CN114039084A - High-safety polymer flexible package lithium ion battery - Google Patents
High-safety polymer flexible package lithium ion battery Download PDFInfo
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- CN114039084A CN114039084A CN202111234844.9A CN202111234844A CN114039084A CN 114039084 A CN114039084 A CN 114039084A CN 202111234844 A CN202111234844 A CN 202111234844A CN 114039084 A CN114039084 A CN 114039084A
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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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
- H01M4/661—Metal or alloys, e.g. alloy coatings
- H01M4/662—Alloys
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention discloses a high-safety polymer flexible package lithium ion battery which comprises a positive electrode, a negative electrode, a diaphragm, electrolyte and an aluminum-plastic composite film. In the manufacturing step of the negative electrode, a shape memory alloy is adopted as a current collector, a negative electrode active substance is coated on the surface of the current collector to manufacture the negative electrode of the flexible package lithium ion battery, and then the negative electrode, the positive electrode of the lithium ion battery, a diaphragm, electrolyte and an aluminum-plastic composite membrane are assembled into the flexible package lithium ion battery. When the battery is in abnormal conditions such as internal short circuit, external short circuit, overcharge and overdischarge in the use process, the internal temperature of the battery rises, and when the temperature reaches the phase change temperature of the shape memory alloy current collector, the shape memory alloy current collector deforms, a large number of gaps between the positive electrode and the negative electrode of the internal lithium ion battery are formed, and ion and electron conducting channels between the positive electrode and the negative electrode are damaged, so that the internal resistance of the battery rises rapidly, the internal electrochemical process is blocked, and the thermal runaway of the battery is avoided.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery manufacturing, and particularly relates to a high-safety polymer flexible package lithium ion battery with a self-blocking mechanism and a manufacturing method thereof.
Background
The lithium ion battery is widely applied to the product fields of automobiles, 3C, bicycles and the like due to the advantages of higher energy density, environmental protection and the like. However, in recent years, as the lithium ion battery is expanded in various industries, a lot of problems are accompanied, and among them, the most serious is the safety accident of the lithium ion battery. Due to the higher energy density, when the battery is abnormal, thermal runaway is easily caused, so that serious fire and explosion occur, and product damage and even personal safety are caused.
Under the general condition, various external protection designs are carried out on the lithium ion battery, and the external protection design schemes including a protection circuit, a shell protection and the like can realize the protection of external factors of the lithium ion battery, so that the lithium ion battery has a remarkable effect on the electrical/thermal damage of the lithium ion battery caused by mechanical damage, overcharge, overdischarge, external short circuit, overload, overheating and other abuse conditions of the lithium ion battery due to external force impact, extrusion, deformation and the like, but the method is always incapable of thermal runaway caused by short circuit generated inside the battery, and therefore the improvement of the intrinsic safety of the lithium ion battery is in the forefront.
Disclosure of Invention
The invention carries out self-blocking design aiming at the process of thermal runaway occurring inside the existing lithium ion battery, and can block the continuous occurrence of the short circuit process at the initial stage of the occurrence of the internal short circuit of the battery, thereby essentially improving the safety of the lithium ion battery.
The invention adopts the technical scheme that a high-safety polymer flexible package lithium ion battery adopts shape memory alloy as a negative electrode current collector, firstly, the shape memory alloy current collector is pretreated to enable the shape memory alloy current collector to have a three-dimensional high-temperature form, and then, the shape memory alloy current collector is cold-deformed into a planar low-temperature form. Coating the negative active material on the surface of the lithium ion battery to prepare the negative electrode of the flexible package lithium ion battery. The laminated structure lithium ion battery is manufactured by adopting a common lithium ion anode, a diaphragm, electrolyte, an aluminum-plastic composite film and the like.
When the lithium ion battery is in abnormal conditions such as internal short circuit, external short circuit, overcharge and overdischarge in the use process, the internal temperature of the battery rises, and when the temperature reaches the phase change temperature of the shape memory alloy current collector, the shape memory alloy current collector deforms and recovers to a high-temperature three-dimensional form, so that a gap is formed between the positive electrode and the negative electrode in the battery, an ion and electron conduction channel between the positive electrode and the negative electrode is damaged, the internal resistance of the battery rises rapidly, the internal electrochemical process is blocked, and the thermal runaway of the battery is avoided.
The flexible package lithium ion battery adopts a shape memory alloy as a negative current collector, wherein the shape memory alloy comprises but is not limited to TiNi alloy, various Cu-based shape memory alloys and the like.
The shape memory alloy current collector needs to be subjected to high-temperature shape treatment in advance, and the high-temperature shape meets the following conditions: (1) the high-temperature current collector has a regular or approximately regular three-dimensional form, and the space occupied by the current collector in the thickness direction is not less than the thickness of the current collector; (2) the current collector is in a three-dimensional shape, and two surfaces in the thickness direction of the current collector can bear a plane; (3) the three-dimensional morphology of the current collector does not contain sharp corners or may pierce the separator or the aluminum-plastic composite membrane of claim 1. And then shaping the current collector by adopting a special die in a high-temperature environment, wherein the high-temperature environment is between 200 and 1000 ℃, and the adjustment is specifically carried out according to the type and the components of the shape memory alloy.
The thickness of the shape memory alloy current collector is between 0.005 and 0.3 mm, and the phase change temperature is between 30 and 200 ℃.
And after the shape memory alloy current collector is subjected to heat setting, cooling and taking out, and deforming the shape memory alloy current collector into a low-temperature shape in a two-dimensional form in a plane foil, strip or plate shape by adopting a rolling or other deformation mode.
In the flexible package battery, all or part of the negative current collector adopts the shape memory alloy as the negative current collector.
Compared with the prior art, the invention has the following advantages:
1. the flexibly packaged lithium ion battery adopts the shape memory alloy current collector, and can trigger the shape memory alloy current collector to deform through temperature when the battery is abnormal, so that the distance between the positive electrode and the negative electrode in the battery is manufactured in the battery, a large amount of space is generated, the propagation channel of lithium ions and electrons is greatly blocked, the ion path in the battery is interrupted, the internal short circuit or the charge-discharge loop is interrupted, and the occurrence of thermal runaway can be effectively avoided;
2. the flexible package lithium ion battery adopts the very reliable material property of the shape memory alloy temperature triggered phase change, the reaction mechanism is very reliable, and the failure condition can not exist. The temperature rise is just the premise that thermal runaway of the battery occurs, and the shape memory alloy is triggered to deform at the temperature which does not cause the thermal runaway so as to enable the inside of the battery to be broken, so that the thermal runaway of the battery can be effectively avoided.
3. The flexibly packaged lithium ion battery does not change the electrochemical system of the battery, has no influence on the electrochemical performance of the battery, does not sacrifice any battery performance, and has great advantages compared with the prior art that the battery performance is reduced by other technical methods.
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Drawings
FIG. 1 is a schematic structural view of the present invention;
FIG. 2 is a schematic view of a shape memory alloy current collector of example 1 of the present invention before heat treatment;
FIG. 3 is a schematic view of a shape memory alloy current collector after heat treatment according to example 1 of the present invention;
FIG. 4 is a schematic view of a shape memory alloy current collector deformed after being coated with a negative electrode in example 1 of the present invention;
fig. 5 is a schematic cross-sectional view of the flexibly packaged lithium ion battery according to example 1 of the present invention after deformation of the negative electrode during abnormal heat generation;
fig. 6 is a schematic plan view of the high temperature morphology of the shape memory alloy current collector pretreatment in example 3 of the present invention.
Description of reference numerals:
1-positive current collector; 2-a separator; 3-negative shape memory alloy current collector; 4-positive electrode active material; 5-negative electrode active material; 6-aluminum-plastic composite film;
Detailed Description
In order to clearly understand the technical features, objects and advantages of the present invention, the technical solutions of the present invention will be described in detail below with reference to the accompanying drawings, but the present invention is not limited to the practical scope of the present invention.
Example 1:
preparation of a shape memory alloy current collector: selecting TiNi shape memory alloy with the thickness of 0.1mm and the phase transition temperature of 80 ℃; the TiNi alloy sheet is pre-deformed into a wavy cross-section by using a special die, as shown in figure 3. Then keeping the shape, putting the shape into an environment with the temperature of 450 ℃ for heat preservation for 4 hours, and then naturally cooling. The cooled TiNi shape memory alloy was again pressed flat to the configuration shown in fig. 2.
Preparation of negative electrode: mixing graphite, conductive carbon black, sodium polymethylcellulose and styrene butadiene rubber emulsion according to a mixing ratio of 94: 1: 1.5: 2.5 and deionized water to form slurry, then coating a proper amount of negative electrode slurry on the surface of the prepared shape memory alloy current collector, and then carrying out vacuum drying at the temperature of 60 ℃.
Manufacturing of the soft package battery: the negative electrode prepared by the method, the positive electrode, the diaphragm, the electrolyte and the aluminum-plastic composite film are assembled into the laminated flexible package lithium ion battery 1 according to the manufacturing method commonly used in the industry.
In the soft package lithium ion battery in this embodiment, during the overcharge experiment, when the internal temperature reaches 80 ℃, the negative electrode shape memory alloy current collector deforms, and returns to the high-temperature shape of the shape memory alloy, as shown in fig. 5, the internal positive electrode and the negative electrode are disconnected, and the charging process is blocked, so that the thermal runaway of the battery is avoided.
Example 2:
preparation of a shape memory alloy current collector: selecting TiNi shape memory alloy with the thickness of 0.15mm and the phase transition temperature of 105 ℃; and pre-deforming the TiNi alloy sheet into a concave-convex reticulate pattern by using a special tool clamp. Then keeping the shape, putting the shape into an environment with the temperature of 600 ℃ for heat preservation for 4 hours, and then naturally cooling. The cooled TiNi shape memory alloy was pressed flat to the flat configuration shown in FIG. 2.
Referring to fig. 1, the prepared shape memory alloy current collector is coated with negative electrode slurry, and then assembled with a positive electrode, a diaphragm, an electrolyte and an aluminum-plastic composite film to form a flexible package lithium ion battery 1.
In the soft package lithium ion battery in the embodiment, when the internal temperature reaches 105 ℃ in an abuse test, the negative electrode shape memory alloy current collector deforms and recovers to the high-temperature shape of the shape memory alloy, so that the internal disconnection is formed, the charging process is blocked, and the thermal runaway of the battery is avoided.
Example 3:
preparation of a shape memory alloy current collector: selecting a TiNi shape memory alloy foil coiled material with the thickness of 0.008mm and the phase transition temperature of 85 ℃; the TiNi shape memory alloy foil coil is embossed by using a roller press die, and the surface appearance of the TiNi shape memory alloy foil coil is shown in figure 6. And (3) simultaneously heating in the embossing process to keep the rolling embossing die at 200 ℃, keeping the rolling speed at a relatively slow degree, ensuring that the TiNi shape memory alloy foil coiled material can keep a deformation state for more than 30min in the embossing process, and after leaving a high-temperature area, cooling the coiled material to normal temperature, rolling the coiled material with a smooth surface, and flattening the coiled material into the coiled material.
Coating the prepared shape memory alloy current collector coil with negative electrode slurry by using coating equipment for large-scale production, drying at the temperature below 80 ℃ to obtain a negative electrode plate, and assembling the negative electrode plate, a lithium cobaltate positive electrode, a diaphragm, electrolyte and an aluminum-plastic composite film into a winding type flexible package lithium ion battery.
In the soft package lithium ion battery in the embodiment, when the internal temperature reaches 85 ℃ in an abuse test, the negative electrode shape memory alloy current collector deforms and recovers to the high-temperature shape of the shape memory alloy, so that the internal disconnection is formed, the charging process is blocked, and the thermal runaway of the battery is avoided.
Example 4:
shape memory alloy current collector and use the negative pole of shape memory alloy current collector preparation: prepared as described in example 1.
Preparation of Bicell: and (3) using a conventional positive electrode, a conventional negative electrode and a conventional diaphragm, sequentially laminating and assembling the diaphragm/the positive electrode/the diaphragm/the negative electrode/the diaphragm/the positive electrode/the diaphragm, and then performing hot press molding to manufacture the bicell.
Manufacturing of the soft package battery: and (3) alternately laminating the bicell and the shape memory alloy negative plates prepared by the method for a certain number in sequence to form the battery cell. Then the laminated soft package lithium ion battery is manufactured with the aluminum-plastic composite film and the electrolyte according to the common method of the lithium ion battery industry.
In the soft-package lithium ion battery in the embodiment, when heat is generated due to abnormality and the temperature reaches 80 ℃, the shape memory alloy negative plate in the battery deforms to form a gap between the bicells, so that the internal resistance of the battery is greatly increased, and thermal runaway of the battery is avoided to a great extent.
In the further details of the present invention, the shape memory alloy current collector may be a TiNi alloy, or may be other alloys with shape memory effect, such as a Cu-based alloy. The pre-treated hot state shape of the shape memory alloy current collector may be any shape that satisfies claim 4. The application of the present embodiment can ensure that the flexible package battery is internally disconnected before thermal runaway, thereby blocking further heat generation reaction.
The above-mentioned embodiments do not constitute a limitation to the protection of the technical solution, and it should be understood that a person skilled in the technical field of the present invention may make several simple deductions or substitutions without departing from the concept of the present invention, and all of them should be considered as belonging to the protection scope of the present invention.
Claims (8)
1. The utility model provides a high security polymer soft package lithium ion battery, includes positive pole, negative pole, diaphragm, electrolyte and plastic-aluminum complex film, its characterized in that adopts shape memory alloy as the negative pole mass flow body, adopts the lithium ion battery negative pole thick liquids of formula proportion commonly used, with its coating on the negative pole mass flow body, prepare out the negative pole of soft package lithium ion battery, will the negative pole, with lithium ion battery positive pole, diaphragm, electrolyte and the plastic-aluminum complex film commonly used according to the lamination assembly lithium ion battery, the negative pole both sides all place corresponding positive pole, and the negative pole with all separate by the diaphragm between the positive pole, one deck or multilayer diaphragm should be placed between negative pole and the plastic-aluminum complex film.
2. The high-safety polymer flexible-package lithium ion battery as claimed in claim 1, wherein the negative electrode current collector is made of shape memory alloy, wherein the shape memory alloy includes but is not limited to TiNi alloy, Cu-M, M is one or more alloys of Sn, Zn, Al, Ni, Au, Mo, Be, Si, Ga, Fe-M, M is one or more alloys of Pt, Ni, Co, Mn, Si, Pd.
3. The high-safety polymer flexible-package lithium ion battery according to claim 1, wherein the thickness of the negative electrode current collector is 0.005-3.0 mm, preferably 0.006-0.5 mm.
4. The high-safety polymer flexible-package lithium ion battery as claimed in claim 2, wherein the negative electrode current collector is pre-processed with a high-temperature shape, and the high-temperature shape satisfies the following conditions: (1) the high-temperature current collector has a regular or approximately regular three-dimensional form, and the space occupied by the negative current collector in the thickness direction is not less than the thickness of the negative current collector; (2) the three-dimensional shape of the negative current collector has the advantages that two surfaces in the thickness direction of the negative current collector can bear a plane; (3) the three-dimensional morphology of the negative current collector does not contain sharp corners or may pierce the separator or the aluminum-plastic composite film.
5. The high-safety polymer flexible-package lithium ion battery according to claim 2, wherein the high-temperature shape of the negative electrode current collector is shaped in a high-temperature environment, the high-temperature environment is between 100 ℃ and 2000 ℃, and the high-temperature environment is specifically adjusted according to the type and components of the shape memory alloy.
6. The high-safety polymer flexible package lithium ion battery according to claim 1, wherein the phase transition temperature of the shape memory alloy current collector is between 30 ℃ and 200 ℃, preferably between 70 ℃ and 120 ℃.
7. The high-safety polymer flexible-package lithium ion battery according to claim 1, wherein the low-temperature-state shape of the negative electrode current collector is a two-dimensional shape, and is a planar foil or a plate.
8. The high-safety polymer flexible-package lithium ion battery as claimed in claim 1, wherein all or part of the negative electrode current collector adopts shape memory alloy as the negative electrode current collector.
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Cited By (2)
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| CN116031412A (en) * | 2023-02-27 | 2023-04-28 | 华中科技大学 | Memory composite current collector and preparation method thereof |
| CN116031413A (en) * | 2023-02-27 | 2023-04-28 | 华中科技大学 | Shape memory composite current collector and preparation method thereof |
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