WO2014111036A1

WO2014111036A1 - Production of porous electrode, production of electrochemical energy storing device, and production of combination of electrochemical energy storing devices

Info

Publication number: WO2014111036A1
Application number: PCT/CN2014/070777
Authority: WO
Inventors: 陈永胜; 侯栋; 马春印
Original assignee: 天津普兰纳米科技有限公司
Priority date: 2013-01-21
Filing date: 2014-01-17
Publication date: 2014-07-24
Also published as: CN104969385A

Abstract

Disclosed are a method for producing a porous electrode and the porous electrode produced by using the method, a method for producing an electrochemical energy storing device and the electrochemical energy storing device produced by using the method, and a method for producing a combination of the electrochemical energy storing devices and the combination of the electrochemical energy storing devices produced by using the method.

Description

Porous electrode preparation, electrochemical energy storage device preparation, and chemical energy storage device assembly preparation

The present disclosure relates to the field of electrochemistry. In particular, the present disclosure relates to a method of preparing a porous electrode, a porous electrode prepared by the method, a method of preparing an electrochemical energy storage device, an electrochemical energy storage device prepared by the method, and a method of preparing a chemical energy storage device assembly, and A chemical energy storage device assembly prepared by this method. Background

Electrochemical power sources have been widely used as energy storage electrical components. With the development of China's power supply industry, the demand for electrochemical power supplies is increasing, and its performance requirements are getting higher and higher. Supercapacitor is a new type of charge storage component. Compared with general batteries, it has the advantages of large capacity, support for large current charge and discharge, long cycle life and environmental pollution, and can provide fast energy release and meet high power requirements. Therefore, supercapacitors have broad application prospects in the fields of new energy, transportation, and industry. It has been used in wind power, solar power, hybrid vehicles, UPS, subway, elevator, robot automation and other applications.

The commonly used supercapacitor comprises a metal casing, a core and a cover plate which are open at one end and closed at the other end, wherein the closed end of the metal casing extends outward to form a pole, and the exterior of the metal casing is covered with an insulating material. The core is generally used for rolling groove and laser welding or ultrasonic welding technology, the process is relatively complicated and the cost is high.

In actual use, a single supercapacitor cannot meet the requirements of high output and high energy density devices, and multiple supercapacitor cells need to be constructed in series or in parallel to form an ultracapacitor bank. At the same time, in order to ensure that the supercapacitor combination can be applied in different occasions, especially in the state where vibration is applied, it is necessary to fix the supercapacitor unit constituting the assembly to have seismic performance to avoid structural damage, for example, The current collector is broken, the current collector welded portion is broken, and the single dielectric connecting piece is broken.

In the assembled battery, the prominent problem of connecting the single cells in series is the fluctuation between the individual cells. If batteries of different capacities are connected in series, in the fully charged state of the assembled battery, there are battery cells having a voltage higher than the average voltage or battery cells having a lower average voltage, thereby causing degradation of the performance of the high voltage battery cells. In addition, during the assembly process, along with the battery cells The increase in the number, in the process of large current discharge, due to the heating of the battery cells, the accumulation of heat in the battery pack, resulting in battery expansion and other adverse consequences. Overview

One aspect of the present disclosure relates to a method of producing a porous electrode, comprising: kneading an active material, a binder, a conductive agent, and a small amount of a solvent to form a micelle; rolling the micelle to form an active material film Forming a conductive coating on the current collector by the conductive paste; and thermocompression bonding the active material film and the current collector forming the conductive coating.

Another aspect of the present disclosure relates to a porous electrode which is prepared by: kneading an active material, a binder, a conductive agent, and a small amount of a solvent to form a micelle; rolling the micelle to form an active material a film; forming a conductive coating on the current collector by the conductive paste; and thermocompression bonding the active material film and the current collector forming the conductive coating.

One aspect of the present disclosure relates to a method of preparing a chemical energy storage device, comprising: (1) providing a porous electrode; (2) preparing a core of a chemical energy storage device using the porous electrode; and (3) assembling using the core a chemical storage device; wherein the method for preparing the porous electrode comprises: kneading an active material, a binder, a conductive agent and a small amount of solvent to form a micelle; rolling the micelle to form an activity a material film; forming a conductive coating on the current collector by the conductive paste; and thermocompression bonding the active material film and the current collector forming the conductive coating.

Another aspect of the present disclosure relates to a chemical energy storage device prepared by: (1) providing a porous electrode; (2) preparing a core of a chemical energy storage device using the porous electrode; and (3) using the core The chemical storage device is assembled; wherein the method for preparing the porous electrode comprises: kneading an active material, a binder, a conductive agent and a small amount of solvent to form a micelle; rolling the micelle to form An active material film; forming a conductive coating on the current collector by the conductive paste; and thermocompression bonding the active material film and the current collector forming the conductive coating.

One aspect of the present disclosure relates to a method of preparing a chemical energy storage device assembly, comprising: (1) providing a porous electrode; (2) preparing a core of a chemical energy storage device using the porous electrode; (3) using the core Assembling a chemical energy storage device monomer; and (4) fixing a plurality of the chemical energy storage device monomers in a support body, and connecting a plurality of the chemical energy storage device monomers through a connection piece in series or in parallel, thereby obtaining a combined chemical energy storage device; wherein, the porous electricity is prepared The polar method comprises: kneading an active material, a binder, a conductive agent and a small amount of solvent to form a micelle; rolling the micelle to form an active material film; forming a conductive paste on the current collector a conductive coating; and thermocompression bonding the active material film and the current collector forming the conductive coating.

Another aspect of the present disclosure relates to a chemical energy storage device assembly prepared by the following method:

(1) providing a porous electrode; (2) preparing a core of a chemical energy storage device using the porous electrode; (3) assembling a chemical energy storage device monomer using the core; and (4) using the plurality of the chemistry The energy storage device unit is fixed in the support body, and a plurality of the chemical energy storage device monomers are connected in series or in parallel through the connecting piece, thereby obtaining a combined chemical energy storage device; wherein the method for preparing the porous electrode comprises: The active material, the binder, the conductive agent and a small amount of solvent are kneaded to form a micelle; the micelle is rolled to form an active material film; the conductive paste is formed on the current collector to form a conductive coating; The active material film and the current collector forming the conductive coating are subjected to hot press bonding. BRIEF DESCRIPTION OF THE DRAWINGS

1 is a schematic flow chart of preparing a porous electrode according to an embodiment of the present disclosure.

2 is a schematic view showing the principle of a mixing apparatus used in an embodiment of the present disclosure.

3 is a schematic diagram of the principle of a production line used in an embodiment of the present disclosure.

4 is a scanning electron micrograph of a pole piece according to an embodiment of the present disclosure.

FIG. 5 is a scanning electron micrograph of a pole piece according to an embodiment of the present disclosure.

6 is a scanning electron micrograph of a pole piece according to an embodiment of the present disclosure.

Figure 7 is a scanning electron micrograph of a pole piece according to an embodiment of the present disclosure.

Figure 8 is a schematic flow chart of a winding core according to an embodiment of the present disclosure.

Fig. 9 is a schematic view showing the structure of a circular supercapacitor of a positive and negative electrode of a positive and negative electrode according to an embodiment of the present disclosure.

Fig. 10 is a partially enlarged plan view showing a top cover of a circular supercapacitor unit according to an embodiment of the present disclosure.

Fig. 11 is a structural schematic view showing a circular supercapacitor unit of the same end of the positive and negative electrodes according to an embodiment of the present disclosure.

FIG. 12 is a schematic overall view of a 3*6 size supercapacitor assembly according to an embodiment of the present disclosure. Fig. 13 is a schematic view showing the internal structure of a 3*6 size supercapacitor assembly according to an embodiment of the present disclosure. Detailed

In the following description, certain specific details are included in the description of the various embodiments. However, one skilled in the relevant art will recognize that the embodiments may be practiced without the use of one or more of these specific details and other methods, components, materials, and the like.

Unless otherwise required in this application, the words "including" and "comprising" are intended to be interpreted as an open, inclusive meaning, that is, "including but not limited to".

The word "one embodiment" or "an embodiment" or "in another embodiment" or "in some embodiments" as referred to throughout the specification is meant to include in at least one embodiment with the embodiment. Relevant specific reference elements, structures or features described. Thus, appearances of the phrases "in an embodiment" or "in an embodiment" or "in another embodiment" or "in some embodiments" are not necessarily referring to the same embodiment. Furthermore, the specific elements, structures, or characteristics may be combined in any suitable manner in one or more embodiments. Definition

Therefore, unless otherwise stated to the contrary, the following terms used in the specification and the appended claims have the following meanings:

In the present disclosure, the term "porous electrode" means an electrode which is deposited by small particles into a porous structure to facilitate material reaction and transfer.

In the present disclosure, the term "active substance" means a relatively active element or compound.

In the present disclosure, the term "binder" means a substance which can be added to a powder to be removed before or during sintering in order to increase the strength of the green compact or prevent powder segregation.

In the present disclosure, the term "conductive agent" means that in order to ensure good charge and discharge performance of the electrode, a certain amount of conductive material is usually added during the production of the pole piece, which is between the active material and the active material and the current collector. To collect the effect of microcurrent to reduce the connection of the electrodes The contact resistance accelerates the rate of movement of electrons, and at the same time, it can effectively increase the migration rate of ions in the electrode material, thereby improving the charge and discharge efficiency of the electrode.

In the present disclosure, the term "solvent" means a liquid which can dissolve a solid, liquid or gaseous solute.

In the present disclosure, the term "kneading" refers to a process in which various compounding agents (mainly active materials) and materials having plasticity are mixed together.

In the present disclosure, the term "conductive paste" means an adhesive having a certain electrical conductivity after curing or drying.

In the present disclosure, the term "current collector" refers to a structure or part that collects current, the function of which is mainly to collect currents generated by the battery active material to form a large current output.

In the present disclosure, the term "powder form" means fine particles composed of dry, dispersed solid particles. detailed description

In certain embodiments, the active material is in powder form.

Illustrative examples of active materials that can be used in the present disclosure include, but are not limited to, activated carbon, graphene, modified graphene materials, activated carbon and graphene composites, mesocarbon microbeads, natural graphite, modified graphite, coated graphite. , carbon nanofibers, carbon nanotubes, coke, lithium-containing anode materials used in silicon cells.

In certain embodiments, the binder is in the form of a powder. In certain embodiments the binder is in the form of an ultrafine powder. In certain embodiments, the binder has a particle size of from 0.2 to 2 μηι.

Illustrative examples of binders that can be used in the present disclosure include, but are not limited to, polyacrylic acid, decyl methacrylate, polytetrafluoroethylene, polyvinylidene fluoride, styrene butadiene rubber, and carboxymethyl cellulose. In certain embodiments, the electrically conductive agent is in the form of a powder.

Illustrative examples of the conductive agent that can be used in the present disclosure include, but are not limited to, acetylene black, conductive fibers, and wires.

Illustrative examples of solvents that can be used in the present disclosure include, but are not limited to, water, liquid organic solvents, and inorganic mineral oils.

Illustrative examples of the kneading method that can be used in the present disclosure include, but are not limited to, open-type kneading, dense kneading, frame agitation kneading, or anchor agitation kneading.

In certain embodiments, the compounding process is carried out for about 5 to 300 minutes. In certain embodiments, the compounding process is carried out for about 30 to 120 minutes. In certain embodiments, the mixing process is carried out for about 60 minutes.

In certain embodiments, the kneaded micelles are rolled using a cold rolling process, thereby eliminating the need for any heating or auxiliary heating processes.

In certain embodiments, the kneaded micelles are subjected to multiple rolling to form a continuous active film. In certain embodiments, the kneaded micelles are subjected to two roll presses using a roll press to form a continuous active film.

In some embodiments, the kneaded micelles are rolled to obtain a single layer of active material film.

Illustrative examples of current collectors that can be used in the present disclosure include, but are not limited to, copper foil, aluminum foil, and a conductive polymer film having a viscosity.

In certain embodiments, the conductive coating is formed by a micro transfer coating process.

In certain embodiments, the amount of solvent is from about 3% to 50% by mass based on the total mass of the electrode constituent materials. In certain embodiments, the amount of solvent is from about 3% to 30% by mass based on the total mass of the electrode constituent materials. In certain embodiments, the amount of solvent is from about 5% to 10% by mass based on the total mass of the electrode constituent materials.

In certain embodiments, based on the total mass of the electrode constituent materials, the active material is about

50% to 98% by mass. In certain embodiments, the active material is from about 80% to 98% by mass based on the total mass of the electrode constituent materials. In certain embodiments, the active material is from about 90% to 98% by mass based on the total mass of the electrode constituent materials.

In certain embodiments, the binder is from about 0.1% to 20% by mass based on the total mass of the electrode constituent materials. In certain embodiments, the binder is from about 1% to 10% by mass based on the total mass of the electrode constituent materials. In certain embodiments, based on electrode composition The total mass of the binder, the binder is about 1% to 6% by mass.

In certain embodiments, based on the total mass of the electrode constituent materials, the conductive agent is about

0.1% to 30% by mass. In certain embodiments, the conductive agent is from about 1% to 15% by mass based on the total mass of the electrode constituent materials. In certain embodiments, the conductive agent is from about 3% to 6% by mass based on the total mass of the electrode constituents.

In some embodiments, the active material film and the conductive paste are both in a semi-dry state, so that after the hot press compounding, the active material film and the solvent in the conductive paste are volatilized to form a dried finished porous electrode. The production of pole pieces, the production of fuel cell pole pieces and other flexible porous electrodes in the production process.

Large-scale production can be carried out by using the method of the present disclosure, and the roll-pressing film process is carried out under normal temperature and normal pressure, the production speed is fast, the production energy consumption is small, and the manufacturing cost is low.

In certain embodiments, the active material is in powder form.

In certain embodiments, the binder is in the form of a powder. In certain embodiments the binder is in the form of an ultrafine powder. In certain embodiments, the particle size of the binder is 0.2 to 2 μηι.

Illustrative examples of binders that can be used in the present disclosure include, but are not limited to, polydecylacrylic acid, decyl decyl acrylate, polytetrafluoroethylene, polyvinylidene fluoride, styrene butadiene rubber, and carboxy fluorenyl cellulose.

In certain embodiments, the electrically conductive agent is in the form of a powder.

In certain embodiments, based on the total mass of the electrode constituent materials, the amount of solvent is about

3% to 50% by mass. In certain embodiments, the amount of solvent is from about 3% to 30% by mass based on the total mass of the electrode constituent materials. In certain embodiments, the amount of solvent is from about 5% to 10% by mass based on the total mass of the electrode constituent materials.

In certain embodiments, the active material is from about 50% to 98% by mass based on the total mass of the electrode constituent materials. In certain embodiments, the active material is from about 80% to 98% by mass based on the total mass of the electrode constituent materials. In certain embodiments, based on electrode composition The total mass of the substance, the active substance is about 90% to 98% by mass.

In certain embodiments, based on the total mass of the electrode constituent materials, the binder is about

0.1% to 20% by mass. In certain embodiments, the binder is from about 1% to 10% by mass based on the total mass of the electrode constituent materials. In certain embodiments, the binder is from about 1% to about 6% by mass based on the total mass of the electrode constituents.

In certain embodiments, the conductive agent is from about 0.1% to 30% by mass based on the total mass of the electrode constituent materials. In certain embodiments, the conductive agent is from about 1% to 15% by mass based on the total mass of the electrode constituent materials. In certain embodiments, the conductive agent is from about 3% to 6% by mass based on the total mass of the electrode constituents.

In some embodiments, the active material film and the conductive paste are both in a semi-dry state, so that after the hot press compounding, the active material film and the solvent in the conductive paste are volatilized to form a dried finished porous electrode.

In certain embodiments, the prepared porous electrodes are used as a positive electrode tab and a negative electrode tab, respectively.

In certain embodiments, two layers of separator are alternately spaced between the positive and negative sheets and wound together into a cylindrical core.

In certain embodiments, the positive and negative sheets have a foil length of from 1 mm to 20 mm. In certain embodiments, the positive and negative sheets have a foil length of 7 mm.

In some embodiments, the positive electrode leaving foil and the negative electrode leaving foil are formed by shaping, leaving the foil bent and concentrated.

In certain embodiments, the height of the core in the chemical energy storage device is in a wire-controlled manner to ensure a consistent core height in the fabricated chemical energy storage device.

In certain embodiments, the core is assembled in a metal housing that is open at both ends to assemble the chemical energy storage device.

In certain embodiments, the positive and negative electrode sheets employ a hetero-end structure or a homo-end structure. In some embodiments, when the positive electrode tab and the negative electrode tab are in an opposite-end configuration, the core is separately welded to the upper current collector and the lower current collector, and the upper current collector and the lower current collector are respectively coupled to the pole The column is welded to the metal housing.

In certain embodiments, when the positive and negative sheets are of the same end configuration, the core is separately welded to the upper current collector and the lower current collector, and the upper current collector and the lower current collector are respectively welded to the poles. In some embodiments, the metal housing is interference fit and welded to the upper and lower covers, respectively.

In some embodiments, when the positive electrode tab and the negative electrode tab have the same end structure, the large separation between the lower current collector and the lower cover is 1 mm to 5 mm, preferably 1.5 mm.

In certain embodiments, there is an insulating spacer and a Type 0 gasket between the upper cover and the post.

In some embodiments, when the positive and negative sheets are of the same end configuration, there is an insulating spacer and a 0-type gasket between the lower cover and the post.

In some embodiments, the nut is secured between the pole drawn from the upper cover and the upper cover.

In some embodiments, when the positive and negative plates are of the same end configuration, the nut is secured between the pole and the lower cover from which the lower cover is drawn.

Exemplary materials that can be used with the Type 0 gasket of the present disclosure include, but are not limited to, ethylene propylene diene monomer (EPDM) and fluorosilica.

In certain embodiments, the Type 0 gasket has a diameter of from 1 111111 to 3 111111. In some embodiments, the Type 0 gasket has a diameter of 1.78 mm.

Insulating gasket materials that can be used in the present disclosure include, but are not limited to, polypropylene (PP).

Welding methods that can be used in the present disclosure include, but are not limited to, laser welding and ultrasonic welding.

Large-scale production can be carried out by using the method of the present disclosure, and the roll-pressing film process is carried out under normal temperature and normal pressure, the production speed is fast, the production energy consumption is small, and the manufacturing cost is low. In addition, the outer casing of the chemical energy storage device adopts the form of opening at both ends, and the design and assembly process are relatively simple, and the cost is low, and can be applied to large-scale production of supercapacitors and lithium ion batteries.

One aspect of the present disclosure relates to a method of preparing a chemical energy storage device assembly, comprising: (1) Providing a porous electrode; (2) preparing a core of a chemical energy storage device using the porous electrode; (3) assembling a chemical energy storage device monomer using the core; and (4) using the plurality of chemical energy storage devices The monomer is fixed in the support, and a plurality of the chemical energy storage device monomers are connected in series or in parallel through the connecting piece, thereby obtaining a combined chemical energy storage device; wherein the method for preparing the porous electrode comprises: The binder, the conductive agent and a small amount of solvent are kneaded to form a micelle; the micelle is rolled to form an active material film; the conductive paste is formed on the current collector to form a conductive coating; and the activity is The material film and the current collector forming the conductive coating are subjected to hot press bonding.

In certain embodiments, the active material is in powder form.

In certain embodiments, the kneaded micelles are rolled using a cold rolling process, This eliminates the need for any heating or auxiliary heating processes.

In certain embodiments, the active material is from about 50% to 98% by mass based on the total mass of the electrode constituent materials. In certain embodiments, the active material is from about 80% to 98% by mass based on the total mass of the electrode constituent materials. In certain embodiments, the active material is from about 90% to 98% by mass based on the total mass of the electrode constituent materials.

In certain embodiments, the binder is from about 0.1% to 20% by mass based on the total mass of the electrode constituent materials. In certain embodiments, the binder is from about 1% to 10% by mass based on the total mass of the electrode constituent materials. In certain embodiments, the binder is from about 1% to about 6% by mass based on the total mass of the electrode constituents.

In certain embodiments, two separators are alternately spaced in the positive and negative sheets, Coiled together into a cylindrical core.

In some embodiments, when the positive and negative sheets are of the same end configuration, the core is separately welded to the upper and lower current collectors, and the upper and lower current collectors are respectively welded to the poles.

In some embodiments, the metal housing is interference fit and welded to the upper and lower covers, respectively.

In some embodiments, when the positive electrode tab and the negative electrode tab have the same end structure, the distance between the lower current collector and the lower cover is 1 mm to 5 mm, preferably 1.5 mm.

In certain embodiments, the Type 0 gasket has a diameter of 1 111111 to 3 111111. In a certain In some embodiments, the Type 0 gasket has a diameter of 1.78 mm.

In certain embodiments, the chemical energy storage device assembly and the equalization circuit board are placed within the housing.

Illustrative examples of housings that can be used with the present disclosure include, but are not limited to, aluminum housings. In certain embodiments, the inner wall of the outer casing is covered with an insulating plate. In certain embodiments, the inner wall of the outer casing is covered with an epoxy insulating sheet.

Illustrative examples of supports that can be used in the present disclosure include, but are not limited to, aluminum supports.

Illustrative examples of tabs that can be used in the present disclosure include, but are not limited to, copper tabs. Specifications of supports that can be used in the present disclosure include, but are not limited to, 3*4 and 3*6 for placing 12 or 18 supercapacitor cells. To meet the demand, it is also possible to set up a support for more supercapacitor cells.

(1) providing a porous electrode; (2) preparing a core of a chemical energy storage device using the porous electrode; (3) assembling a chemical energy storage device monomer using the core; and (4) using the plurality of the chemistry The energy storage device unit is fixed in the support body, and a plurality of the chemical energy storage device monomers are connected in series or in parallel through the connecting piece, thereby obtaining a combined chemical energy storage device; wherein the method for preparing the porous electrode comprises: The active material, the binder, the conductive agent and a small amount of solvent are kneaded to form a micelle; the micelle is rolled to form an active material film; the conductive paste is formed on the current collector to form a conductive coating; The active material film and the current collector forming the conductive coating are subjected to hot press bonding. Hereinafter, the present disclosure will be explained in detail by the following examples in order to better understand the various aspects of the present disclosure and the advantages thereof. However, it should be understood that the following implementation The examples are non-limiting and are merely illustrative of certain embodiments of the invention. Example

I. Preparation of porous electrode

Activated carbon produced by Japan Kuraray Co., Ltd. as an active material, and its specific surface area is

1300 to 1500 m ² /g, D ₅ . It is 10 μηι.

The graphene produced by Tianjin Pulan Nano Technology Co., Ltd. is mainly a single layer of graphene with a purity of more than 95%.

The mesophase carbon microspheres produced by Betray have a mass specific capacity of about 300 mAh/g and a low irreversible specific capacity of about 20 mAh/g.

Using lithium titanate produced by Tianjin Pulan Nano Technology Co., Ltd., the specific capacity of 1 C is about 155 mAh/g, and the purity is over 99%.

Using graphene-modified lithium titanate produced by Tianjin Pulan Nano Technology Co., Ltd., the specific capacity of 1C is about 165mAh/g, and the purity is over 99%.

The polydecyl methacrylate granules produced by Arkema were used as a binder, which was 0 ₅ . for

0.25 μηι.

Super Ρ manufactured by Changzhou Trioco Co., Ltd. is used as a conductive agent.

EB012 produced by Henkel was used as the conductive paste.

Referring to Figure 2, there is shown a schematic diagram of a mixing apparatus used in an embodiment of the present disclosure, wherein 1 is a motor; 22 is a reduction gearbox; 23 is a transmission gear; and 24 is a mixing roller.

3, which is a schematic diagram of a production line used in an embodiment of the present disclosure, wherein 1 is a finished electrode; 16 is a current collector; 20 is a composite step; 31 is a loading machine; 32 is a single rolling step; One dry film step; 34 is a secondary rolling step; 35 is an auxiliary nozzle; 36 is a back roll; 37 is a printing roll; 39 is a secondary dry film step. Example 1

The activated carbon produced by Kuraray, the polydecyl acrylate granules produced by Arkema, and the Super P produced by Changzhou Temco are weighed by mass, and the mass ratio is 95:2:3, based on the total electrode material. The mass is 10% by mass of water, the above materials are mixed by open-mixing, and the mixing process is carried out for 60 minutes to obtain 1 kg of micelles; the formed micelles are subjected to cold rolling mill rolling to form an active material film; Using copper foil as the current collector, using micro transfer coating The epoxy conductive adhesive EB012 is coated on the copper foil to form a conductive coating; the obtained active material film and the copper foil forming the conductive coating are hot-pressed, and the solvent in the active material film and the conductive paste is volatilized. When completed, a dry porous electrode is formed.

Fig. 4 is a scanning electron micrograph of the obtained porous electrode sheet. Example 2

The activated carbon produced by Kuraray, the polydecyl acrylate granules produced by Arkema, and the Super P produced by Changzhou Temco are weighed by mass, and the mass ratio is 94:3:3, based on the total electrode material. The mass is 10% by mass of water, the above materials are mixed by open-mixing, and the mixing process is carried out for 100 minutes to obtain a lkg of micelles; the formed micelles are subjected to cold rolling mill rolling to form an active material film; The copper foil is used as a current collector, and the aqueous conductive adhesive EB012 is coated on the copper foil by a micro-transfer coating method to form a conductive coating; the obtained active material film and the copper foil forming the conductive coating are hot-pressed, After the solvent in the active material film and the conductive paste is volatilized, a dry porous electrode is formed.

The scanning electron micrograph of the porous electrode sheet obtained in this example was similar to that of Example 1. Example 3

The activated carbon produced by Kuraray, the polydecyl acrylate granules produced by Arkema, and the Super P produced by Changzhou Temco are weighed by mass, the mass ratio is 90:3:7, based on the total electrode material. The mass is 15% by mass of water, the above materials are mixed by open-mixing, and the mixing process is carried out for 30 minutes to obtain 2 kg of micelles; the formed micelles are subjected to cold rolling mill rolling to form an active material film; The copper foil is used as a current collector, and the aqueous conductive adhesive EB012 is coated on the copper foil by a micro-transfer coating method to form a conductive coating; the obtained active material film and the copper foil forming the conductive coating are hot-pressed, After the solvent in the active material film and the conductive paste is volatilized, a dry porous electrode is formed.

The scanning electron micrograph of the porous electrode sheet obtained in this example was similar to that of Example 1. Example 4

The graphene produced by Tianjin Pulan Nano Technology Co., Ltd., the polydecyl acrylate acrylate particles produced by Arkema, and the Super P produced by Changzhou Temico Co., Ltd. are weighed by mass, and the mass ratio is 95:2:3, based on The total mass of the electrode material, add 10% by mass of water to The upper material is subjected to open-mixing mixing, and the mixing process is carried out for 60 minutes to obtain 0.5 kg of micelles; the formed micelles are subjected to cold rolling mill rolling to form an active material film; copper foil is used as a current collector, and a trace amount is used. The aqueous conductive adhesive EB012 is coated on the copper foil by a transfer coating method to form a conductive coating; the obtained active material film and the copper foil forming the conductive coating are hot-pressed and composited, and are in the active material film and the conductive adhesive. After the solvent is volatilized, a dry porous electrode is formed.

Fig. 5 is a scanning electron micrograph of the obtained porous electrode sheet. Example 5

The graphene produced by Tianjin Pulan Nano Technology Co., Ltd., the polytetrafluoroethylene particles produced by Arkema, and the Super P produced by Changzhou Temico Co., Ltd. are weighed by mass, and the mass ratio is 90:2:8, based on the electrode material. The total mass, 10% by mass of water is added, the above materials are mixed by open-mixing, and the mixing process is carried out for 120 minutes to obtain 0.5 kg of micelles; the formed micelles are subjected to cold rolling mill rolling to form active a material film; using an aluminum foil as a current collector, applying an aqueous conductive adhesive EB012 on an aluminum foil by a micro-transfer coating method to form a conductive coating; and subjecting the obtained active material film and the aluminum foil forming the conductive coating to hot pressing, After the solvent in the active material film and the conductive paste is volatilized, a dry porous electrode is formed.

The scanning electron micrograph of the porous electrode sheet obtained in this example was similar to that of Example 4. Example 6

The modified graphene produced by Tianjin Pulan Nano Technology Co., Ltd., the polydecyl methacrylate granules produced by Arkema, and the Super P produced by Changzhou Temico Co., Ltd. are weighed by mass, and the mass ratio is 90:5:5. , based on the total mass of the electrode material, adding 10% by mass of water, the above materials are mixed by open-mixing, and the mixing process is carried out for 30 minutes to obtain 2 kg of micelles; the formed micelles are subjected to cold rolling mill rolling Forming an active material film; using a copper foil as a current collector, coating the aqueous conductive adhesive EB012 on the copper foil by a micro transfer coating method to form a conductive coating; and obtaining the active material film and the copper forming the conductive coating The foil is subjected to hot press lamination, and after the solvent in the active material film and the conductive paste is volatilized, a dry porous electrode is formed.

The scanning electron micrograph of the porous electrode sheet obtained in this example was similar to that of Example 4. Example 7

Modified graphene and Arkema produced by Tianjin Pulan Nano Technology Co., Ltd. The polymethyl methacrylate particles and the Super P produced by Changzhou Trimco Company are weighed by mass, and the mass ratio is 90:5:5. Based on the total mass of the electrode material, 20% by mass of ethanol is added, and the above substances are used. The mixing process is carried out for 30 minutes to obtain a lkg of micelles; the formed micelles are subjected to cold rolling mill rolling to form an active material film; copper foil is used as a current collector, and a micro-transfer coating method is used. The aqueous conductive adhesive EB012 is coated on the copper foil to form a conductive coating; the obtained active material film and the copper foil forming the conductive coating are hot-pressed, and the solvent in the active material film and the conductive paste is volatilized. That is, a dry porous electrode is formed.

The scanning electron micrograph of the porous electrode sheet obtained in this example was similar to that of Example 4. Example 8

The mesocarbon microbeads produced by Betray, the polytetrafluoroethylene particles produced by Arkema, and the Super P produced by Changzhou Temco are weighed by mass, and the mass ratio is 90:1:9, based on the electrode material. The total mass is 10% by mass of water, the above materials are mixed and mixed, and the mixing process is carried out for 60 minutes to obtain 5 kg of micelles; the formed micelles are subjected to cold rolling mill rolling to form active materials. Film; using copper foil as a current collector, coating the aqueous conductive adhesive EB012 on the copper foil by a micro-transfer coating method to form a conductive coating; and hot-pressing the obtained active material film and the copper foil forming the conductive coating After compounding, the solvent in the active material film and the conductive paste is volatilized to form a dry porous electrode.

The scanning electron micrograph of the porous electrode sheet obtained in this example was similar to that of Example 1. Example 9

The lithium titanate produced by Tianjin Pulan Nano Technology Co., Ltd., the polymethyl methacrylate particles produced by Arkema, and the acetylene black produced by Changzhou Temico Co., Ltd. are weighed by mass, and the mass ratio is 90:4:6. Based on the total mass of the electrode material, 10% by mass of water is added, the above materials are mixed and kneaded, and the mixing process is carried out for 60 minutes to obtain 0.2 kg of micelles; the formed micelles are subjected to cold rolling mill rolling Forming an active material film; using a copper foil as a current collector, coating the aqueous conductive adhesive EB012 on the copper foil by a micro transfer coating method to form a conductive coating; and obtaining the active material film and the copper forming the conductive coating The foil is subjected to hot press lamination, and after the solvent in the active material film and the conductive paste is volatilized, a dry porous electrode is formed.

Fig. 6 is a scanning electron micrograph of the obtained porous electrode sheet. Example 10

The graphene-modified lithium titanate produced by Tianjin Pulan Nano Technology Co., Ltd., the polydecyl methacrylate granules produced by Arkema, and the Super P produced by Changzhou Temico Co., Ltd. are weighed by mass, and the mass ratio is 95: 3:2, based on the total mass of the electrode material, adding 14% by mass of water, the above materials are mixed and mixed, and the mixing process is carried out for 60 minutes to obtain a lkg of micelle; the formed micelle is cold rolled. Rolling the machine to form an active material film; using a copper foil as a current collector, applying an aqueous conductive adhesive EB012 on the copper foil by a micro transfer coating method to form a conductive coating; and obtaining the active material film and forming a conductive coating The copper foil of the layer is subjected to hot press lamination, and the solvent in the active material film and the conductive paste is volatilized to form a dry multi-electrode.

Fig. 7 is a scanning electron micrograph of the obtained porous electrode sheet. Example 1 1

The graphene-modified lithium titanate produced by Tianjin Pulan Nano Technology Co., Ltd., the polytetrafluoroethylene particles produced by Arkema, and the Super P produced by Changzhou Temico Co., Ltd. are weighed by mass, and the mass ratio is 95:3: 2, based on the total mass of the electrode material, adding 14% by mass of water, the above materials are mixed and mixed, and the mixing process is carried out for 60 minutes to obtain a lkg of micelle; the formed micelle is subjected to a cold rolling mill roll. Pressing, forming an active material film; using a copper foil as a current collector, coating the aqueous conductive adhesive EB012 on the copper foil by a micro transfer coating method to form a conductive coating; and obtaining the active material film and forming a conductive coating layer The copper foil is subjected to hot press lamination, and after the solvent in the active material film and the conductive paste is volatilized, a dry porous electrode is formed.

The scanning electron micrograph of the porous electrode sheet obtained in this example was similar to that of Example 10. Example 12

The graphene produced by Tianjin Pulan Nano Technology Co., Ltd., the polytetrafluoroethylene particles produced by Arkema, and the Super P produced by Changzhou Temico Co., Ltd. are weighed by mass, and the mass ratio is 92:3:5, based on the electrode material. The total mass, 14% by mass of water is added, the above materials are mixed and mixed, and the mixing process is carried out for 60 minutes to obtain 0.2 kg of micelles; the formed micelles are subjected to cold rolling mill rolling to form active a material film; using a copper foil as a current collector, coating the aqueous conductive adhesive EB012 on the copper foil by a micro transfer coating method to form a conductive coating; and heating the obtained active material film and the copper foil forming the conductive coating Compressive compound, to be alive The solvent in the material film and the conductive paste is evaporated, that is, a dry porous electrode is formed.

The scanning electron micrograph of the porous electrode sheet obtained in this example was similar to that of Example 4.

II. Preparation of supercapacitor core

The prepared porous electrodes were respectively used as a positive electrode sheet and a negative electrode sheet, and two separators were alternately spaced in the positive electrode sheet and the negative electrode sheet, and wound up by a winder manufactured by Zhuhai Huaguan Electronic Technology Co., Ltd. (HFW-4570) to form a cylinder. The shape of the core, the positive electrode and the negative electrode have a foil length of 10 mm. By shaping, the foil is bent and concentrated to form a positive electrode leaving foil and a negative electrode leaving foil. The height of the supercapacitor core is wire-controlled, ensuring a consistent height of the prepared supercapacitor core.

III. Preparation of supercapacitor monomer

For the form of the positive and negative ends, refer to Figures 6 and 7.

First, the core 2 is welded to the upper current collector 3 and the lower current collector 4, respectively, into the casing 1, the lower current collector 4 is welded to the casing 1, and the lower cover 6 is interference-fitted and welded to the casing 1, wherein There is a 3 mm gap between the lower current collector 4 and the lower cover 6. The upper current collector 3 is welded to the pole 7 and then the cover plate 5 is attached, and the pole 7 is led out, wherein the upper cover 5 and the pole 7 are separated by an insulating spacer 9 and a 0-type gasket 圏8, the upper cover The plate 5 is interference fit and welded to the housing 1. In order to ensure the tightness of the structure, the nut 10 is fixed between the pole 7 and the upper cover 5 of the upper cover 5, and the insulating spacer 9 is spaced. This design reduces the internal resistance of the supercapacitor and improves the current conduction performance of the supercapacitor.

For the form of the same end of the positive and negative poles, refer to Figure 8. The positive and negative electrodes have the same sealing structure.

First, the core 2 is welded to the upper current collector 3 and the lower current collector 3, respectively, into the casing 1, the upper current collector 3 is welded to the pole 7, and the cover 5 is attached, and the pole 7 is led out. The upper cover 5 and the pole 7 are separated by an insulating spacer 9 and a 0-type gasket 圏8, and the upper cover 5 is interference-fitted with the housing 1 and welded. In order to ensure the tightness of the structure, the nut 10 is fixed between the pole 7 drawn from the upper cover 5 and the upper cover 5, and the insulating spacer 9 is spaced. The lower current collector 3 is welded to the pole 7', the lower cover 5' is attached, and the pole 7' is taken out, and the same insulating spacer 9, and the 0-type gasket 圏8 are used. The lower cover 5 is in interference fit with the housing 1 and welded, the lower cover 5, the extracted pole 7 and the lower cover 5 are fixed with the nut 10, and the insulating spacer 9 is spaced apart. This The design structure can ensure that the housing is not charged, suitable for the combination of super capacitors, and is also suitable for assembly of circular lithium ion battery cells and assembly of lithium ion battery packs.

IV. Preparation of Supercapacitor Assembly

The supercapacitor assembly includes: an aluminum support 4; a plurality of circular supercapacitor cells 5 disposed in the support; an aluminum casing 2, the inner wall of which is covered by an insulating plate; and an equalization circuit board.

First, a plurality of supercapacitor cells 5 are fixed in the aluminum support 4 according to actual needs, and fixed by nuts, and the supercapacitor cells 5 are connected in series or in parallel to the assembly 1 through the copper tabs 6. A balanced circuit board is provided to control the charging and discharging of the supercapacitor assembly 1. The assembly 1 and the equalization circuit board are placed in an aluminum casing 2, and the positive and negative poles 3 are led out. The method of the present disclosure uses a small amount of solvent, and the solvent is completely volatilized during the preparation of the porous electrode, avoiding additional heat energy loss, and the production process is reduced, so that the production cost can be reduced and the productivity can be improved in the preparation process.

The outer casing of the electrochemical energy storage device of the present disclosure adopts the form of open ends, and the design and assembly process are relatively simple, and the cost is low, and can be applied to large-scale pipeline production of supercapacitors and lithium ion batteries. At the same time, the supercapacitor unit assembled in the same end of the positive and negative poles can ensure that the housing is not charged, suitable for the combination of super capacitors, and is also suitable for assembly of circular lithium ion battery cells and assembly of lithium ion battery packs. .

In addition, a plurality of electrochemical energy storage device monomers are fixed in the support body, so that the super-capacitor assembly has good seismic performance and can protect the electrochemical energy storage device unit from damage. At the same time, the equalization circuit and good heat dissipation performance attached to the assembly can ensure long-term stable operation of the assembly, and is suitable for large-scale application of the electrochemical energy storage device assembly. It is to be understood that the various embodiments of the present invention may be made by those skilled in the art without departing from the spirit and scope of the invention. Such variations or modifications are intended to fall within the scope of the appended claims.

Claims

claims

1. A method of preparing a porous electrode, which includes:

Mix the active material, binder, conductive agent and a small amount of solvent to form micelles; roll the micelles to form an active material film;

Apply conductive glue to form a conductive coating on the current collector; and

The active material film and the current collector forming the conductive coating are hot-pressed and combined.

2. The method of claim 1, wherein the active material is in powder form, and is preferably activated carbon, graphene, modified graphene materials, activated carbon and graphene composite materials, mesocarbon microspheres, natural graphite, Modified graphite, coated graphite, carbon nanofibers, carbon nanotubes, coke, silicon powder, silicon wire, lithium-containing positive electrode powder materials used in lithium-ion batteries, lithium-containing negative electrode powder used in lithium-ion batteries Materials and mixtures thereof.

3. The method of claim 1 or 2, wherein the binder is in powder form, preferably ultrafine powder form, and more preferably has a particle size of 0.2 to 2 μm, and the binder is preferably in the form of ultrafine powder Polymethacrylic acid, polymethylmethacrylate, polytetrafluoroethylene, polyvinylidene fluoride, styrene-butadiene rubber, carboxymethylcellulose and mixtures thereof.

4. The method according to any one of claims 1 to 3, wherein the conductive agent is in powder form, and is preferably acetylene black, conductive fibers, metal wires and mixtures thereof.

5. The method according to any one of claims 1 to 4, wherein the solvent is selected from the group consisting of water, liquid organic solvents, inorganic mineral oils and mixtures thereof.

6. The method according to any one of claims 1 to 5, wherein the mixing is selected from the group consisting of open mixing, internal mixing, frame mixing and anchor mixing.

7. The method of any one of claims 1 to 6, wherein the mixing is performed for about 5 to 300 minutes.

8. The method of any one of claims 1 to 7, wherein cold rolling is used The process is carried out by rolling.

9. The method according to any one of claims 1 to 8, wherein the active material film is a single-layer active material film.

10. The method according to any one of claims 1 to 9, wherein the current collector is selected from copper foil, aluminum foil or a sticky conductive polymer film.

11. The method according to any one of claims 1 to 10, wherein the conductive adhesive is selected from the group consisting of aqueous conductive adhesive, organic conductive adhesive and mixtures thereof.

12. The method of any one of claims 1 to 11, wherein the conductive coating is formed by a micro transfer coating method.

13. The method according to any one of claims 1 to 12, wherein based on the total mass of the electrode constituent materials, the amount of the solvent is 3% to 50% mass ratio, preferably 3% to 30% mass ratio , more preferably 5% to 10% mass ratio.

14. The method according to any one of claims 1 to 13, wherein based on the total mass of the electrode constituent materials, the active material is 50% to 98% mass ratio, and the binder is 0.1% to 20% mass ratio, The conductive agent is 0.1% to 30% mass ratio.

15. The method according to any one of claims 1 to 14, wherein the active material film and the conductive adhesive are both in a semi-dry state.

16. The porous electrode prepared by the method of any one of claims 1 to 15.

17. Method for preparing chemical energy storage devices, including:

(1) Provide porous electrodes;

(2) Use the porous electrode to prepare the core of a chemical energy storage device; and (3) Use the core to assemble a chemical energy storage device;

Wherein, the porous electrode is prepared by the method described in any one of claims 1 to 15.

18. The method of claim 17, wherein the porous electrodes are used as positive electrode sheets and negative electrode sheets respectively.

19. The method of claim 18, wherein the remaining foil length of the positive electrode sheet and the negative electrode sheet is 1 mm to 20 mm, preferably 7 mm.

20. The method according to any one of claims 17 to 19, wherein the chemical energy storage device is assembled by installing the core in a metal shell with openings at both ends.

21. The method according to claim 20, wherein the positive electrode piece and the negative electrode piece adopt a different end structure or a same end structure.

21. The method of claim 20, wherein when the positive electrode sheet and the negative electrode sheet adopt a heterodox structure, the core is welded to the upper current collector and the lower current collector respectively, and the upper current collector and the lower current collector are welded. The current collector is welded to the pole and the metal shell respectively.

22. The method of claim 20, wherein when the positive electrode piece and the negative electrode piece adopt a same-end structure, the core is welded to the upper current collector and the lower current collector respectively, and the upper current collector and the lower current collector are welded. The lower current collector is welded to the pole respectively.

23. The method of claim 21 or 22, wherein the metal shell is interference-fitted and welded to the upper cover plate and the lower cover plate respectively.

24. The method of claim 21, wherein the distance between the lower current collector and the lower cover plate is 1 mm to 5 mm, preferably 1.5 mm.

25. The method of claim 21 or 22, wherein the upper cover plate and the pole are There are insulating gaskets and O-rings between them.

26. The method of claim 22, wherein there is an insulating gasket and an O-shaped sealing ring between the lower cover plate and the pole.

27. The method of claim 25, wherein the nut is fixed between the pole led out from the upper cover plate and the upper cover plate.

28. The method of claim 26, wherein the nut is fixed between the pole led out from the lower cover plate and the lower cover plate.

29. The chemical energy storage device prepared by the method of any one of claims 17 to 28.

30. A method of preparing a chemical energy storage device assembly, comprising:

(1) Provide porous electrodes;

(2) Use the porous electrode to prepare the core of a chemical energy storage device;

(3) Use the core to assemble chemical energy storage device monomers; and

(4) Fix a plurality of the chemical energy storage device monomers in a support body, and connect a plurality of the chemical energy storage device monomers in series or in parallel through connecting sheets, thereby obtaining the chemical energy storage device assembly;

31. The method of claim 30, wherein the chemical energy storage device assembly and the balancing circuit board are placed in a housing, preferably in an aluminum housing.

32. The method of claim 31, wherein the inner wall of the housing is covered with an insulating board, preferably an epoxy resin insulating board.

33. The method of any one of claims 30 to 32, wherein said The support body is made of aluminum.

34. The method of any one of claims 30 to 33, wherein the connecting piece is a copper connecting piece.

35. The chemical energy storage device prepared by the method of any one of claims 30 to 34.