WO2016015486A1

WO2016015486A1 - Manufacturing method for electro-chemical electrical conducting functional membrane

Info

Publication number: WO2016015486A1
Application number: PCT/CN2015/075837
Authority: WO
Inventors: 熊逸民
Original assignee: 东莞斯巴复新能源有限公司
Priority date: 2014-07-30
Filing date: 2015-04-03
Publication date: 2016-02-04
Also published as: CN104201005A

Abstract

Disclosed is a manufacturing method for an electro-chemical electrical conducting functional membrane. In the present invention, an active substance, an auxiliary material, an adhesive and a lubricant are processed into a granular substance suitable for injection molding, and the granular substance is heated and subjected to plate injection molding, hot pressing vulcanization and cold pressing forming to form a coil film; printing processing is used for an intermediate supporter, to be specific, a thermosetting adhesive is printed on the intermediate supporter to form a needed pattern or a special shape; the film coil is compounded with the intermediate supporter, and die cutting, discharging and rolling are performed to form the electro-chemical electrical conducting functional membrane that can be used for the subsequent processing for a battery. The present invention is simple in technique and easy to implement, a functional membrane meeting high technical requirements can be manufactured, and the production cost is greatly lowered.

Description

Description: A method for manufacturing an electrochemically conductive functional film

[0001] The present invention relates to the field of electrode sheets in electrochemical power sources and electrolytic plating processes, and more particularly to a method of manufacturing electrochemical conductive function films.

Background technique

[0002] In the prior art, electrochemical power sources have been used in our fields from lead-acid batteries one hundred years ago to lithium ion batteries, nickel-metal hydride batteries, etc., and play an important role in people's lives. With the advancement of science and technology, the demand for electrochemical power supplies is increasing, and the performance requirements are getting higher and higher.

[0003] The most important of the electrochemical power source and the electric double layer capacitor is a lamellar structure or film composed of an active material, and the lamellar structure or film composed of the active material and the auxiliary material is electrochemically conductive. Functional diaphragm. The electrochemically conductive functional membrane constitutes the basic skeleton of the electrochemical reaction, provides mechanical strength, electrical conductivity, exhaust gas and liquid penetration for the electrochemical reaction, and is a key component of the electrochemical power source and the electric double layer capacitor.

[0004] Electric double layer capacitors are a power compensating period developed in recent years. Compared with conventional capacitors, they have a capacity density of more than 1000 times, and the current density can reach 10 or more of lead-acid batteries. Transition compensation device between battery and battery.

technical problem

[0005] At present, manufacturers of batteries and supercapacitors use a coating method to manufacture an electrochemically conductive functional film containing an active material. This manufacturing method uses a large amount of liquid as an auxiliary agent, and the manufacturing process is complicated, the type is single, and the special shape cannot be performed. Molding or multi-level blank processing. Therefore, it is necessary to improve.

Problem solution

Technical solution

[0006] In view of the deficiencies of the prior art, an object of the present invention is to provide a method for manufacturing an electrochemical conductive function film, which is simple in process, easy to implement, and produces a functional film with high technical requirements, which is greatly reduced. Cost of production.

In order to achieve the above object, the technical solution adopted by the present invention is. [0008] A method for manufacturing an electrochemical conductive function film, comprising the following steps,

[0009] In the printing step, the intermediate support is used as a mold skeleton, and the thermal adhesive is formed on the intermediate support by printing, and the heat-sensitive adhesive formed on the intermediate support forms a set pattern or shape, and the other of the intermediate support Part is a blank part;

[0010] a compounding step of mixing the active material, the auxiliary substance, the plasticizer and the wetting agent to form a primary masterbatch; [0011] a mixing step of performing the master batch by a large shear mixer or a roll mill Mixing, forming a secondary masterbatch

[0012] in the granulation step, the secondary masterbatch is put into a screw granulator, and the master granule is produced by a screw granulator, and the master granule is granular;

[0013] The film injection step, the masterbatch is put into a flat-plate injection molding machine or a hot roll press, and extruded into a film; [0014] a film vulcanization step, the film is vulcanized by hot pressing;

[0015] The film is subjected to a cold rolling setting step, and the film is cold-rolled and shaped by a cold rolling mill to form a semi-finished film;

[0016] In the compounding step, the intermediate support body printed in the printing step and the semi-finished film are heat-compressed by hot rolling composite processing to form a semi-finished electrochemical conductive functional film having a two-layer structure, a three-layer structure or a multi-layer structure. The sheet, the semi-finished film and the intermediate support are alternately stacked in a stacking order;

[0017] a discharge die cutting step, a semi-finished electrochemical conductive function film for discharging and die cutting;

[0018] Finished product, electrochemically conductive functional film.

[0019] In a further technical solution, in the compounding step, the components of the following weight ratio are included,

[0020] active substance 80~95<3⁄4,

[0021] auxiliary substance 0.5~10<3⁄4,

[0022] plasticizer 0.5~5<3⁄4,

[0023] Wetting agent balance.

[0024] In a further technical solution, in the compounding step, the active material is selected from activated carbon, the auxiliary material is selected from a conductive agent and a fine powder of aluminum oxide, the wetting agent is selected from paraffin oil, and the plasticizer is selected from POE particles, and the weight thereof is as follows.

[0025] Activated carbon 80~95<3⁄4,

[0026] Conductive agent 1~5<3⁄4,

[0027] aluminum oxide fine powder 0.5~2%, [0028] POE particles 0.5 to 5<3⁄4,

[0029] Paraffin oil balance.

[0030] In a further technical solution, in the granulation step, the granulation process of the screw granulator comprises one of an extrusion granulation process, a spray granulation process or a ball milling granulation process, and the granulation process The particles are formed to have a diameter of 3 to 8 mm and a length of 2 to 5 mm.

[0031] In a further technical solution, the active material includes activated carbon, graphene, modified graphene material, graphene composite material, mesophase carbon microsphere, natural graphite, modified graphite, coated graphite, carbon nanofiber, carbon a mixture of one or more of a lithium-containing positive electrode powder material used for a nanotube, a coke, a silicon powder, a silicon wire, a lithium ion battery, or a lithium element-containing negative electrode powder material used for a lithium ion battery;

[0032] The plasticizer includes polymethacrylic acid, polymethyl methacrylate, polytetrafluoroethylene, polyvinylidene fluoride, styrene butadiene rubber, carboxymethyl cellulose, polyvinyl pyrrolidone, polyvinyl alcohol or modified One or more mixtures of rubber;

[0033] Wetting agents and auxiliary substances include paraffin, tetrahydrofuran, inorganic mineral oil, conductive agent, carbon black, carbon fiber

One or a mixture of one or more of alumina or silica.

[0034] In a further technical solution, in the printing step, the printing mode of the intermediate support body is selected from an anilox roller printing method, a rubber roller printing method, a screen printing method, a transfer printing method or a spray printing method.

[0035] In a further technical solution, the die cutting step, the die cutting method of the semi-finished electrochemical conductive function film is selected by a flat die cutting or a hob die cutting, and the die cutting process comprises a discharge process, the die cut film The sheet is a single piece or a roll.

[0036] In a further technical solution, the film is subjected to a cold rolling setting step, and the film is cold rolled to a set thickness by a cold rolling mill, and is wound into a semi-finished film.

Advantageous effects of the invention

Beneficial effect

[0037] After adopting the above structure, the present invention has the advantages compared with the prior art: the process of the invention is simple, easy to implement, and the functional film with high technical requirements is manufactured, and the production cost is greatly reduced.

[0038] The present invention processes the active material, the auxiliary material, the binder and the lubricant into a particulate material suitable for injection molding, and heats the particulate matter to perform flat plate injection molding, hot press vulcanization, cold press setting, and constitutes a coil film; The intermediate support is printed, and the thermosetting adhesive is formed by printing on the intermediate support. The desired pattern or special shape; the film roll is combined with the intermediate support, and then die-cut, discharged, and wound to form an electrochemical conductive function film which can be used for subsequent processing of the battery. Brief description of the drawing

DRAWINGS

[0039] The present invention will be further described below in conjunction with the accompanying drawings and embodiments.

1 is a schematic view of a process flow of the present invention.

2 is a schematic structural view of a first electrochemical conductive function film produced by the present invention.

3 is a schematic structural view of a second electrochemical conductive function film produced by the present invention.

4 is a schematic structural view of a third electrochemical conductive function film produced by the present invention.

[0044] FIG. 5 is a schematic view of a three-layer structure electrochemically conductive functional film.

6 is a schematic view of a five-layer electrochemically conductive functional film.

BEST MODE FOR CARRYING OUT THE INVENTION

The following description is only a preferred embodiment of the present invention, and does not limit the scope of the present invention.

Example

[0047] A method of manufacturing an electrochemical conductive function film, as shown in FIGS. 1 to 6, includes the following steps.

[0048] In the printing step, the intermediate support body 1 is made of 25um corroded aluminum foil produced by Dongyang Sunlight, and the intermediate support body 1 is used as a mold skeleton, and the thermal adhesive is formed on the intermediate support body 1 by printing, and the heat formed in the intermediate support body is formed. The sensitive gel forms a set pattern or shape, and the other portion of the intermediate support is a blank portion. The printing method of the intermediate support 1 is selected by an anilox printing method, a rubber roller printing method, a screen printing method, a transfer printing method or a spray printing method.

[0049] a compounding step of mixing the active material, the auxiliary substance, the plasticizer and the wetting agent in the following proportion by weight to form a primary master batch,

[0050] Active substance 80~95<3⁄4,

[0051] auxiliary substance 0.5~10<3⁄4,

[0052] plasticizer 0.5~5<3⁄4, [0053] Wetting agent balance.

[0054] Specifically, in the specific formula of the primary masterbatch, the active material is selected from activated carbon, the auxiliary material is selected from a conductive agent and a fine powder of aluminum oxide, the wetting agent is selected from paraffin oil, and the plasticizer is selected from POE particles, and the weight thereof is as follows. ,

[0055] Activated carbon 80~95<3⁄4,

[0056] Conductive agent 1~5<3⁄4,

[0057] Al2O3 fine powder 0.5~2<3⁄4,

[0058] POE particles 0.5~5<3⁄4,

[0059] Paraffin oil

[0060] More specifically, the activated carbon is made of activated carbon made from coconut shells of Sri Lanka. The manufacturer is Haycarb, model 202A, and the auxiliary materials are SuperP li conductive agent produced by Changzhou Trioco Co., Ltd. and Nano-Al2O3 powder of Sumitomo of Japan. The lubricant is selected from GE paraffin oil of the United States, and the plasticizer is selected from Sinopec POE pellets. The preferred ratio of the primary masterbatch is as follows.

[0061] activated carbon 90%,

[0062] Conductive agent 4%,

[0063] aluminum oxide fine powder 1%,

POE particles 4%

[0065] Paraffin oil 1%.

[0067] In the granulation step, the second-stage masterbatch is put into a screw granulator, and the master granule is produced by a screw granulator, and the master granule is granular; the granulation process of the screw granulator includes extrusion molding One of the granule process, the spray granulation process or the ball mill granulation process, the granulation process forms particles having a diameter of 3 to 8 mm and a length of 2 to 5 m. A preferred particle size is that the particles have a diameter of 6 mm and a length of 4 mm.

[0068] In the film injection step, the masterbatch is put into a flat-plate injection molding machine or a hot roll press, and is extruded into a film; specifically, the film injection molding is performed using a flat-plate injection molding machine manufactured by Beijing Materialization Co., Ltd., and the injection-molded film is formed. The thickness is 1 50um, the width is 300mm, and the length is 800mm.

[0069] In the film vulcanization step, the film is vulcanized by hot pressing. Among them, the hot pressing equipment is equipped with a number of hot rolls, the diameter of the hot roll is 200 mm, the number of hot rolls is more than 10, the vulcanization temperature is 190 degrees Celsius, and the crucible is 5 minutes. [0070] In the film cold rolling setting step, the film is cold-rolled and shaped by a cold rolling mill to form a semi-finished film 2; the film is cold-rolled to a set thickness by a cold rolling mill, and wound into a semi-finished film 2. The cold rolling mill uses Xingtai Nakonor 40 0 cold rolling equipment, and the thickness of the film is 120um~125um.

[0071] In the compounding step, the intermediate support body 1 and the semi-finished film sheet 2 printed in the printing step are hot-compressed by hot rolling composite processing to form a semi-finished product of two-layer structure, three-layer structure or multi-layer structure. The functional film, the semi-finished film 2 and the intermediate support 1 are alternately stacked in a stacking order. Among them, the hot rolling composite hot roll has a diameter of 200 mm, a number of hot rolls of 4, a vulcanization temperature of 180 ° C, and a line speed of 8 m per minute.

[0072] The discharge die-cutting step, the semi-finished electrochemical conductive function film is used for discharging and die-cutting; the die-cutting mode of the semi-finished electrochemical conductive function film is selected by flat die cutting or hob die cutting, and the die cutting process comprises a row. In the material process, the die-cut diaphragm is a single piece or a coil.

[0073] Finished product, electrochemically conductive functional film.

[0074] In the whole processing process of the present invention, the intermediate support body 1 is used as a mold skeleton, and the heat-sensitive adhesive is formed on the intermediate support body 1 by printing according to a desired pattern or shape, and other portions are blank portions, according to the lower portion. The one-step process requires die-cutting, nesting, etc. to form a pattern or pattern of a specific need.

[0075] The active material and the auxiliary substance form a particulate material under high pressure extrusion by the action of a plasticizer and a wetting agent, and the pellet material is used for the injection molding of the film, and the injection molded film is vulcanized by a hot roll. The strength is greatly increased, and the film is rolled to a desired thickness by cold rolling, and is wound into a semi-finished film 2.

[0076] The present invention processes the printed intermediate support 1 and the semi-finished film 2 by hot rolling, then die-cutting, and physically discharging the film into a pattern or shape, which may be The flakes can also be coiled.

[0077] This production process is a processing method with high technical content, low cost, high degree of automation, and low personnel usage, and is particularly suitable for functional diaphragm processing of special shapes.

[0078] In the present invention, the active material includes activated carbon, graphene, modified graphene material, graphene composite material, mesophase carbon microsphere, natural graphite, modified graphite, coated graphite, carbon nanofiber, carbon nanotube One or a mixture of one or more of a lithium-containing positive electrode powder material used for a coke, a silicon powder, a silicon wire, a lithium ion battery, or a lithium element-containing negative electrode powder material used for a lithium ion battery.

[0079] The plasticizer includes polymethacrylic acid, polymethyl methacrylate, polytetrafluoroethylene, polyvinylidene fluoride, and butyl One or a mixture of one or more of benzene rubber, carboxymethyl cellulose, polyvinyl pyrrolidone, polyvinyl alcohol or modified rubber.

[0080] Wetting agents and auxiliary substances include paraffin, tetrahydrofuran, inorganic mineral oil, conductive agent, carbon black, carbon fiber

One or a mixture of one or more of alumina or silica.

2 to 4 are schematic views of a particularly shaped electrochemically conductive functional film produced by the present invention.

The intermediate portion of the electrochemically-conductive functional film in FIG. 2 is a blank region surrounded by a semi-finished film 2 around the blank region.

[0083] The electrochemical conductive function film in FIG. 3 is in the shape of a conventional lithium ion battery or a supercapacitor battery film, and the intermediate portion has a pattern portion as a region with a semi-finished film 2, and the blank regions on both sides are intermediate supports. 1.

[0084] The electrochemical conductive function film in FIG. 4 is in the shape of a special shape lithium ion battery or a super capacitor battery film, and the intermediate portion has a pattern portion as a region with a semi-finished film 2, and the blank regions on both sides are intermediate supports. Body 1.

5 is a schematic view of a three-layer structure electrochemically conductive function film, the upper and lower sides of which are semi-finished films 2

In the middle is the structure of the support.

6 is a schematic view of a five-layer electrochemically-conductive functional membrane, from the top to the bottom, the third, third and fifth layers are semi-finished membranes 2, the second and fourth layers are Intermediate support 1.

[0087] The industrial applicability of the present invention, the present invention can be used in the fields of electrochemically controlled batteries, separation and absorption, particularly in lithium ion batteries, lead acid batteries, nickel hydrogen batteries, nickel cadmium batteries and fuel cells; There are also a large number of practical applications in supercapacitors and hybrid capacitors with double layer reaction, and also have great applications in sewage treatment, adsorption, recovery and separation of trace substances. The invention can process very complicated shapes of electricity. The chemical conductive function diaphragm can be used in different shapes and different forms of products, and the cost is low and the production speed is fast.

[0088] The application range of the invention is an electrochemical battery electrode, an electric double layer capacitor electrode, an electrolytic cell electrode, an electrophoresis electrode, an electrolysis water electrode, a fuel cell electrode, a water treatment electrode, a filter filter membrane, a water treatment filter membrane, a biological Electrochemical analysis of the electrode and filter membrane.

The above content is only a preferred embodiment of the present invention. For those skilled in the art, according to the idea of the present invention, there are some changes in the specific implementation manner and application scope, and the contents of this specification should not be considered. The solution is a limitation of the invention.

Claims

Claim

[Claim 1] A method for manufacturing an electrochemical conductive function film, comprising the steps of: printing a step of forming a heat-sensitive adhesive on an intermediate support by a printing method using an intermediate support as a mold skeleton; The heat-sensitive adhesive formed on the intermediate support forms a set pattern or shape, and the other portion of the intermediate support is a blank portion;

In the compounding step, the active material, the auxiliary substance, the plasticizer and the wetting agent are mixed to form a primary master batch; in the mixing step, the master batch is kneaded by a large shear mixer or a roller mill to form a secondary layer Masterbatch

In the granulation step, the secondary masterbatch is put into a screw granulator, and the master granule is produced by a screw granulator, and the master granule is granular;

In the film injection step, the masterbatch is put into a flat-plate injection molding machine or a hot roll press, and extruded into a film;

a vulcanization step of the film, the film is vulcanized by hot pressing;

The film is subjected to a cold rolling setting step, the film is cold-rolled by a cold rolling mill to form a semi-finished film; and a composite step is performed by hot rolling composite processing to heat-combine the printed intermediate support and the semi-finished film after the printing step. Forming a semi-finished electrochemically conductive functional film having a two-layer structure, a three-layer structure or a multi-layer structure, and the semi-finished film and the intermediate support are alternately stacked in a stacking order;

The discharge die-cutting step, the semi-finished electrochemical conductive function film is used for discharging and die-cutting; the finished product, the electrochemical conductive function film.

[Claim 2] The method for producing an electrochemical conductive function film according to claim 1, wherein: the compounding step includes components of the following weight ratio,

Active substance 80~95%,

Auxiliary substance 0.5~10%,

Plasticizer 0.5~5<3⁄4,

Wetting agent balance.

[Claim 3] A method of manufacturing an electrochemically conductive functional film according to claim 1, characterized in that In the batching step, the active material is made of activated carbon, the auxiliary material is made of conductive agent and aluminum oxide micropowder, the wetting agent is made of paraffin oil, and the plasticizer is made of POE particles. The weight is as follows.

Activated carbon 80~95<3⁄4,

Conductive agent 1~5<3⁄4,

Al2O3 micropowder 0.5~2%,

POE particles 0.5~5<3⁄4,

Paraffin oil balance.

[Claim 4] The method for producing an electrochemical conductive function film according to claim 1, wherein: in the granulation step, the granulation process of the screw granulator includes an extrusion granulation process, One of the spray granulation process or the ball mill granulation process, the granulation process forms particles having a diameter of 3 to 8 mm and a length of 2 to 5 mm.

[Claim 5] The method for producing an electrochemical conductive function film according to claim 1, wherein the active material comprises activated carbon, graphene, modified graphene material, graphene composite material, mesophase carbon Microspheres, natural graphite, modified graphite, coated graphite, carbon nanofibers, carbon nanotubes, coke, silicon powder, silicon wire, lithium-ion battery, lithium-containing positive electrode powder material or lithium ion battery One or a mixture of one or more of lithium anode materials;

Plasticizers include polymethacrylic acid, polymethyl methacrylate, polytetrafluoroethylene, polyvinylidene fluoride, styrene butadiene rubber, carboxymethyl cellulose, polyvinyl pyrrolidone, polyvinyl alcohol or modified rubber. One or more mixtures;

The wetting agent and auxiliary substances include one or a mixture of one or more of paraffin, tetrahydrofuran, inorganic mineral oil, conductive agent, carbon black, carbon fiber, alumina or silica.

[Claim 6] The method for manufacturing an electrochemical conductive function film according to claim 1, wherein: in the printing step, the printing method of the intermediate support body is selected by an anilox roll printing method, a rubber roller printing method, Screen printing, transfer printing or spray printing.

[Claim 7] The method for manufacturing an electrochemical conductive function film according to claim 1, wherein: the die cutting step, the die cutting method of the semi-finished electrochemical conductive film is selected Die cutting or hob die cutting, the die cutting process contains a discharge process, and the die cut film is a single piece or a coil.

[Claim 8] The method for manufacturing an electrochemical conductive function film according to claim 1, wherein: the film is subjected to a cold rolling setting step, and the film is cold rolled to a set thickness by a cold rolling mill. The roll becomes a semi-finished film.