CN112952103B - Preparation method and application of intelligent temperature-regulating current collector - Google Patents

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

Preparation method and application of an 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 the ability to intelligently adjust temperature.

Background technique

Lithium-ion batteries have the advantages of high open-circuit voltage, high energy density, long cycle life, environmental friendliness, and low self-discharge, and are widely used in electronic equipment, electric vehicles, and energy storage systems. However, during the use of lithium-ion batteries, if the battery temperature exceeds the normal operating range (0~40 ^o C), it will cause harmful effects. For example, when the battery temperature rises suddenly (above 60 ^oC ), irreversible side reactions will occur inside the lithium-ion battery, resulting in irreversible attenuation of battery capacity, and even the risk of battery combustion or explosion. Another example is that in a low-temperature environment (generally refers to sub-zero temperature), the use of lithium-ion batteries is limited, and there are problems such as sudden power drop and charging difficulties, which seriously affect the user experience. Therefore, how to control the temperature of lithium-ion batteries within the normal operating range is a major challenge.

In the relevant literature, it is often used to regulate the temperature of the battery cell or battery module by means of external energy (such as heating elements, cooling devices, etc.). For example, the patent CN108107940A proposes a temperature regulation integrated control system and a battery pack. The temperature regulation integrated control system includes a controller, a first temperature sensor connected to the controller, a second temperature sensor, a heating device and an air cooling device, and the heating device and the air cooling device are arranged outside the battery box; the first The temperature sensor is used to detect the temperature of the battery box, and the second temperature sensor is used to detect the temperature of the heating device. According to the temperature feedback detected by the first temperature sensor, the controller selects and controls the heating device to heat the battery box or the air cooling device to cool the battery box; when the second temperature sensor detects that the temperature of the heating device itself exceeds its temperature threshold, the controller Control the heating device to turn off and stop heating to protect the heating device and realize automatic control of the battery box. As another example, patent CN208939113U proposes a temperature-controlled energy storage module consisting of a cabinet, 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 electric core, and the temperature sensor is used to detect the temperature value of the electric core; the temperature sensor is connected with the controller; the surface of the electric core is arranged with a metal heat pipe; the metal heat pipe passes through the flow controller and the liquid nitrogen source connected; the flow controller is used to control the flow rate and flow of liquid nitrogen; the flow controller is controlled by the controller.

Obviously, such patents all have the need for external additional energy, lag in response time (generally requires a temperature sensor to measure the temperature, and then start heating or cooling), slow temperature adjustment (the way the battery conducts from the outside to the inside of the battery), complex structure (requires A large number of components, including heating elements or cooling devices, thermistors, fuses, switches, etc.), low space utilization of the battery module (resulting in a significant reduction in the volume-specific capacity and mass-specific capacity of the battery module), complex processes, and cost High disadvantages.

Contents of the invention

In order to solve the above-mentioned deficiencies in the prior art, the present invention proposes 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. When the battery is overheated, the intelligent temperature-regulating layer in the current collector will store excess heat and reduce the battery temperature; and when the battery is cold, the intelligent temperature-regulating layer inside the current collector will The temperature layer releases the stored heat and increases the battery temperature. Therefore, the intelligent temperature regulation layer can manage the heat of the battery in a "peak-shaving and valley-filling" manner to achieve the purpose of intelligent temperature control. The specific technical scheme is as follows:

A method for preparing an intelligent temperature-regulating current collector, comprising the steps of:

S1: Prepare phase change heat storage composite slurry with inorganic phase change heat storage materials, organic phase change heat storage materials, binders, flame retardants, and solvents as raw materials;

S2: Evenly coat the phase-change heat storage composite slurry obtained in S1 on the non-conductive surface of the single-sided aluminum/copper-plastic composite film, and obtain an intelligent temperature-regulating layer after curing;

S3: 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 S2 are stacked in sequence, and then hot-pressed and laminated to obtain an intelligent temperature-regulating current collector.

Further, the phase change heat storage composite slurry is made of the following components by weight: 50-55 parts by weight of inorganic phase change heat storage materials, 30-35 parts by weight of organic phase change heat storage materials, 5 parts by weight - 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 curing condition of the intelligent temperature-regulating layer is 60-120° C. for 4-8 hours.

Further, the intelligent temperature-regulating layer has the advantages of stable and controllable heat storage/radiation process, the working temperature is 30-60°C, and the thickness of the intelligent temperature-regulating layer is 5-10 μm.

Further, the single-sided aluminum-plastic composite film is single-sided aluminized PET, single-sided aluminized PP, single-sided aluminized PE, single-sided aluminized PI, single-sided aluminized PVC, etc., which are used to load the positive electrode material of the battery. The thickness is 10-20 μm; the single-sided copper-plastic composite film is single-sided copper-plated PET, single-sided copper-plated PP, single-side copper-plated PE, single-side copper-plated PI, single-side copper-plated PVC, etc., used for load batteries The negative electrode material has a thickness of 10-20 μm.

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, EVA hot-melt adhesive film, with a thickness of 5- 10 μm.

Further, the hot-pressing composite conditions are pressure 1-6MPa and temperature 80-180°C.

An application of the intelligent temperature-regulating current collector prepared by the method for preparing the intelligent temperature-regulating current collector as a lithium-ion battery current collector.

Beneficial effect:

The intelligent temperature-regulating current collector prepared by the present invention does not need additional energy provided by the outside, and has the characteristics of fast response, stable and controllable heat storage and discharge process, high integration, simple structure, no temperature control elements and systems, and no battery modules. Group space, low cost and other characteristics.

Description of drawings

Fig. 1 is a structural diagram of an intelligent temperature-regulating current collector of the present invention.

Detailed ways

The technical solution of the present invention will be further elaborated below through the embodiments, in conjunction with the accompanying drawings, but the protection scope of the present invention is not limited thereto.

As shown in Figure 1, the preparation method of the intelligent temperature-regulating current collector of the present invention comprises the following steps:

S1: Prepare phase change heat storage composite slurry with inorganic phase change heat storage materials, organic phase change heat storage materials, binders, flame retardants, and solvents as raw materials;

S2: Evenly apply the phase-change heat storage composite slurry obtained in S1 on the non-conductive surface of the single-sided aluminum/copper-plastic composite film 1, and obtain the intelligent temperature-regulating layer 2 after curing;

S3: The intelligent temperature-regulating layer 2 obtained in S2, the hot-melt adhesive film, and the non-conductive surface of the single-sided aluminum/copper-plastic composite film 1 are stacked in sequence, and then hot-pressed and laminated to obtain an intelligent temperature-regulating current collector.

The phase change heat storage composite slurry is made of the following components by weight: 50-55 parts by weight of inorganic phase change heat storage materials (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 materials (such as paraffin, lauric acid , capric acid, capric acid, etc.), 5-15 parts by weight of binders (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 conducting 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 solvents (such as N-methylpyrrolidone, isopropanol, N,N-dimethylformamide, ethyl acetate, N,N-dimethylacetamide, acetonitrile, toluene, etc. ).

The curing condition of the intelligent temperature-regulating layer 2 is 60-120° C. for 4-8 hours.

The intelligent temperature-regulating layer 2 has the advantages of a stable and controllable heat storage/release process, the working temperature is 30-60° C., and the thickness of the intelligent temperature-regulating layer is 5-10 μm.

The single-sided aluminum-plastic composite film is single-sided aluminized PET, single-sided aluminized PP, single-sided aluminized PE, single-sided aluminized PI, single-sided aluminized PVC, etc., and is used to load the positive electrode material of the battery, with a thickness of 10 -20 μm; the single-sided copper-plastic composite film is single-sided copper-plated PET, single-sided copper-plated PP, single-side copper-plated PE, single-side copper-plated PI, single-side copper-plated PVC, etc., used to load the negative electrode material of the battery, The thickness is 10-20 μm.

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., with a thickness of 5-10 μm.

The hot-pressing composite conditions are pressure of 1-6 MPa and temperature of 80-180°C.

The application of the intelligent temperature-regulating current collector as a lithium-ion battery current collector.

Example 1:

First, a phase change heat storage composite was prepared according to the formula of 50 parts by weight of Na ₂ SO ₄ ·10H ₂ O, 35 parts by weight of paraffin, 10 parts by weight of PEO, 5 parts by weight of Al ₂ O ₃ , and 300 parts by weight of acetonitrile. slurry. The phase change heat storage composite slurry was uniformly coated on the non-aluminized surface of the single-sided aluminized PET film (thickness 20 μm), and dried and cured at 60°C for 8 hours to obtain an intelligent temperature-regulating layer with a thickness of 10 μm. Then, stack the single-side aluminized PET film with the intelligent temperature-regulating layer, EVA hot-melt adhesive film (thickness 5 μm), and the non-aluminized side of the single-side aluminized PET film, under the conditions of pressure of 1MPa and temperature of 80°C The intelligent temperature-regulating current collector is obtained by hot-pressing and compounding.

Example 2:

First, prepare the phase transition according to the formula of 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 , and 300 parts by weight of N-methylpyrrolidone Heat storage composite slurry. The phase change heat storage composite slurry was uniformly coated on the non-copper-plated surface of the single-sided copper-plated PI film (thickness 10 μm), and dried and cured at 120 °C for 8 hours to obtain an intelligent temperature-regulating layer with a thickness of 10 μm. Then, the single-sided copper-plated PI film with the intelligent temperature-regulating layer, the PES hot-melt adhesive film (thickness 5 μm), and the non-copper-plated surface of the single-sided copper-plated PI film are stacked under the conditions of pressure 6 MPa and temperature 180 ° C. Hot-compression composite to obtain 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-dimethyl Formamide was used as formula to prepare phase change heat storage composite slurry. The phase-change heat storage composite slurry was uniformly coated on the non-aluminized surface of the single-sided aluminized PVC film (thickness 12 μm), and dried and cured at 80°C for 8 hours to obtain an intelligent temperature-regulating layer with a thickness of 6 μm. Then, stack the single-sided aluminized PVC film with the intelligent temperature-regulating layer, the TPU hot-melt adhesive film (thickness 6 μm), and the non-aluminized surface of the single-sided aluminized PVC film, under the conditions of pressure 2MPa and temperature 100°C Hot-compression composite to obtain intelligent temperature-regulating current collector.

The embodiments described above are only preferred solutions of the present invention, and do not limit the present invention in any form. There are other variations and modifications on the premise of not exceeding the technical solutions described 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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