Organic liquid electrolyte battery with fire extinguishing agent in battery cell and preparation method and application of organic liquid electrolyte battery

Abstract

The invention relates to the field of organic liquid electrolyte batteries, in particular to an organic liquid electrolyte battery with a battery cell internally provided with a fire extinguishing agent and a preparation method and application thereof.The battery comprises a shell, an electrode assembly and battery cell liquid, and the battery cell liquid comprises 85%-98% of electrolyte and 2%-15% of a fluorine-containing liquid fire extinguishing agent; the fluorine-containing liquid fire extinguishing agent and the electrolyte are insoluble, and a layered structure of lower-layer fire extinguishing liquid and upper-layer electrolyte is formed in the battery cell. According to the invention, the defects of cell deflagration, slow response of an external fire extinguishing system and influence of an electrolyte additive on performance during thermal runaway under the abuse condition in the prior art are overcome, the intrinsic safety of the cell of a liquid battery with related liquid organic solvents such as lithium ions and sodium ions is realized, the cost is low, and the method is easy to realize.

Description

Technical Field

[0001] The present invention relates to the field of organic liquid electrolyte batteries, and in particular to an organic liquid electrolyte battery with a built-in fire extinguishing agent in the battery core, and a preparation method and application thereof. Background Art

[0002] Organic solvent liquid battery cells refer to battery cells that use organic solvents as key components of the electrolyte, such as common liquid lithium-ion batteries and sodium-ion batteries. However, these battery cells are at risk of combustion and explosion when subjected to abuse such as squeezing and needle puncture.

[0003] At present, whether it is the large-scale power battery packs widely used in power systems or energy storage devices, their internal structures have not yet achieved the intrinsic safety of the battery cells. In order to ensure the safety of the battery packs, they have to rely on a large number of external fire-fighting devices and materials, which undoubtedly greatly increases the complexity of technical implementation and production costs.

[0004] In reality, the organic electrolyte inside organic solvent liquid battery cells is highly flammable. As a high-energy-density electrochemical system, batteries themselves are difficult to reverse once thermal runaway begins, leading to immeasurable losses, including but not limited to damage to the vehicle and energy storage device itself, casualties, property damage, and environmental harm caused by the spread of fire. Existing external fire extinguishing systems can temporarily control fires, but they are unable to fundamentally resolve the problem. While seemingly effective for a short period of time, the fire will flare up again.

[0005] Existing lithium-ion batteries of this type cannot achieve reliable intrinsic safety. When a single cell experiences thermal runaway, it can trigger a massive chain reaction, causing serious damage. Currently, there is a lack of practical, convenient, and effective methods to achieve intrinsic safety in batteries. External fire extinguishing devices can only be used for limited control, but this approach is still insufficient to address the risk of large-scale power battery or energy storage device runaway. Summary of the Invention

[0006] (1) Technical issues to be resolved The problem to be solved by the present invention is to provide an organic liquid electrolyte battery with a built-in fire extinguishing agent in the battery cell, as well as a preparation method and application, so as to overcome the defects of the prior art such as battery cell explosion during thermal runaway under abuse conditions, slow response of the external fire extinguishing system, and performance impact of electrolyte additives, and realize the intrinsic safety of battery cells of related liquid organic solvent electrolytes such as lithium ions and sodium ions, and at low cost and easy to implement.

[0007] (2) Technical solution To solve the technical problem, the first aspect of the present invention provides an organic liquid electrolyte battery with a built-in fire extinguishing agent in the battery cell. The battery includes a shell, an electrode assembly and a battery cell liquid. The battery cell liquid includes 85%-98% electrolyte and 2%-15% fluorine-containing liquid fire extinguishing agent. The fluorine-containing liquid fire extinguishing agent and the electrolyte are immiscible with each other, and a layered structure of a lower layer of fire extinguishing liquid and an upper layer of electrolyte is formed in the battery cell.

[0008] Furthermore, the battery core liquid includes 90%-95% electrolyte and 5%-10% fluorine-containing liquid fire extinguishing agent.

[0009] Furthermore, the fluorine-containing liquid includes a fluorine-containing fire extinguishing agent and a fluorine-containing solvent.

[0010] Furthermore, the fluorine-containing liquid fire extinguishing agent has a greater density than the electrolyte. Since the fluorine-containing liquid fire extinguishing agent has a greater density than the electrolyte, it can be deposited at the bottom of the housing without affecting the normal contact between the electrolyte and the positive and negative electrodes.

[0011] Furthermore, the density of the fluorine-containing liquid fire extinguishing agent is 10%-50% greater than that of the electrolyte.

[0012] Furthermore, the fluorine-containing liquid fire extinguishing agent is selected from any one of perfluorohexanone, perfluorobutyl methyl ether, perfluoropolyether, hydrofluoroether and fluorophosphate, preferably perfluorohexanone.

[0013] Furthermore, the shape of the shell includes any one of a cylindrical, square and blade-type structure.

[0014] Furthermore, the shell material includes any one of a steel shell, an aluminum shell and a soft-package composite film.

[0015] Furthermore, a pressure relief valve or a rupture inducing structure is provided at the bottom of the battery, and when the internal pressure exceeds a threshold, the fire extinguishing liquid and the electrolyte are ejected synchronously through the pressure relief channel.

[0016] Furthermore, the battery includes any one of a lithium-ion battery, a sodium-ion battery and a zinc-ion battery. Lithium-ion batteries, sodium-ion batteries and zinc-ion batteries are organic electrolyte batteries, while lead-acid batteries, nickel-cadmium batteries and nickel-metal hydride batteries are aqueous electrolyte batteries, which usually do not have the risk of thermal runaway caused by combustion or explosion.

[0017] In order to achieve the aforementioned objectives, the second aspect of the present invention provides a method for preparing an organic liquid electrolyte battery using a built-in fire extinguishing agent in a battery cell as described in any one of the first aspects of the present invention. In the battery injection step of the preparation process, 2%-15% fluorine-containing liquid fire extinguishing agent is first injected into the electrolyte injection port, and then 85%-98% electrolyte is injected. The two liquids form a layered structure under the action of gravity, and the fire extinguishing liquid is deposited in the bottom area of the shell.

[0018] Traditional electrolyte and fire extinguishing liquid are injected directly from the electrolyte injection port. Because the specific gravity of the fluorine-containing fire extinguishing liquid is much greater than that of the electrolyte and it is completely immiscible with the electrolyte, during the battery's charge and discharge process, the fire extinguishing liquid, due to its higher specific gravity, accumulates in the gap between the battery cell shell and the lower end of the battery cell, and does not mix with the normal electrolyte to affect the battery's charge and discharge performance. When the internal pressure of the battery increases sharply due to abuse and then depressurizes, the fluorine-containing fire extinguishing liquid such as perfluorohexanone is ejected together with the flammable and explosive electrolyte, directly solving the fire problem at the source.

[0019] Furthermore, the fluorine-containing liquid fire extinguishing agent in the layered structure occupies the vertical space at the lower end of the shell, forms a stable phase separation state with the electrolyte, and maintains interface stability during the charge and discharge process.

[0020] Furthermore, in the layered structure, the fluorine-containing liquid fire extinguishing agent occupies 1-5% of the vertical space at the lower end of the shell. If the fluorine-containing liquid fire extinguishing agent occupies too much space at the lower end of the shell, it may affect the effective utilization of the internal space of the battery.

[0021] In order to achieve the aforementioned objectives, the third aspect of the present invention provides an application of an organic liquid electrolyte battery using a battery cell with a built-in fire extinguishing agent as described in any one of the first aspects of the present invention.

[0022] Furthermore, the applications include the use of organic liquid electrolyte batteries with built-in fire extinguishing agents in automotive batteries, smart device batteries and energy storage batteries.

[0023] (3) Beneficial effects The present invention provides an organic liquid electrolyte battery with a built-in fire extinguishing agent in the battery cell and a preparation method thereof, which has the following beneficial effects: The battery cell of the present invention is added with a fluorine-containing fire extinguishing agent at the same time as the electrolyte. Since the density of the fluorine-containing fire extinguishing agent is greater than that of the electrolyte and the fluorine-containing fire extinguishing agent and the electrolyte are mutually immiscible, the fluorine-containing fire extinguishing agent will be deposited at the bottom of the battery cell to avoid mixing with the electrolyte, thereby not interfering with the electrochemical performance of the battery. This stratification mechanism ensures that the fire extinguishing agent will not affect the normal operation of the battery under normal operating conditions, and can quickly take effect in the event of thermal runaway.

[0024] When a battery experiences thermal runaway, the pressure relief valve automatically opens. At this point, the fire extinguishing agent is ejected synchronously with the electrolyte, directly enveloping the electrolyte vapor and flames. Perfluorohexanone molecules, at high temperatures, capture free radical ions, interrupting the combustion chain reaction and thereby suppressing the spread of the fire. Perfluorohexanone rapidly vaporizes upon ejection, absorbing significant heat, lowering the fire temperature and further suppressing the fire. Therefore, the battery cell of the present invention ensures that the fire extinguishing agent can quickly and effectively extinguish flames in the event of thermal runaway, preventing the spread of the fire.

[0025] The present invention adopts a method of mixing a fluorine-containing fire extinguishing agent with an electrolyte and adding it to a battery. When the battery burns or explodes due to abuse, the fluorine-containing electrolyte is ejected together, thereby achieving the effect of preventing the battery from burning or exploding. Only 2%-15% of the volume of the electrolyte required for injection into the battery cell needs to be replaced with perfluorohexanone (or a similar fluorine-containing fire extinguishing liquid that is completely insoluble in the electrolyte). The other manufacturing processes and links of the battery cell can remain unchanged. In addition, the cost of the fluorine-containing fire extinguishing agent is relatively low. Therefore, the solution of the present invention is low-cost and easy to implement. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0027] Figure 1 This is a cross-sectional view of an organic liquid electrolyte battery with a built-in fire extinguishing agent in the battery cell of the present invention.

[0028] The names of the components corresponding to the various reference numerals in the figure are: 1-shell; 2-battery cell; 3-electrolyte; 4-fluorine-containing liquid fire extinguishing agent. DETAILED DESCRIPTION

[0029] The present application is described in detail below with reference to the accompanying drawings and specific embodiments.

[0030] The following describes the embodiments of the present application through specific examples, and those skilled in the art can easily understand other advantages and effects of the present application from the contents disclosed in this specification. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. The present application can also be implemented or applied through other different specific embodiments, and the details in this specification can also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present application. It should be noted that, in the absence of conflict, the features in the following embodiments and embodiments can be combined with each other. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without making creative work are within the scope of protection of this application.

[0031] It should be noted that various aspects of the embodiments within the scope of the appended claims are described below. It should be apparent that the aspects described herein can be embodied in a wide variety of forms, and any specific structure and / or function described herein is merely illustrative. Based on this application, it should be understood by those skilled in the art that an aspect described herein can be implemented independently of any other aspect, and two or more of these aspects can be combined in various ways. For example, any number and aspect described herein can be used to implement an apparatus and / or practice a method. In addition, other structures and / or functionalities other than one or more of the aspects described herein can be used to implement this apparatus and / or practice this method.

[0032] It should also be noted that the illustrations provided in the following embodiments are only schematic illustrations of the basic concept of the present application. The illustrations only show components related to the present application and are not drawn according to the number, shape and size of components in actual implementation. In actual implementation, the type, quantity and proportion of each component can be changed at will, and the component layout type may also be more complicated.

[0033] Additionally, in the following description, specific details are provided to provide a thorough understanding of the examples, however, one skilled in the art will appreciate that the examples can be practiced without these specific details.

[0034] The following describes the technical solutions provided by the embodiments of the present application in conjunction with the accompanying drawings. Example 1

[0035] See Figure 1 The present invention provides an organic liquid electrolyte battery with a built-in fire extinguishing agent in the battery cell. The battery includes a shell 1, an electrode assembly and a battery cell 2 liquid. The battery cell 2 liquid includes 95% electrolyte 3 and 5% fluorine-containing liquid fire extinguishing agent 4. The fluorine-containing liquid fire extinguishing agent 4 and the electrolyte 3 are insoluble in each other. A layered structure of a lower layer of fluorine-containing liquid fire extinguishing agent 4 and an upper layer of electrolyte 3 is formed in the battery cell 2.

[0036] Please refer again Figure 1 The battery housing 1 is a cylindrical aluminum shell, the battery is a lithium-ion battery, and the fluorine-containing liquid fire extinguishing agent 4 uses perfluorohexanone. The density of perfluorohexanone is higher than that of the lithium-ion battery electrolyte, so the fire extinguishing agent is deposited at the bottom of the shell 1; a pressure relief valve or a rupture inducing structure is provided at the bottom of the battery. When the internal pressure exceeds the threshold, the perfluorohexanone and the lithium-ion battery electrolyte are synchronously ejected through the pressure relief channel.

[0037] Please refer again Figure 1In the battery injection process of the preparation process, 5% perfluorohexanone is first injected into the electrolyte injection port, and then 95% lithium-ion battery electrolyte is injected. The two liquids form a layered structure under the action of gravity. In the layered structure, perfluorohexanone occupies the vertical space at the lower end of the shell 1, forming a stable phase separation state with the lithium-ion battery electrolyte, maintaining interface stability during the charge and discharge process. Example 2

[0038] See Figure 1 The present invention provides an organic liquid electrolyte battery with a built-in fire extinguishing agent in the battery cell. The battery includes a shell 1, an electrode assembly and a battery cell 2 liquid. The battery cell 2 liquid includes 95% electrolyte 3 and 5% fluorine-containing liquid fire extinguishing agent 4. The fluorine-containing liquid fire extinguishing agent 4 and the electrolyte 3 are insoluble in each other. A layered structure of a lower layer of fluorine-containing liquid fire extinguishing agent 4 and an upper layer of electrolyte 3 is formed in the battery cell 2.

[0039] Please refer again Figure 1 The battery housing 1 is a cylindrical aluminum shell, the battery is a sodium ion battery, and the fluorine-containing liquid fire extinguishing agent 4 uses perfluoropolyether. The density of perfluoropolyether is higher than that of the sodium ion battery electrolyte, so the fire extinguishing agent is deposited at the bottom of the shell 1; a pressure relief valve or a rupture inducing structure is provided at the bottom of the battery. When the internal pressure exceeds the threshold, the perfluoropolyether and the sodium ion battery electrolyte are synchronously ejected through the pressure relief channel.

[0040] Please refer again Figure 1 In the battery injection process of the preparation process, 5% perfluoropolyether is first injected into the electrolyte injection port, followed by 95% sodium ion battery electrolyte. The two liquids form a layered structure under the action of gravity. In the layered structure, perfluoropolyether occupies the vertical space at the lower end of the shell 1, forming a stable phase separation state with the sodium ion battery electrolyte, maintaining interface stability during the charge and discharge process.

[0041] The same or similar parts between the embodiments in this specification can be referred to each other, and each embodiment focuses on the differences from other embodiments.

[0042] The above description is merely a specific embodiment of the present application, but the scope of protection of the present application is not limited thereto. Any changes or substitutions that can be easily conceived by a person skilled in the art within the technical scope disclosed in the present application should be included in the scope of protection of the present application. Therefore, the scope of protection of the present application should be based on the scope of protection of the claims.

Claims

1. An organic liquid electrolyte battery with a built-in fire extinguishing agent, characterized in that: The battery comprises a housing (1), an electrode assembly and a battery cell (2) liquid. The battery cell (2) liquid comprises 85%-98% of an electrolyte (3) and 2%-15% of a fluorine-containing liquid fire extinguishing agent (4). The fluorine-containing liquid fire extinguishing agent (4) and the electrolyte (3) are incompatible with each other, and a layered structure of a lower layer of the fluorine-containing liquid fire extinguishing agent (4) and an upper layer of the electrolyte (3) is formed in the battery cell (2).

2. The organic liquid electrolyte battery with a built-in fire extinguishing agent as claimed in claim 1, characterized in that: The density of the fluorine-containing liquid fire extinguishing agent (4) is greater than that of the electrolyte (3).

3. The organic liquid electrolyte battery with a built-in fire extinguishing agent as claimed in claim 1, characterized in that: The fluorine-containing liquid fire extinguishing agent (4) is selected from any one of perfluorohexanone, perfluorobutyl methyl ether, perfluoropolyether, hydrofluoroether and fluorophosphate.

4. The organic liquid electrolyte battery with a built-in fire extinguishing agent as claimed in claim 1, characterized in that: The shape of the housing (1) includes any one of a cylindrical, square and blade-type structure.

5. The organic liquid electrolyte battery with a built-in fire extinguishing agent as claimed in claim 1, characterized in that: The shell (1) is made of any one of a steel shell, an aluminum shell and a soft-package composite film.

6. The organic liquid electrolyte battery with a built-in fire extinguishing agent as claimed in claim 1, characterized in that: A pressure relief valve or a rupture induction structure is provided at the bottom of the battery. When the internal pressure exceeds a threshold value, the fluorine-containing liquid fire extinguishing agent (4) and the electrolyte (3) are ejected synchronously through the pressure relief channel.

7. The organic liquid electrolyte battery with a built-in fire extinguishing agent as claimed in claim 1, characterized in that: The battery includes any one of a lithium ion battery, a sodium ion battery and a zinc ion battery.

8. A method for preparing an organic liquid electrolyte battery with a built-in fire extinguishing agent as claimed in claim 1, characterized in that: In the battery injection process of the preparation process, 2%-15% fluorine-containing liquid fire extinguishing agent (4) is first injected into the electrolyte injection port, and then 85%-98% electrolyte (3) is injected. The two liquids form a layered structure under the action of gravity, and the fluorine-containing liquid fire extinguishing agent (4) is deposited in the bottom area of the shell (1).

9. The method for preparing an organic liquid electrolyte battery with a built-in fire extinguishing agent according to claim 8, characterized in that: The fluorine-containing liquid fire extinguishing agent (4) in the layered structure occupies the vertical space at the lower end of the shell (1), forms a stable phase separation state with the electrolyte (3), and maintains interface stability during the charge and discharge process.

10. Application of the organic liquid electrolyte battery with a built-in fire extinguishing agent as claimed in claim 1 in automobile batteries, smart device batteries and energy storage batteries.

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