CN112599785B - Self-temperature-control current collector of lithium ion battery and preparation method and application thereof - Google Patents
Self-temperature-control current collector of lithium ion battery and preparation method and application thereof Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000005485 electric heating Methods 0.000 claims abstract description 78
- 238000000576 coating method Methods 0.000 claims abstract description 49
- 239000011248 coating agent Substances 0.000 claims abstract description 47
- 229920006254 polymer film Polymers 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 239000011159 matrix material Substances 0.000 claims abstract description 5
- 239000007772 electrode material Substances 0.000 claims abstract description 3
- 229920001940 conductive polymer Polymers 0.000 claims description 36
- 239000010408 film Substances 0.000 claims description 29
- 239000010409 thin film Substances 0.000 claims description 23
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 238000013329 compounding Methods 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- 230000008020 evaporation Effects 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 12
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000007731 hot pressing Methods 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 239000004332 silver Substances 0.000 claims description 8
- -1 polypropylene Polymers 0.000 claims description 7
- 238000007650 screen-printing Methods 0.000 claims description 7
- 238000007747 plating Methods 0.000 claims description 6
- 229920006393 polyether sulfone Polymers 0.000 claims description 6
- 238000007581 slurry coating method Methods 0.000 claims description 6
- 239000004695 Polyether sulfone Substances 0.000 claims description 5
- 239000004642 Polyimide Substances 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 239000004020 conductor Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000670 limiting effect Effects 0.000 abstract description 3
- 229910052744 lithium Inorganic materials 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 106
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- 229920001610 polycaprolactone Polymers 0.000 description 4
- 239000004632 polycaprolactone Substances 0.000 description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000002109 single walled nanotube Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
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- 238000002425 crystallisation Methods 0.000 description 1
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- 238000004146 energy storage Methods 0.000 description 1
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- 239000003574 free electron Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
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Classifications
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/60—Heating or cooling; Temperature control
- H01M10/61—Types of temperature control
- H01M10/615—Heating or keeping warm
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/60—Heating or cooling; Temperature control
- H01M10/63—Control systems
- H01M10/637—Control systems characterised by the use of reversible temperature-sensitive devices, e.g. NTC, PTC or bimetal devices; characterised by control of the internal current flowing through the cells, e.g. by switching
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/60—Heating or cooling; Temperature control
- H01M10/65—Means for temperature control structurally associated with the cells
- H01M10/654—Means for temperature control structurally associated with the cells located inside the innermost case of the cells, e.g. mandrels, electrodes or electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/60—Heating or cooling; Temperature control
- H01M10/65—Means for temperature control structurally associated with the cells
- H01M10/657—Means for temperature control structurally associated with the cells by electric or electromagnetic means
- H01M10/6571—Resistive heaters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a self-temperature-control current collector of a lithium ion battery and a preparation method thereof, and aims to solve the problems of poor charge and discharge performance, poor rate performance and the like of the lithium ion battery and a solid lithium battery in a low-temperature environment. This automatic temperature control mass flow body includes: a conductive coating for supporting an electrode material; the polymer film layer is used as a matrix part of the current collector, and is loaded with a conductive coating and packaged with an automatic temperature control electric heating layer; the electric heating layer electrode is used for driving the automatic temperature control electric heating layer to work; the self-control temperature electric heating layer is arranged between the first polymer film layer and the second polymer film layer, converts electric energy into heat energy through an external power supply, has a self-control temperature characteristic, and is used for self-limiting temperature heating of the lithium battery. The invention has the advantages of high heating speed, high heating efficiency, simple structure, no temperature control element and system, simple manufacturing process, low cost, self-temperature limiting property and the like.
Description
Technical Field
The invention relates to a self-temperature-control current collector, in particular to a preparation method and application of a lithium ion battery current collector with the capability of self-controlling temperature.
Background
The lithium ion battery, as a "green secondary battery" in the 21 st century, has the advantages of high energy density, high open circuit voltage, long service life, environmental friendliness, small self-discharge and the like, and is widely applied to the fields of portable electronic equipment, new energy vehicles, energy storage systems and the like. However, in a low temperature environment, the electrochemical performance of the lithium ion battery, including the charge and discharge performance, the rate performance, and the like, is greatly limited. The problem is widely reflected in the problems that the electric quantity of the smart phone suddenly drops in a cold environment, the charging time of the electric automobile is doubled in winter, the endurance mileage is shortened, and the like. Therefore, how to ensure that the lithium ion battery is used in a cold environment is an inexhaustible practical problem.
In the description of the related document, a heating element is generally used to heat a battery cell or a battery module. For example, the solution proposed in patent CN107591589A is to measure the temperature of the battery cell by using a thermistor, collect the voltage of the battery cell by using a load cell, and heat the battery cell to the upper limit of the preheating temperature range if the battery cell is not in the charging and discharging state and the battery cell temperature is lower than the preheating temperature range; and if the battery cell is in a charging and discharging state and the temperature of the battery cell is lower than the normal working temperature range, heating the battery cell to the upper limit of the normal working temperature range. The heating system is composed of a heating film, a fuse, a plurality of switches and a circuit. For another example, patent CN110931675A proposes that a heating device is introduced between the cell units in a series-parallel circuit manner, and the heating device is composed of a heating element (a silica gel heating plate) and a heating relay, and is finally assembled into a whole battery module.
Obviously, such patents all have the disadvantages of response time lag (generally requiring a thermistor to measure temperature and then starting heating), slow heating (manner of heating the battery to the outside of the battery and the inside of the battery), complex structure (requiring a large number of components including a heating element, a heating relay, a thermistor, a fuse, a switch and the like), low space utilization rate of the battery module (causing the volumetric capacity and the volumetric capacity of the battery module to be greatly reduced), complex process, high cost and the like.
Disclosure of Invention
In order to solve the problems of long response time, low heating speed, complex structure and the like when heating a lithium battery cell or a battery module in the prior art, the invention provides a self-temperature-control current collector of a lithium ion battery, which comprises a conductive coating, a polymer film layer, an electric heating layer electrode and a self-temperature-control electric heating layer, wherein the conductive coating comprises a first conductive coating and a second conductive coating, the polymer film layer comprises a first polymer film layer and a second polymer film layer, and the conductive coating is used for loading a positive electrode material or a negative electrode material; the polymer film layer is used for loading the conductive coating and packaging the automatic temperature control electric heating layer and is used as a matrix part of the automatic temperature control current collector of the lithium ion battery; the electric heating layer electrode is arranged on the second polymer film layer and applies direct current or alternating current to the second polymer film layer to drive the automatic temperature control electric heating layer to work; the automatic temperature control electric heating layer is arranged between the first polymer film layer and the second polymer film layer. The working principle is that under the external voltage, free electrons in the self-temperature-control electric heating composite material of the self-temperature-control electric heating layer move along the direction of an external electric field to form current, and heat is generated along with the extension of time according to the Joule-Lenz law, namely, electric energy is converted into heat energy. The temperature control principle is that when the temperature approaches the melting point of the crystalline matrix of the self-temperature-control electrothermal composite material, the volume is expanded due to the crystallization and melting, so that an internal conductive path is rapidly damaged, the resistivity of the self-temperature-control electrothermal composite material is sharply increased, an obvious PTC effect is generated, and the effect of controlling the heating temperature is realized.
Further, the first conductive coating and the second conductive coating are made of aluminum, copper, silver or platinum, and are respectively compounded with any one surface of the first polymer thin film layer and the second polymer thin film layer through evaporation coating, magnetron sputtering and slurry coating to obtain a single-sided conductive polymer thin film layer, and the thickness of the conductive coating is 5-20 microns.
Further, the polymer film layer is one or more of polyimide, polyether sulfone resin, polypropylene, polyethylene and polyvinyl chloride, and the thickness of the polymer film layer is 5-20 μm.
Further, the electric heating layer electrode takes copper, silver or platinum as an electrode material, and the copper, silver or platinum electrode is arranged on the non-conductive surface of the single-surface conductive polymer film layer formed by the first conductive coating and the first polymer film layer through screen printing, evaporation coating, magnetron sputtering and attaching and is in contact with the self-temperature-control electric heating layer.
Further, the self-temperature-control electric heating layer has a positive temperature coefficient effect, realizes self-temperature limitation, has the working temperature of 40-60 ℃, is coated on the non-conductive surface of the single-surface conductive polymer film layer provided with the electric heating layer electrode through the self-temperature-control electric heating ink, and is obtained after drying and curing for 4-8 hours at the temperature of 60-120 ℃, and the thickness of the self-temperature-control electric heating layer is 5-10 microns.
Further, the self-temperature-control electric heating ink is prepared by uniformly stirring the following components in parts by weight: 5-20 parts by weight of high resistance carbon, 5-20 parts by weight of low resistance carbon, 1-5 parts by weight of high aspect ratio carbon, 60-85 parts by weight of polymer and 200 parts by weight of solvent.
Further, the non-conductive surface of the single-sided conductive polymer film layer and the self-temperature-control electric heating layer are subjected to hot-pressing compounding under the conditions that the pressure is 1-10MPa and the temperature is 60-120 ℃.
The invention also provides a preparation method of the self-temperature-control current collector, which comprises the following steps:
plating a conductive material on any one surface of a polymer thin film layer through evaporation coating, magnetron sputtering or slurry coating to obtain a single-sided conductive polymer thin film layer;
compounding high-conductivity metal on the non-conductive surface of the single-side conductive polymer film layer through screen printing, evaporation coating, magnetron sputtering or attaching to form an electric heating layer electrode;
step three, preparing self-temperature-control electric heating ink slurry, coating the slurry on the non-conductive surface of the single-surface conductive polymer film layer provided with the electric heating layer electrode, and drying and curing at 60-120 ℃ for 4-8 hours to obtain a self-temperature-control electric heating layer;
and fourthly, carrying out hot-pressing compounding on the non-conductive surface of the other single-side conductive polymer film layer and the automatic temperature control electric heating layer under the conditions that the pressure is 1-10MPa and the temperature is 60-120 ℃ to obtain the automatic temperature control current collector.
The invention also provides application of the self-temperature-control current collector of the lithium ion battery in heating of the lithium ion battery in a low-temperature state. The direct current or alternating current is applied to the automatic temperature control electric heating layer through an external power supply to drive the automatic temperature control electric heating layer to work, so that the lithium ion battery is heated to the working temperature.
Has the advantages that:
the lithium ion self-temperature-control current collector has the characteristics of quick response time, quick heating, high heating efficiency, simple structure, no temperature control element or system, no occupation of battery module space, simple process, low cost, self-temperature limiting property and the like through the property of self-temperature-control electric heating ink.
Drawings
Fig. 1 is a structural view of a self temperature controlling current collector of the present invention;
fig. 2 is a cross-sectional view of the self temperature controlling current collector of the present invention.
Detailed Description
The technical solution of the present invention is further illustrated by the following embodiments and the accompanying drawings, but the scope of the present invention is not limited thereto.
As shown in fig. 1 and 2, the self-temperature-control current collector of the lithium ion battery of the present invention comprises a conductive coating, a polymer film layer, an electric heating layer electrode 3 and a self-temperature-control electric heating layer 4, wherein the conductive coating comprises a first conductive coating 1 and a second conductive coating 6, the polymer film layer comprises a first polymer film layer 2 and a second polymer film layer 5, and the conductive coating is used for loading a positive electrode material or a negative electrode material; the polymer film layer is used as a matrix part of the current collector, and is loaded with a conductive coating and packaged with a self-temperature-control electric heating layer 4; the electric heating layer electrode 3 is used for driving the automatic temperature control electric heating layer 4 to work; and the automatic temperature control electric heating layer 4 is arranged between the first polymer film layer 2 and the second polymer film layer 5 and is used for controlling the temperature of the heating battery.
The first conductive coating 1 and the second conductive coating 6 are made of conductive materials such as aluminum, copper, silver, platinum and the like, and are respectively compounded with any one surface of the first polymer thin film layer 2 and the second polymer thin film layer 5 in the modes of evaporation coating, magnetron sputtering, slurry coating and the like to obtain a single-sided conductive polymer thin film layer, and the thickness of the conductive coating is 5-20 mu m.
The polymer film layer is a polymer film of Polyimide (PI), polyether sulfone resin (PES), polypropylene (PP), Polyethylene (PE), polyvinyl chloride (PVC) and the like, and the thickness of the polymer film layer is 5-20 mu m.
The electric heating layer electrode 3 is made of high-conductivity metal such as copper, silver and platinum, is arranged on the non-conductive surface of the single-surface conductive polymer thin film layer formed by the first conductive coating 1 and the first polymer thin film layer 2 through screen printing, evaporation coating, magnetron sputtering, fitting and the like, is in contact with the automatic temperature control electric heating layer 4, and is driven to work by applying direct current or alternating current through the external power supply 7.
The self-temperature-control electric heating layer 4 has positive temperature coefficient effect, can realize self-temperature limitation, has the working temperature of 40-60 ℃, is coated on the non-conductive surface of the single-surface conductive polymer film layer provided with the electric heating layer electrode, and is dried and cured at the temperature of 60-120 ℃ for 4-8 hours to obtain the self-temperature-control electric heating layer 4 with the thickness of 5-10 microns.
The self-temperature-control electric heating ink is prepared by uniformly stirring the following components in parts by weight: 5-20 parts by weight of high-resistance carbon (such as N991 carbon black, N330 pigment carbon black, N220 pigment carbon black and activated carbon), 5-20 parts by weight of low-resistance carbon (such as acetylene black, Ketjen black, Cabot conductive carbon black, ultra-dense high-conductive carbon black Super P Li, graphene and the like), 1-5 parts by weight of high-aspect-ratio carbon (such as single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon fibers and the like), 60-85 parts by weight of polymer (such as thermoplastic polyurethane elastomer rubber (TPU), polyethylene oxide (PEO), polyvinyl chloride (PVC), ethylene-vinyl acetate copolymer (EVA), Polycaprolactone (PCL), ethylene-octene copolymer (POE) and the like) and 200 parts by weight of solvent (such as N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC), N-methylpyrrolidone (NMP) Ethyl acetate, butyl butyrate, toluene, acetonitrile, etc.).
The non-conductive surface of the single-sided conductive polymer film layer and the self-temperature-control electric heating layer 4 are compounded by hot pressing under the conditions that the pressure is 1-10MPa and the temperature is 60-120 ℃.
Example 1:
the preparation method of the self-temperature-control current collector comprises the steps of firstly plating platinum on any one surface of a PI polymer thin film layer (with the thickness of 10 mu m) through magnetron sputtering to obtain a single-side conductive polymer thin film layer, wherein the thickness of the conductive coating is 5 mu m. And secondly, compounding the copper electrode on the non-conductive surface of the single-surface conductive polymer film layer by a screen printing method. Then, a self-temperature-controlled electrical heating ink slurry was prepared by using 10 parts by weight of N991 carbon black, 10 parts by weight of ketjen black, 5 parts by weight of single-walled carbon nanotubes, 75 parts by weight of thermoplastic polyurethane elastomer rubber (TPU), and 300 parts by weight of N-methylpyrrolidone (NMP) as a formulation. The slurry is coated on the non-conductive surface of the single-surface conductive polymer film layer provided with the electric heating layer electrode, and the self-temperature-control electric heating layer is obtained after drying and curing for 4 hours at 120 ℃ and the thickness of the self-temperature-control electric heating layer is 5 microns. And finally, carrying out hot-pressing compounding on the non-conductive surface of the single-sided conductive polymer film layer and the self-temperature-control electric heating layer under the conditions of the pressure of 10MPa and the temperature of 120 ℃ to obtain the self-temperature-control current collector. The obtained self-temperature-control current collector is heated from room temperature and is constant to 60 ℃ within 9 seconds under the drive of a 220V alternating current power supply.
Example 2:
the preparation method of the self-temperature-control current collector comprises the steps of firstly plating aluminum on any one surface of a PES (polyether sulfone) polymer thin film layer (with the thickness of 20 mu m) by an evaporation coating method to obtain a single-side conductive polymer thin film layer, wherein the thickness of the conductive coating is 10 mu m. And secondly, compounding the double-sided conductive copper adhesive tape electrode on the non-conductive surface of the single-sided conductive polymer film layer in a gluing mode. Then, a self-temperature-controlled electrical heating ink slurry was prepared by using 20 parts by weight of N330 pigment carbon black, 15 parts by weight of Super P Li, 1 part by weight of multi-walled carbon nanotubes, 64 parts by weight of polyethylene oxide (PEO), and 460 parts by weight of acetonitrile as a formulation. The slurry is coated on the non-conductive surface of the single-surface conductive polymer film layer provided with the electric heating layer electrode, and the self-temperature-control electric heating layer is obtained after drying and curing for 8 hours at 60 ℃ and the thickness of the self-temperature-control electric heating layer is 10 microns. And finally, carrying out hot-pressing compounding on the non-conductive surface of the single-sided conductive polymer film layer and the automatic temperature control electric heating layer under the conditions of the pressure of 1MPa and the temperature of 60 ℃ to obtain the automatic temperature control current collector. Under the drive of a 6V direct current power supply, the obtained self-temperature-control current collector is heated from room temperature and is constant to 40 ℃ within 30 seconds.
Example 3:
the preparation method of the self-temperature-control current collector comprises the steps of firstly plating copper on any one surface of a PVC polymer film layer (with the thickness of 20 mu m) by a magnetron sputtering method to obtain a single-side conductive polymer film layer, wherein the thickness of the conductive coating is 5 mu m. And secondly, compounding the copper electrode on the non-conductive surface of the single-side conductive polymer film layer by an evaporation coating method. Then, a self-temperature-control electrical heating ink slurry was prepared by using 20 parts by weight of N220 carbon black, 10 parts by weight of graphene, 5 parts by weight of single-walled carbon nanotubes, 65 parts by weight of ethylene-vinyl acetate copolymer (EVA), and 400 parts by weight of N, N-Dimethylformamide (DMF) as a formulation. The slurry is coated on the non-conductive surface of the single-surface conductive polymer film layer provided with the electric heating layer electrode, and the self-temperature-control electric heating layer is obtained after drying and curing for 6 hours at 80 ℃ and the thickness of the self-temperature-control electric heating layer is 8 microns. And finally, carrying out hot-pressing compounding on the non-conductive surface of the single-sided conductive polymer film layer and the self-temperature-control electric heating layer under the conditions of 6MPa of pressure and 72 ℃ to obtain the self-temperature-control current collector. The obtained self-temperature-control current collector is heated from room temperature and is constant to 55 ℃ within 22 seconds under the drive of a 12V direct-current power supply.
Example 4:
firstly, plating conductive silver paste on any one surface of a PP polymer film layer (with the thickness of 5 mu m) by a slurry coating method to obtain a single-sided conductive polymer film layer, wherein the thickness of the conductive coating layer is 20 mu m. And secondly, compounding the copper electrode on the non-conductive surface of the single-surface conductive polymer film layer by a screen printing method. Then, a self-temperature-control electrical heating ink slurry was prepared by using 20 parts by weight of activated carbon, 5 parts by weight of graphene, 1 part by weight of carbon fiber, 74 parts by weight of Polycaprolactone (PCL), and 200 parts by weight of N, N-Dimethylacetamide (DMAC) as a formulation. The slurry is coated on the non-conductive surface of the single-surface conductive polymer film layer provided with the electric heating layer electrode, and the self-temperature-control electric heating layer is obtained after drying and curing for 6 hours at 80 ℃ and the thickness of the self-temperature-control electric heating layer is 8 microns. And finally, carrying out hot-pressing compounding on the non-conductive surface of the single-sided conductive polymer film layer and the automatic temperature control electric heating layer under the conditions that the pressure is 3.5MPa and the temperature is 80 ℃ to obtain the automatic temperature control current collector. Under the drive of a 36V direct-current power supply, the obtained self-temperature-control current collector is heated from room temperature and is kept at 45 ℃ within 15 seconds.
The above-described embodiments are merely preferred embodiments of the present invention, which is not intended to be limiting in any way, and other variations and modifications are possible without departing from the scope of the invention as set forth in the appended claims.
Claims (9)
1. The utility model provides a lithium ion battery is from accuse temperature mass flow body, includes conductive coating, polymer thin film layer, electric heating layer electrode (3), automatic control temperature electric heating layer (4), conductive coating includes first conductive coating (1) and second conductive coating (6), the polymer thin film layer includes first polymer thin film layer (2) and second polymer thin film layer (5), its characterized in that: the conductive coating is used for loading a positive electrode material or a negative electrode material; the polymer film layer is used for loading the conductive coating and packaging the self-temperature-control electric heating layer (4) and is used as a matrix part of the self-temperature-control current collector of the lithium ion battery; the electric heating layer electrode (3) is arranged on the first polymer film layer (2) and is used for driving the automatic temperature control electric heating layer (4) to work; the automatic temperature control electric heating layer (4) is arranged between the first polymer film layer (2) and the second polymer film layer (5).
2. The self temperature controlling current collector of a lithium ion battery as claimed in claim 1, wherein: the first conductive coating (1) and the second conductive coating (6) are made of aluminum, copper, silver or platinum, and are respectively compounded with any one surface of the first polymer thin film layer (2) and the second polymer thin film layer (5) through evaporation coating, magnetron sputtering or slurry coating to obtain a single-sided conductive polymer thin film layer, and the thickness of the conductive coating is 5-20 mu m.
3. The self temperature controlling current collector of a lithium ion battery as claimed in claim 1, wherein: the polymer film layer is one or more of polyimide, polyether sulfone resin, polypropylene, polyethylene and polyvinyl chloride, and the thickness of the polymer film layer is 5-20 mu m.
4. The self temperature controlling current collector of a lithium ion battery as claimed in claim 2, wherein: the electric heating layer electrode (3) takes copper, silver or platinum as an electrode material, and the copper, silver or platinum electrode is arranged on the non-conductive surface of the single-surface conductive polymer film layer formed by the first conductive coating (1) and the first polymer film layer (2) through screen printing, evaporation coating, magnetron sputtering or fitting and is in contact with the automatic control temperature electric heating layer (4).
5. The self temperature controlling current collector of the lithium ion battery as claimed in claim 4, wherein: the self-temperature-control electric heating layer (4) has a positive temperature coefficient effect, realizes self-temperature limitation, has a working temperature of 40-60 ℃, is coated on the non-conductive surface of the single-surface conductive polymer film layer provided with the electric heating layer electrode (3) through self-temperature-control electric heating ink, and is obtained after drying and curing for 4-8 hours at a temperature of 60-120 ℃, and the thickness of the self-temperature-control electric heating layer is 5-10 microns.
6. The self temperature controlling current collector of a lithium ion battery as claimed in claim 5, wherein: the self-temperature-control electric heating ink is prepared by uniformly stirring the following components in parts by weight: 5-20 parts by weight of high resistance carbon, 5-20 parts by weight of low resistance carbon, 1-5 parts by weight of high aspect ratio carbon, 60-85 parts by weight of polymer and 200 parts by weight of solvent.
7. The self temperature controlling current collector of a lithium ion battery as claimed in claim 2, wherein: the non-conductive surface of the single-sided conductive polymer film layer and the self-temperature-control electric heating layer (4) are compounded by hot pressing under the conditions that the pressure is 1-10MPa and the temperature is 60-120 ℃.
8. The preparation method of the self temperature-controlling current collector of the lithium ion battery as claimed in claim 1, characterized by comprising the following steps:
plating a conductive material on any one surface of a polymer thin film layer through evaporation coating, magnetron sputtering or slurry coating to obtain a single-sided conductive polymer thin film layer;
compounding high-conductivity metal on the non-conductive surface of the single-side conductive polymer film layer through screen printing, evaporation coating, magnetron sputtering or attaching to form an electric heating layer electrode;
step three, preparing self-temperature-control electric heating ink slurry, coating the slurry on the non-conductive surface of the single-surface conductive polymer film layer provided with the electric heating layer electrode, and drying and curing at 60-120 ℃ for 4-8 hours to obtain a self-temperature-control electric heating layer;
and fourthly, carrying out hot-pressing compounding on the non-conductive surface of the other single-side conductive polymer film layer and the automatic temperature control electric heating layer under the conditions that the pressure is 1-10MPa and the temperature is 60-120 ℃ to obtain the self temperature control current collector of the lithium ion battery.
9. The application of the self-temperature-control current collector of the lithium ion battery as claimed in any one of claims 1 to 7 in heating of the lithium ion battery at a low temperature, wherein the self-temperature-control electric heating layer (4) is driven to operate by applying direct current or alternating current to the self-temperature-control electric heating layer through an external power supply, so that the temperature of the lithium ion battery is raised to the operating temperature.
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