CN110911774A - Adsorption powder for reducing oxygen content in lithium ion battery pack, composite support substrate and battery - Google Patents
Adsorption powder for reducing oxygen content in lithium ion battery pack, composite support substrate and battery Download PDFInfo
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- CN110911774A CN110911774A CN201911253306.7A CN201911253306A CN110911774A CN 110911774 A CN110911774 A CN 110911774A CN 201911253306 A CN201911253306 A CN 201911253306A CN 110911774 A CN110911774 A CN 110911774A
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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
- H01M10/52—Removing gases inside the secondary cell, e.g. by absorption
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62C—FIRE-FIGHTING
- A62C3/00—Fire prevention, containment or extinguishing specially adapted for particular objects or places
- A62C3/16—Fire prevention, containment or extinguishing specially adapted for particular objects or places in electrical installations, e.g. cableways
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
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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 provides adsorption powder for reducing the oxygen content in a lithium ion battery pack, a composite support substrate and a battery, which comprise iron powder, chloride inorganic salt and a deoxidizer, wherein the mass of the iron powder is 1-5 times that of the chloride inorganic salt, and the mass of the chloride inorganic salt is 0.7-1.2 times that of the deoxidizer. The adsorption powder for reducing the oxygen content in the lithium ion battery pack, the composite support substrate and the battery can eliminate oxygen and moisture in the battery pack, and even the support substrate can still absorb oxygen released by the anode of the battery cell when thermal runaway occurs, so that the thermal runaway can be prevented and controlled, and the safety of a battery system is improved.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to adsorption powder for reducing oxygen content in a lithium ion battery pack, a composite support substrate and a battery.
Background
The ideal vehicles for future fuel-oil vehicle replacement are undoubtedly Hybrid Electric Vehicles (HEV), electric only vehicles (BEV), and fuel cell vehicles (fuel cell). Compared with traditional batteries such as nickel-hydrogen batteries and lead-acid batteries, the lithium ion batteries have higher energy density and functional density and longer service life. However, as the energy density increases, safety problems begin to manifest themselves. According to incomplete statistics, accidents of spontaneous combustion and fire of electric automobiles are frequent since 2019, and the accidents are often accompanied by phenomena of smoking, fire and explosion. For the occurrence of spontaneous combustion accidents, mechanical abuse and electrical abuse are the main reasons, and thermal abuse can directly cause thermal runaway. Thermal management techniques for batteries therefore present an unprecedented challenge. The thermal management technology needs to consider not only the self-thermal balance problem of the battery in normal operation, but also the risk of battery ignition and explosion after thermal runaway of the battery. The current thermal management technology is not mature enough, so that the early stage of thermal runaway needs to be effectively prevented, the risk of personal safety accidents is reduced, and the improvement on the safety performance of the electric automobile is of great significance.
In the existing battery thermal management technology, a battery thermal management system BMS is basically adopted for detection and early warning, and the main task of the Battery Management System (BMS) is to ensure the design performance of the battery system: 1) safety, the single battery or the battery pack is protected from being damaged, and safety accidents are prevented; 2) the durability ensures that the battery works in a reliable safe area, and the service life of the battery is prolonged; 3) and the dynamic property is realized, and the battery is maintained to work in a state of meeting the vehicle requirement.
Patent CN107987594A describes a fire-resistant flame-retardant coating for magnesium aluminum alloy of battery pack of electric vehicle. The fireproof flame-retardant coating comprises the following raw material components in parts by weight: 80-120 parts of acrylic emulsion; 10-20 parts of ammonium polyphosphate; 10-20 parts of melamine; 20-30 parts of pentaerythritol; 1-3 parts of surfactant and 1-3 parts of defoaming agent. The flame-retardant coating has a good flame-retardant effect, can expand by dozens of times after being coated on a magnesium-aluminum alloy of a battery pack of an electric automobile and is heated, and a compact carbon layer is formed, so that heat is prevented from being transferred to the inside, and the effect of protecting the inside of a lithium battery is achieved. However, this patent is primarily functionally singular and acts primarily on the flame retardant layer and does not maintain the interior of the battery pack in an oxygen-free state. Secondly, no measures are taken with respect to the problem of oxygen evolution of the positive electrode material upon temperature increase. Still other patents incorporate oxygen absorbing additives into the positive electrode of a lithium battery which are rapidly absorbed by the oxygen absorbing additive incorporated into the positive electrode when the positive electrode decomposes to release oxygen at high temperatures, but this reduces the cycle life of the battery and the energy density of the cell. In the prior art, the battery pack is sealed or the BMS system is controlled and maintained. In the presence of air and moisture, when thermal runaway occurs, the generation of oxygen can exacerbate the occurrence of thermal runaway. Therefore, the service life and performance of the battery pack can be prolonged by reducing the influence of oxygen in the battery pack on the battery.
Disclosure of Invention
In view of the above, the present invention is directed to an adsorption powder for reducing oxygen content in a lithium ion battery pack, a composite support substrate and a battery, so as to eliminate oxygen and moisture in the battery pack, and even provide a support substrate capable of absorbing oxygen released from a positive electrode of a battery cell when thermal runaway occurs, thereby preventing and controlling the thermal runaway, and improving the safety of a battery system.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
the adsorption powder for reducing the oxygen content in the lithium ion battery pack comprises iron powder, chloride inorganic salt and a deoxidizer, wherein the mass of the iron powder is (1-5) times that of the chloride inorganic salt, and the content of the chloride inorganic salt is (0.7-1.2) times that of the deoxidizer.
Preferably, the mass of the iron powder is (1-3) times of that of the chloride inorganic salt.
Preferably, the mass of the chloride inorganic salt is (0.9-1.0) times the mass of the diatomaceous earth.
Preferably, the deoxidizer is diatomite, forsterite or fused magnesia. The deoxidizer of the invention is a heat-resistant deoxidizer, has the function of increasing the de-densification of the adsorption powder and has the function of promoting oxygen consumption.
The composite support substrate comprises a support substrate and a coating layer formed by coating the powder on the support substrate, wherein a binder is coated between the support substrate and the coating layer.
Further, the thickness of the coating layer is 5-20 mm.
Preferably, the thickness of the coating layer is 15-20 mm.
Further, the material of the supporting substrate includes, but is not limited to, flame retardant fibers made of polyphenylene sulfide, flame retardant glass fibers, flame retardant polypropylene materials or flame retardant ABS materials.
A battery comprises the composite support substrate, wherein a coating layer in the composite support substrate is positioned on one side of a battery pack and is adjacent to a shell.
Compared with the prior art, the powder for reducing the oxygen content in the lithium ion battery pack, the composite supporting substrate and the battery have the following advantages:
(1) the invention relates to prevention and control of thermal runaway practice, which is mainly used in a lithium ion power battery pack.
(2) The adsorption powder material has a wide working temperature application range, and can ionize 2-valent iron ions under certain conditions, wherein the ionized iron ions react as follows:
2Fe-4e-＝2Fe2+(1)
O2+2H2O+4e-＝4OH-(2)
Fe2++2OH-＝Fe(OH)2(3)
4Fe(OH)2+O2+2H2O＝4Fe(OH)3→
[Fe2O3·nH2O](4)
according toThe above reaction shows that the 2-valent iron ions and O generated in the powder are adsorbed2And H2The combination of hydroxyl generated by the O reaction can play a role in consuming oxygen and water, and meet the requirement of absorbing oxygen under normal conditions or high temperature.
(3) The adsorption powder iron powder and the calcium chloride are mixed, the adding proportion of the adsorption powder iron powder and the calcium chloride is adjustable according to specific requirements, and then the non-woven fabric attached with the powder is tightly attached to the inner surface of the battery can body.
(4) The adsorption powder is separated from the module by the supporting substrate, so that the adsorption powder cannot contact the surface of the module to cause hidden danger, and meanwhile, the air permeability can be ensured.
(5) The support substrate is made of flame-retardant, high-temperature-resistant and light-weight materials, has flame resistance, can prevent materials from being ignited, can inhibit flame propagation, can be self-extinguished or has a self-extinguishing tendency, and can be quickly decomposed to absorb heat when the lithium ion battery is obviously warmed.
(6) After the fiber support substrate is applied to the surfaces of light alloy and polymer composite materials, the lightweight of an electric automobile can be guaranteed, and meanwhile, the fiber support substrate has the capability of resisting flame in a short time, so that the life saving or escaping time of personnel on the automobile can be prolonged.
(7) Sufficient space is reserved between the fiber supporting substrate and the in-package module, so that short circuit in the battery caused by the entry of iron powder is prevented, and meanwhile, the circulation of gas is ensured.
Drawings
FIG. 1 is a graph showing the relationship between oxygen consumption time and compounding ratio in examples 1 to 6 of the present invention.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
Example 1
The adsorption powder for reducing the oxygen content in the lithium ion battery pack comprises iron powder, inorganic chloride salt and kieselguhr, wherein the mass ratio of the iron powder to the anhydrous calcium chloride to the kieselguhr is 1: 1: 5.
when the battery is assembled, the surface of the supporting substrate made of the flame-retardant glass fiber material is coated with one layer of adhesive, powder is coated on the surface of the supporting substrate, the supporting substrate is attached to the battery pack, the coating surface is positioned on one side of the battery pack and is adjacent to the shell, the deoxidizer is prevented from contacting the module, the thickness of the adsorbed powder is 15mm, and the battery pack is filled with nitrogen, so that the oxygen content in the battery pack is adjusted, and the battery pack is in an oxygen-free state. Once abnormal temperature rise occurs in the battery cell body, the anode slowly releases oxygen at the initial stage of temperature rise, and iron powder in the coating film starts to adsorb oxygen, so that the danger level caused by thermal runaway is reduced.
Example 2
The adsorption powder for reducing the oxygen content in the lithium ion battery pack comprises iron powder, inorganic chloride salt and kieselguhr, wherein the mass ratio of the iron powder to the anhydrous calcium chloride to the kieselguhr is (4): 2: 5.
when the battery is assembled, the surface of a supporting substrate made of a flame-retardant ABS material is coated with a layer of adhesive, powder is coated on the surface of the supporting substrate, the supporting substrate is attached to the battery pack, the coating surface is located on one side of the battery pack and adjacent to the shell, the deoxidizer is prevented from contacting the module, the thickness of the adsorbed powder is 20mm, and the battery pack is filled with nitrogen, so that the oxygen content in the battery pack is adjusted, and the battery pack is in an oxygen-free state. Once abnormal temperature rise occurs in the battery cell body, the anode slowly releases oxygen at the initial stage of temperature rise, and iron powder in the coating film starts to adsorb oxygen, so that the danger level caused by thermal runaway is reduced.
Example 3
The adsorption powder for reducing the oxygen content in the lithium ion battery pack comprises iron powder, inorganic chloride salt and kieselguhr, wherein the mass ratio of the iron powder to the anhydrous calcium chloride to the kieselguhr is 9: 3: 5.
when the battery is assembled, the surface of the supporting substrate made of the flame-retardant polypropylene material is coated with one layer of adhesive, powder is coated on the surface of the supporting substrate, the supporting substrate is attached to the battery pack, the coating surface is positioned on one side of the battery pack and is adjacent to the shell, the deoxidizer is prevented from contacting with the module, the thickness of the adsorbed powder is 20mm, and the battery pack is filled with nitrogen, so that the oxygen content in the battery pack is adjusted, and the battery pack is in an oxygen-free state. Once abnormal temperature rise occurs in the battery cell body, the anode slowly releases oxygen at the initial stage of temperature rise, and iron powder in the coating film starts to adsorb oxygen, so that the danger level caused by thermal runaway is reduced.
Example 4
The adsorption powder for reducing the oxygen content in the lithium ion battery pack comprises iron powder, inorganic chloride salt and kieselguhr, wherein the mass ratio of the iron powder to the inorganic chloride salt to the kieselguhr is 8: 4: 5.
when the battery is assembled, the surface of a supporting substrate made of a flame-retardant fiber material and prepared from polyphenylene sulfide is coated with a layer of adhesive, powder is coated on the surface of the supporting substrate, the supporting substrate is attached to the battery pack, the coating surface is positioned on one side of the battery pack and adjacent to the shell, a deoxidizer is prevented from contacting the module, the thickness of the adsorbed powder is 20mm, and the battery pack is filled with nitrogen, so that the oxygen content in the battery pack is adjusted, and the battery pack is in an oxygen-free state. Once abnormal temperature rise occurs in the battery cell body, the anode slowly releases oxygen at the initial stage of temperature rise, and iron powder in the coating film starts to adsorb oxygen, so that the danger level caused by thermal runaway is reduced.
Example 5
The adsorption powder for reducing the oxygen content in the lithium ion battery pack comprises iron powder, inorganic chloride salt and kieselguhr, wherein the mass ratio of the iron powder to the anhydrous calcium chloride to the kieselguhr is 3: 1: 1.
when the battery is assembled, the surface of a supporting substrate made of a flame-retardant fiber material and prepared from polyphenylene sulfide is coated with a layer of adhesive, powder is coated on the surface of the supporting substrate, the supporting substrate is attached to the battery pack, the coating surface is positioned on one side of the battery pack and adjacent to the shell, a deoxidizer is prevented from contacting the module, the thickness of the adsorbed powder is 20mm, and the battery pack is filled with nitrogen, so that the oxygen content in the battery pack is adjusted, and the battery pack is in an oxygen-free state. Once abnormal temperature rise occurs in the battery cell body, the anode slowly releases oxygen at the initial stage of temperature rise, and iron powder in the coating film starts to adsorb oxygen, so that the danger level caused by thermal runaway is reduced.
Example 6
An adsorption powder for reducing oxygen content in a lithium ion battery pack comprises iron powder, inorganic chloride salt and diatomite, wherein the mass ratio of the iron powder to the anhydrous calcium chloride to the diatomite is 30: 6: 5.
when the battery is assembled, the surface of the supporting substrate made of the flame-retardant glass fiber material is coated with one layer of adhesive, powder is coated on the surface of the supporting substrate, the supporting substrate is attached to the battery pack, the coating surface is positioned on one side of the battery pack and is adjacent to the shell, the deoxidizer is prevented from contacting the module, the thickness of the adsorbed powder is 20mm, and the battery pack is filled with nitrogen, so that the oxygen content in the battery pack is adjusted, and the battery pack is in an oxygen-free state. Once abnormal temperature rise occurs in the battery cell body, the anode slowly releases oxygen at the initial stage of temperature rise, and iron powder in the coating film starts to adsorb oxygen, so that the danger level caused by thermal runaway is reduced.
The powders of examples 1-6 were placed in the same transparent heat-resistant bag according to the battery preparation process, and the time required for completion of oxygen consumption in the bag was recorded, with the specific results shown in the following table:
| A/B | 0.2 | 0.4 | 0.6 | 0.8 | 1.0 | 1.2 |
| Time(S) | 7.31 | 6.43 | 6.00 | 5.43 | 4.87 | 5.32 |
the specific relationship between oxygen consumption time and proportion is shown in fig. 1, and it can be seen from the above table and fig. 1 that the battery pack prepared by using the adsorption powder and the support substrate coated with the adsorption powder can consume oxygen in a short time in the process of releasing oxygen when the temperature in the battery rises, so that the purposes of smoking only and not firing are achieved, the occurrence of thermal runaway is prevented and controlled, and the safety of a battery system is improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. The utility model provides a reduce absorption powder of lithium ion battery package internal oxygen content which characterized in that: the deoxidizer comprises iron powder, chloride inorganic salt and the deoxidizer, wherein the mass of the iron powder is 1-5 times of that of the chloride inorganic salt, and the content of the chloride inorganic salt is 0.7-1.2 times of that of the deoxidizer.
2. The adsorption powder for reducing the oxygen content in a lithium ion battery pack according to claim 1, wherein: the mass of the iron powder is 1-3 times of that of the chloride inorganic salt.
3. The adsorption powder for reducing the oxygen content in a lithium ion battery pack according to claim 1, wherein: the mass of the chloride inorganic salt is 0.9-1.0 times of that of the diatomite.
4. The adsorption powder for reducing the oxygen content in a lithium ion battery pack according to claim 1, wherein: the deoxidizer is diatomite, forsterite or fused magnesia.
5. A composite support substrate, characterized by: the composite supporting substrate comprises a supporting substrate and a coating layer formed by coating the adsorption powder body of any one of claims 1 to 4 on the supporting substrate, wherein a binder is coated between the supporting substrate and the coating layer.
6. The composite support substrate of claim 5, wherein: the thickness of the coating layer is 5-20 mm.
7. The composite support substrate of claim 5, wherein: the thickness of the coating layer is 15-20 mm.
8. The composite support substrate of claim 5, wherein: the material of the support substrate includes but is not limited to flame retardant fibers prepared from polyphenylene sulfide, flame retardant glass fibers, flame retardant polypropylene materials or flame retardant ABS materials.
9. A battery, characterized by: the battery includes the composite support substrate of any of claims 5-8, wherein the coating layer is located on one side of the battery pack and adjacent to the housing.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114464908A (en) * | 2022-04-13 | 2022-05-10 | 四川新能源汽车创新中心有限公司 | Three-dimensional porous coating for lithium ion battery and preparation and application thereof |
| WO2022181429A1 (en) * | 2021-02-25 | 2022-09-01 | 三菱瓦斯化学株式会社 | Oxygen scavenger powder |
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