种或混合物；桥连液体的质量占活性物质、导电剂和粘结剂总质量的0.1～30％。
  8. 如权利要求1所述的方法，其特征是所述步骤2)静电喷涂的电压是30～90KV；所述高速粒子流的载气是压缩气体；压缩气体是空气或惰性气体；压缩气体的压力是0.6～0.8MPa。
  9. 如权利要求1所述的方法，其特征是所述步骤2)集流体包括铝箔、铜箔、镍箔、不锈钢、铝网、铜网、镍网或不锈钢网。
  10. 如权利要求1所述的方法，其特征是所述步骤3)层压次数是1～5次；每次电极涂层厚度减少量是5～30％。
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