CN112952103B - Preparation method and application of intelligent temperature-regulating current collector - Google Patents
Preparation method and application of intelligent temperature-regulating current collector Download PDFInfo
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- CN112952103B CN112952103B CN202110233697.7A CN202110233697A CN112952103B CN 112952103 B CN112952103 B CN 112952103B CN 202110233697 A CN202110233697 A CN 202110233697A CN 112952103 B CN112952103 B CN 112952103B
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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
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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
- 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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/60—Heating or cooling; Temperature control
- H01M10/61—Types of temperature control
- H01M10/613—Cooling or keeping cold
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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
- 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
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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
- 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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/60—Heating or cooling; Temperature control
- H01M10/65—Means for temperature control structurally associated with the cells
- H01M10/659—Means for temperature control structurally associated with the cells by heat storage or buffering, e.g. heat capacity or liquid-solid phase changes or transition
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- 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
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Abstract
The invention discloses a preparation method and application of an intelligent temperature-regulating current collector, and aims to keep the temperature of a lithium ion battery constant and solve the problem of performance deterioration when the battery is overheated and cooled. The current collector does not require additional energy supplied from the outside: when the battery is overheated, the intelligent temperature regulating layer in the current collector can store redundant heat, so that the temperature of the battery is reduced; when the battery is cold, the intelligent temperature regulating layer in the current collector releases the stored heat to improve the temperature of the battery. Therefore, the intelligent temperature regulating layer can carry out peak clipping and valley filling type management on the heat of the battery, and the purpose of intelligent temperature control is achieved. The invention has the advantages of high response speed, stable and controllable heat storage and release process, simple structure, high integration level, no temperature control element and system, no occupation of battery module space, low cost and the like without using extra energy provided by the outside.
Description
Technical Field
The invention relates to a preparation method and application of an intelligent temperature-regulating current collector, in particular to a current collector with intelligent temperature-regulating capability.
Background
The lithium ion battery has the advantages of high open circuit voltage, high energy density, long cycle life, environmental protection, small self discharge and the like, and is used in electronic equipment, electric automobiles and the likeThe energy storage system has wide application in the fields of energy storage systems and the like. However, during the use of the lithium ion battery, if the battery temperature exceeds the normal working range (0-40 DEG to o C) When it comes, it may have a detrimental effect. For example, when the battery temperature suddenly rises (above 60 oC Above), irreversible side reactions occur inside the lithium ion battery, leading to irreversible decay of the battery capacity, and even risk of combustion or explosion of the battery. For another example, in a low-temperature environment (generally referred to as subzero temperature), the lithium ion battery is limited in use, and problems such as electric quantity dip and charging difficulty occur, which seriously affect user experience. It is a significant challenge to control the temperature of lithium ion batteries within normal operating ranges.
In the literature, the temperature of the battery cell or the battery module is often regulated by external energy (such as a heating element, a refrigerating device, etc.). For example, patent CN108107940a proposes a temperature regulation integrated control system and a battery pack. The temperature regulation and control integrated control system comprises a controller, a first temperature sensor, a second temperature sensor, a heating device and an air cooling device, wherein the first temperature sensor, the second temperature sensor, the heating device and the air cooling device are connected with the controller, and the heating device and the air cooling device are arranged outside a battery box; the first temperature sensor is used for detecting the temperature of the battery box, and the second temperature sensor is used for detecting the temperature of the heating device. The controller selectively controls the heating device to heat the battery box or controls the air cooling device to cool the battery box according to the temperature feedback detected by the first temperature sensor; when the second temperature sensor detects that the temperature of the heating device exceeds the temperature threshold value in the working process of the heating device, the controller controls the heating device to be closed and stops heating so as to protect the heating device and realize automatic control of the battery box. For another example, patent CN208939113U proposes a temperature-controlled energy storage module consisting of a box, a controller, a battery cell, a temperature sensor, a metal heat pipe, a flow control instrument and a liquid nitrogen source. The temperature sensor is arranged on the battery cell and is used for detecting the temperature value of the battery cell; the temperature sensor is connected with the controller; the surface of the battery core is provided with a metal heat conduction pipe; the metal heat-conducting pipe is connected with a liquid nitrogen source through the flow controller; the flow controller is used for controlling the flow rate and the flow of the liquid nitrogen; the flow controller is controlled by the controller.
Obviously, the patents all have the defects of external extra energy supply, delayed response time (temperature measurement is generally carried out by a temperature sensor, and then heating or refrigerating is started), slow temperature regulation (a mode of conducting outside the battery into the battery), complex structure (a large number of components are needed, including a heating element or a refrigerating device, a thermistor, a fuse, a switch and the like), low space utilization rate of the battery module (the volume specific capacity and the mass specific capacity of the battery module are greatly reduced), complex process, high cost and the like.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a preparation method and application of an intelligent temperature-regulating current collector. The intelligent temperature-regulating current collector does not need extra energy provided by the outside, and when the battery is overheated, the intelligent temperature-regulating layer in the current collector can store excessive heat, so that the temperature of the battery is reduced; when the battery is cold, the intelligent temperature-regulating layer in the current collector releases the stored heat to increase the temperature of the battery. Therefore, the intelligent temperature regulating layer can carry out peak clipping and valley filling type management on the heat of the battery, and the purpose of intelligent temperature control is achieved. The specific technical scheme is as follows:
a preparation method of an intelligent temperature-regulating current collector comprises the following steps:
s1, preparing phase-change heat storage composite slurry by taking an inorganic phase-change heat storage material, an organic phase-change heat storage material, a binder, a flame retardant and a solvent as raw materials;
s2, uniformly coating the phase-change heat storage composite slurry obtained in the step S1 on a non-conductive surface of a single-sided aluminum/copper-plastic composite film, and curing to obtain an intelligent temperature regulating layer;
and S3, stacking the intelligent temperature regulating layer, the hot melt adhesive film and the non-conductive surface of the single-sided aluminum/copper plastic composite film obtained in the step S2 in sequence, and then carrying out hot pressing compounding to obtain the intelligent temperature regulating current collector.
Further, the phase-change heat storage composite slurry is prepared from the following components in parts by weight: 50-55 parts by weight of inorganic phase-change heat storage material, 30-35 parts by weight of organic phase-change heat storage material, 5-10 parts by weight of binder, 5-10 parts by weight of flame-retardant heat-conducting agent and 200-400 parts by weight of solvent.
Further, the solidification condition of the intelligent temperature-regulating layer is that the temperature is kept at 60-120 ℃ for 4-8 hours.
Furthermore, the intelligent temperature regulating layer has the advantages of stable and controllable heat storage/release process and the like, the working temperature is 30-60 ℃, and the thickness of the intelligent temperature regulating layer is 5-10 mu m.
Further, the single-sided aluminum-plastic composite film is formed by single-sided aluminum-plated PET, single-sided aluminum-plated PP, single-sided aluminum-plated PE, single-sided aluminum-plated PI, single-sided aluminum-plated PVC and the like, and is used for loading battery anode materials, and the thickness is 10-20 mu m; the single-sided copper plastic composite film is formed by single-sided copper-plated PET, single-sided copper-plated PP, single-sided copper-plated PE, single-sided copper-plated PI, single-sided copper-plated PVC and the like, and is used for loading battery cathode materials, and the thickness is 10-20 mu m.
Further, the hot melt adhesive film is one or more of PES hot melt adhesive film, PA hot melt adhesive film, TPU hot melt adhesive film, PO hot melt adhesive film and EVA hot melt adhesive film, and the thickness is 5-10 μm.
Further, the hot pressing compounding condition is that the pressure is 1-6MPa and the temperature is 80-180 ℃.
The intelligent temperature-regulating current collector prepared by the preparation method of the intelligent temperature-regulating current collector is applied to a lithium ion battery current collector.
The beneficial effects are that:
the intelligent temperature-regulating current collector prepared by the invention does not need extra energy provided by the outside, and has the characteristics of high response speed, stable and controllable heat storage and release process, high integration level, simple structure, no temperature control element and system, no occupation of battery module space, low cost and the like.
Drawings
Fig. 1 is a structural diagram of an intelligent temperature regulating current collector of the present invention.
Detailed Description
The technical scheme of the present invention is further described below by way of examples with reference to the accompanying drawings, but the scope of the present invention is not limited thereto.
As shown in fig. 1, the preparation method of the intelligent temperature-regulating current collector comprises the following steps:
s1, preparing phase-change heat storage composite slurry by taking an inorganic phase-change heat storage material, an organic phase-change heat storage material, a binder, a flame retardant and a solvent as raw materials;
s2, uniformly coating the phase-change heat storage composite slurry obtained in the step S1 on a non-conductive surface of the single-sided aluminum/copper plastic composite film 1, and curing to obtain an intelligent temperature regulating layer 2;
and S3, stacking the intelligent temperature regulating layer 2, the hot melt adhesive film and the non-conductive surface of the single-sided aluminum/copper plastic composite film 1 obtained in the step S2 in sequence, and then carrying out hot pressing compounding to obtain the intelligent temperature regulating current collector.
The phase-change heat storage composite slurry is prepared from the following components in parts by weight: 50-55 parts by weight of an inorganic phase change heat storage material (such as Na 2 SO 4 ·10H 2 O、NaCH 3 COO·3H 2 O、Na 2 HPO 4 ·12H 2 O、Na 2 CO 3 ·12H 2 O、Ca（NO 3 ） 2 ·4H 2 O, etc.), 30-35 parts by weight of organic phase-change heat storage material (such as paraffin, lauric acid, capric acid, etc.), 5-15 parts by weight of binder (such as polyethylene oxide (PEO), polyethersulfone resin (PES), polyurethane elastomer rubber (TPU), ethylene-vinyl acetate copolymer (EVA), polycaprolactone (PCL), etc.), 1-5 parts by weight of flame retardant heat conductive agent (such as SiO 2 、Al 2 O 3 、MgO、AlN、Si 3 N 4 、BN、SiC、B 4 C, etc.), 200-400 parts by weight of a solvent (e.g., N-methylpyrrolidone, isopropyl alcohol, N-dimethylformamide, ethyl acetate, N-dimethylacetamide, acetonitrile, toluene, etc.).
The solidification condition of the intelligent temperature-regulating layer 2 is that the temperature is kept at 60-120 ℃ for 4-8 hours.
The intelligent temperature regulating layer 2 has the advantages of stable and controllable heat storage/release process and the like, the working temperature is 30-60 ℃, and the thickness of the intelligent temperature regulating layer is 5-10 mu m.
The single-sided aluminum-plastic composite film is formed by single-sided aluminum-plated PET, single-sided aluminum-plated PP, single-sided aluminum-plated PE, single-sided aluminum-plated PI, single-sided aluminum-plated PVC and the like, and is used for loading a battery anode material, and the thickness is 10-20 mu m; the single-sided copper plastic composite film is formed by single-sided copper-plated PET, single-sided copper-plated PP, single-sided copper-plated PE, single-sided copper-plated PI, single-sided copper-plated PVC and the like, and is used for loading battery cathode materials, and the thickness is 10-20 mu m.
The hot melt adhesive film is PES hot melt adhesive film, PA hot melt adhesive film, TPU hot melt adhesive film, PO hot melt adhesive film, EVA hot melt adhesive film, etc., and the thickness is 5-10 μm.
The hot-pressing compounding condition is that the pressure is 1-6MPa and the temperature is 80-180 ℃.
The intelligent temperature-regulating current collector is applied to a lithium ion battery current collector.
Example 1:
first, 50 parts by weight of Na 2 SO 4 ·10H 2 O, 35 parts by weight of paraffin wax, 10 parts by weight of PEO, 5 parts by weight of Al 2 O 3 And 300 parts by weight of acetonitrile is used as a formula to prepare the phase-change heat storage composite slurry. The phase-change heat storage composite slurry is uniformly coated on a non-aluminum-plated surface of a single-sided aluminum-plated PET film (with the thickness of 20 mu m), and an intelligent temperature-regulating layer with the thickness of 10 mu m is obtained after drying and curing for 8 hours at the temperature of 60 ℃. Then, stacking the single-sided aluminized PET film provided with the intelligent temperature regulating layer, the EVA hot melt adhesive film (with the thickness of 5 mu m) and the non-aluminized surface of the single-sided aluminized PET film, and carrying out hot pressing and compounding under the condition that the pressure is 1MPa and the temperature is 80 ℃ to obtain the intelligent temperature regulating current collector.
Example 2:
first, 55 parts by weight of Na 2 HPO 4 ·12H 2 O, 30 parts by weight of lauric acid, 14 parts by weight of TPU, 1 part by weight of SiO 2 300 parts by weight of N-methyl pyrrolidone is used as a formula to prepare the phase-change heat storage composite slurry. The phase-change heat storage composite slurry is uniformly coated on a non-copper-plated surface of a single-sided copper-plated PI film (the thickness is 10 mu m), and an intelligent temperature-regulating layer is obtained after drying and curing for 8 hours at 120 ℃, wherein the thickness is 10 mu m. Then, stacking the single-sided copper-plated PI film provided with the intelligent temperature-regulating layer, a PES hot melt adhesive film (with the thickness of 5 mu m) and a non-copper-plated surface of the single-sided copper-plated PI film, and carrying out hot pressing and compounding under the condition of the pressure of 6MPa and the temperature of 180 ℃ to obtain the intelligent temperature-regulating current collector.
Example 3:
first, 52 parts by weight of Ca (NO 3 ） 2 ·4H 2 O, 33 parts by weight of paraffin, 12 parts by weight of EVA, 3 parts by weight of Al 2 O 3 300 parts by weight of N, N-dimethylformamide is used as a formula to prepare the phase-change heat storage composite slurry. The phase-change heat storage composite slurry is uniformly coated on a non-aluminum-plated surface of a single-sided aluminum-plated PVC film (with the thickness of 12 mu m), and an intelligent temperature-regulating layer with the thickness of 6 mu m is obtained after drying and curing for 8 hours at 80 ℃. And then stacking the single-sided aluminized PVC film provided with the intelligent temperature regulating layer, the TPU hot melt adhesive film (the thickness is 6 mu m) and the non-aluminized surface of the single-sided aluminized PVC film, and carrying out hot pressing and compounding under the condition of the pressure of 2MPa and the temperature of 100 ℃ to obtain the intelligent temperature regulating current collector.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the technical aspects set forth in the claims.
Claims (7)
1. The preparation method of the intelligent temperature-regulating current collector is characterized by comprising the following steps of:
s1, preparing phase-change heat storage composite slurry by taking an inorganic phase-change heat storage material, an organic phase-change heat storage material, a binder, a flame retardant and a solvent as raw materials;
s2, uniformly coating the phase-change heat storage composite slurry obtained in the step S1 on a non-conductive surface of a single-sided aluminum/copper plastic composite film (1), and curing to obtain an intelligent temperature regulating layer (2);
s3, stacking the non-conductive surface of the single-sided aluminum/copper plastic composite film (1), the hot melt adhesive film and the intelligent temperature regulating layer (2) obtained in the S2, the other hot melt adhesive film and the non-conductive surface of the other single-sided aluminum/copper plastic composite film (1) in sequence, and then performing hot pressing compounding to obtain an intelligent temperature regulating current collector;
the single-sided aluminum-plastic composite film is one of single-sided aluminum-plated PET, single-sided aluminum-plated PP, single-sided aluminum-plated PE, single-sided aluminum-plated PI and single-sided aluminum-plated PVC, and is used for loading a battery anode material, and the thickness is 10-20 mu m; the single-sided copper plastic composite film is one of single-sided copper-plated PET, single-sided copper-plated PP, single-sided copper-plated PE, single-sided copper-plated PI and single-sided copper-plated PVC, and is used for loading a battery cathode material, and the thickness is 10-20 mu m.
2. The preparation method of the intelligent temperature-regulating current collector according to claim 1, wherein the phase-change heat storage composite slurry is prepared from the following components in parts by weight: 50-55 parts by weight of inorganic phase-change heat storage material, 30-35 parts by weight of organic phase-change heat storage material, 5-10 parts by weight of binder, 5-10 parts by weight of flame-retardant heat-conducting agent and 200-400 parts by weight of solvent.
3. The method for preparing the intelligent temperature-regulating current collector according to claim 1, wherein the solidification condition of the intelligent temperature-regulating layer (2) is 60-120 ℃ for 4-8 hours.
4. The method for preparing the intelligent temperature-regulating current collector according to claim 1, wherein the intelligent temperature-regulating layer has the advantages of stable and controllable heat storage/release process, the working temperature is 30-60 ℃, and the thickness of the intelligent temperature-regulating layer is 5-10 μm.
5. The method for preparing the intelligent temperature-regulating current collector according to claim 1, wherein the hot melt adhesive film is one or more of PES hot melt adhesive film, PA hot melt adhesive film, TPU hot melt adhesive film, PO hot melt adhesive film and EVA hot melt adhesive film, and the thickness is 5-10 μm.
6. The method for preparing an intelligent temperature-regulating current collector according to claim 1, wherein the hot-pressing compounding condition is that the pressure is 1-6MPa and the temperature is 80-180 ℃.
7. Use of an intelligent temperature regulating current collector manufactured according to the manufacturing method of an intelligent temperature regulating current collector as claimed in claim 1 as a lithium ion battery current collector.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011058979A1 (en) * | 2009-11-10 | 2011-05-19 | トヨタ自動車株式会社 | Lithium secondary battery |
| JP2018014249A (en) * | 2016-07-21 | 2018-01-25 | 日産自動車株式会社 | Method of manufacturing electrode |
| WO2020220945A1 (en) * | 2019-04-29 | 2020-11-05 | 宁德时代新能源科技股份有限公司 | Positive plate of sulfide solid-state battery, sulfide solid-state battery and device |
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| CN103509529B (en) * | 2013-09-29 | 2016-01-20 | 浙江工业大学 | A kind of Phase-change ceramic grain and preparation method thereof |
| WO2018060646A1 (en) * | 2016-09-28 | 2018-04-05 | Valeo Systemes Thermiques | Collector box comprising a phase change material and heat exchanger comprising such a collector box |
| CN110957539B (en) * | 2018-09-27 | 2021-03-12 | 北京好风光储能技术有限公司 | Heatable bipolar battery |
| CN109830774B (en) * | 2019-01-10 | 2021-06-22 | 欣旺达电子股份有限公司 | Self-cooling heat dissipation current collector and power battery cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011058979A1 (en) * | 2009-11-10 | 2011-05-19 | トヨタ自動車株式会社 | Lithium secondary battery |
| JP2018014249A (en) * | 2016-07-21 | 2018-01-25 | 日産自動車株式会社 | Method of manufacturing electrode |
| WO2020220945A1 (en) * | 2019-04-29 | 2020-11-05 | 宁德时代新能源科技股份有限公司 | Positive plate of sulfide solid-state battery, sulfide solid-state battery and device |
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