CN112952103A - Preparation method and application of intelligent temperature-regulating current collector - Google Patents

Preparation method and application of intelligent temperature-regulating current collector Download PDF

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Publication number
CN112952103A
CN112952103A CN202110233697.7A CN202110233697A CN112952103A CN 112952103 A CN112952103 A CN 112952103A CN 202110233697 A CN202110233697 A CN 202110233697A CN 112952103 A CN112952103 A CN 112952103A
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intelligent temperature
current collector
temperature
plated
battery
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CN112952103B (en
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夏阳
余里悦
张文魁
张俊
贺馨平
黄辉
甘永平
梁初
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/64Carriers or collectors
    • H01M4/66Selection of materials
    • H01M4/665Composites
    • H01M4/667Composites in the form of layers, e.g. coatings
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/60Heating or cooling; Temperature control
    • H01M10/61Types of temperature control
    • H01M10/613Cooling or keeping cold
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/60Heating or cooling; Temperature control
    • H01M10/61Types of temperature control
    • H01M10/615Heating or keeping warm
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/60Heating or cooling; Temperature control
    • H01M10/65Means for temperature control structurally associated with the cells
    • H01M10/654Means for temperature control structurally associated with the cells located inside the innermost case of the cells, e.g. mandrels, electrodes or electrolytes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/60Heating or cooling; Temperature control
    • H01M10/65Means for temperature control structurally associated with the cells
    • H01M10/659Means for temperature control structurally associated with the cells by heat storage or buffering, e.g. heat capacity or liquid-solid phase changes or transition
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

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 problems of overheating and performance deterioration of the battery in case of cooling. The current collector does not need additional energy provided by 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 cooled, the intelligent temperature regulating layer in the current collector releases the stored heat, so that the temperature of the battery is increased. 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 no need of extra energy provided by the outside, 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 the space of the battery module, low cost and the like.

Description

Preparation method and application of intelligent temperature-regulating current collector
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 friendliness, small self-discharge and the like, and is widely applied to the fields of electronic equipment, electric automobiles, energy storage systems and the like. However, when the lithium ion battery is in use, if the battery temperature exceeds the normal working range (0-40)oC) And can cause deleterious effects. For example, when the battery temperature suddenly rises (above 60 deg.C) oCAbove), irreversible side reactions occur inside the lithium ion battery, resulting in irreversible degradation of the battery capacity, and even the risk of battery combustion or explosion. For another example, in a low-temperature environment (generally, refer to a temperature below zero), the use of the lithium ion battery is limited, and problems such as sudden drop of electric quantity and difficulty in charging occur, which seriously affects user experience. Therefore, how to control the temperature of the lithium ion battery within the normal operating range is a significant challenge.
In the description of the related documents, the temperature of the battery cell or the battery module is often regulated by means of external energy (such as a heating element, a refrigeration device, etc.). For example, patent CN108107940A proposes an integrated temperature 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; 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 selects the control heating device to heat the battery box or 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 self temperature of the heating device in the working process exceeds the temperature threshold value, the controller controls the heating device to be closed and stops heating, so that the heating device is protected, and the automatic control of the battery box is realized. For another example, patent CN208939113U proposes a temperature-controlled energy storage module consisting of a box, a controller, an electrical core, 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 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 conduction pipe is connected with the liquid nitrogen source through the flow controller; the flow control instrument is used for controlling the flow speed and flow of the liquid nitrogen; the flow controller is controlled by the controller.
Obviously, such patents have the disadvantages of external energy supply, response time lag (generally, a temperature sensor is needed to measure the temperature and then start heating or cooling), slow temperature regulation (the mode of conducting the temperature outside the battery into the battery), complex structure (a large number of components are needed, including a heating element or a cooling device, a thermistor, a fuse, a switch and the like), low space utilization rate of the battery module (the volumetric capacity and the gravimetric 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 to use extra energy provided by the outside, and when the battery is overheated, the intelligent temperature-regulating layer in the current collector can store the extra heat, so that the temperature of the battery is reduced; when the battery is cooled, 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 the non-electric conducting surface of the single-sided aluminum/copper-plastic composite film, and curing to obtain an intelligent temperature-regulating layer;
and S3, stacking the intelligent temperature-regulating layer obtained in the step S2, the hot melt adhesive film and the non-conductive surface of the single-sided aluminum/copper-plastic composite film in sequence, and performing 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 of inorganic phase change heat storage material, 30-35 parts of organic phase change heat storage material, 5-10 parts of binder, 5-10 parts of flame-retardant heat-conducting agent and 200-400 parts of solvent.
Further, the curing condition of the intelligent temperature-regulating layer is that the temperature is kept for 4-8 hours at 60-120 ℃.
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 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, is used for loading a battery anode material, and has the thickness of 10-20 micrometers; the single-sided copper-plastic composite film is made of 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, is used for loading a battery negative electrode material, and has the thickness of 10-20 mu m.
Furthermore, 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 as a lithium ion battery current collector.
Has the advantages that:
the intelligent temperature-regulating current collector manufactured by the invention does not need to use 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 block diagram of an intelligent temperature regulating 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, the method for preparing the intelligent temperature-regulating current collector of the present invention 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 the non-electric conducting 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 obtained in the step S2, a hot melt adhesive film and the non-conductive surface of the single-sided aluminum/copper-plastic composite film 1 in sequence, and performing 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 inorganic phase change heat storage material (such as Na)2SO4·10H2O、NaCH3COO·3H2O、Na2HPO4·12H2O、Na2CO3·12H2O、Ca(NO32·4H2O, etc.), 30-35 parts by weight of organic phase change heat storage material (such as paraffin, lauric acid, caprylic acid, capric acid, etc.), 5-15 parts by weight of binder (such as polyethylene oxide (PEO), polyether sulfone resin (PES), polyurethaneEster elastomer rubber (TPU), ethylene-vinyl acetate copolymer (EVA), Polycaprolactone (PCL) and the like), and 1-5 parts by weight of flame-retardant heat-conducting agent (such as SiO)2、Al2O3、MgO、AlN、Si3N4、BN、SiC、B4C, etc.), 200-400 parts by weight of a solvent (e.g., N-methylpyrrolidone, isopropanol, N-dimethylformamide, ethyl acetate, N-dimethylacetamide, acetonitrile, toluene, etc.).
The curing condition of the intelligent temperature-regulating layer 2 is that the temperature is kept for 4-8 hours at 60-120 ℃.
The intelligent temperature-regulating layer 2 has the advantages of stable and controllable heat storage/release process, working temperature of 30-60 ℃, and thickness of the intelligent temperature-regulating layer of 5-10 μm.
The single-sided aluminum-plastic composite film is 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, is used for loading a battery anode material, and has the thickness of 10-20 mu m; the single-sided copper-plastic composite film is made of 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, is used for loading a battery negative electrode material, and has the thickness of 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 and the like, and the thickness is 5-10 mu m.
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 as a current collector of a lithium ion battery.
Example 1:
first, 50 parts by weight of Na2SO4·10H2O, 35 parts by weight of paraffin wax, 10 parts by weight of PEO, 5 parts by weight of Al2O3And 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 the non-aluminized surface of a single-sided aluminized PET film (the thickness is 20 mu m), and an intelligent temperature-regulating layer is obtained after drying and curing for 8 hours at 60 ℃ and the thickness of the intelligent temperature-regulating layer is 10 mu m. Then, the single-side aluminized PET film provided with the intelligent temperature adjusting layer, the EVA hot melt adhesive film (the thickness is 5 μm) and the non-single-side aluminized PET filmAnd stacking the aluminized surfaces, and performing hot-pressing compounding under the conditions 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 Na2HPO4·12H2O, 30 parts by weight of lauric acid, 14 parts by weight of TPU, 1 part by weight of SiO2And 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-side 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 ℃ and the thickness is 10 mu m. Then, stacking the single-sided copper-plated PI film with the intelligent temperature regulating layer, the PES hot melt adhesive film (the thickness is 5 μm) and the non-copper-plated side of the single-sided copper-plated PI film, and performing hot-pressing compounding under the conditions 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)32·4H2O, 33 parts by weight of paraffin wax, 12 parts by weight of EVA, and 3 parts by weight of Al2O3And 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 the non-aluminized surface of a single-sided aluminized PVC film (the thickness is 12 mu m), and an intelligent temperature-regulating layer is obtained after drying and curing for 8 hours at 80 ℃ and the thickness is 6 mu m. Then, stacking the single-sided aluminum-plated PVC film provided with the intelligent temperature-regulating layer, the TPU hot-melt adhesive film (the thickness is 6 microns) and the non-aluminum-plated surface of the single-sided aluminum-plated PVC film, and performing hot-pressing compounding under the conditions of the pressure of 2MPa and the temperature of 100 ℃ to obtain the intelligent temperature-regulating current collector.
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 (8)

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 the non-electric-conduction 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 non-conductive surfaces of the intelligent temperature-regulating layer (2), the hot-melt adhesive film and the single-sided aluminum/copper-plastic composite film (1) obtained in the step S2 in sequence, and performing hot-pressing compounding to obtain the intelligent temperature-regulating current collector.
2. The preparation method of the intelligent temperature-regulating current collector as claimed in claim 1, wherein the phase-change heat-storage composite slurry is prepared from the following components in parts by weight: 50-55 parts of inorganic phase change heat storage material, 30-35 parts of organic phase change heat storage material, 5-10 parts of binder, 5-10 parts of flame-retardant heat-conducting agent and 200-400 parts of solvent.
3. The preparation method of the intelligent temperature-regulating current collector as claimed in claim 1, wherein the curing condition of the intelligent temperature-regulating layer (2) is 60-120 ℃ for 4-8 hours.
4. The preparation method of the intelligent temperature-regulating current collector as claimed in 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 preparation method of the intelligent temperature-regulating current collector according to claim 1, wherein the single-sided aluminum-plastic composite film is 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, is used for loading a battery anode material, and has a thickness of 10-20 μm; the single-sided copper-plastic composite film is made of 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, is used for loading a battery negative electrode material, and has the thickness of 10-20 mu m.
6. The preparation method of the intelligent temperature-regulating current collector as claimed in 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.
7. The method for preparing the 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 ℃.
8. The application of the intelligent temperature-regulating current collector prepared by the preparation method of the intelligent temperature-regulating current collector according to claim 1 as a lithium ion battery current collector.
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Citations (7)

* Cited by examiner, † Cited by third party
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
CN103509529A (en) * 2013-09-29 2014-01-15 浙江工业大学 Phase-change ceramic grain and preparation method thereof
JP2018014249A (en) * 2016-07-21 2018-01-25 日産自動車株式会社 Method of manufacturing electrode
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
CN109830774A (en) * 2019-01-10 2019-05-31 欣旺达电子股份有限公司 From cooling heat dissipation collector and electrical core of power battery
CN110957539A (en) * 2018-09-27 2020-04-03 北京好风光储能技术有限公司 Heatable bipolar battery
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

Patent Citations (7)

* Cited by examiner, † Cited by third party
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
CN103509529A (en) * 2013-09-29 2014-01-15 浙江工业大学 Phase-change ceramic grain and preparation method thereof
JP2018014249A (en) * 2016-07-21 2018-01-25 日産自動車株式会社 Method of manufacturing electrode
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
CN110957539A (en) * 2018-09-27 2020-04-03 北京好风光储能技术有限公司 Heatable bipolar battery
CN109830774A (en) * 2019-01-10 2019-05-31 欣旺达电子股份有限公司 From cooling heat dissipation collector and electrical core of power battery
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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