CN112018445A - Self-destruction structure, electrolyte, electrode, diaphragm and battery - Google Patents
Self-destruction structure, electrolyte, electrode, diaphragm and battery Download PDFInfo
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- CN112018445A CN112018445A CN202010690360.4A CN202010690360A CN112018445A CN 112018445 A CN112018445 A CN 112018445A CN 202010690360 A CN202010690360 A CN 202010690360A CN 112018445 A CN112018445 A CN 112018445A
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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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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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
- H01M10/42—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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M2200/00—Safety devices for primary or secondary batteries
- H01M2200/10—Temperature sensitive devices
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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
Abstract
The application relates to a self-destruction structure, an electrolyte, an electrode, a diaphragm and a battery. The self-destruction structure is used for being contained in the battery. The self-destructive structure includes a first housing and a chemical inhibitor. The first housing encloses a formation of a first space. The chemical inhibitor is received in the first space. The chemical inhibitor is used for inhibiting oxidation-reduction reaction when the battery is in thermal runaway, and the gasification temperature of the chemical inhibitor is lower than the triggering temperature of the thermal runaway of the battery. When the battery is overcharged, overheated and short-circuited, the redox reaction inside the battery is accelerated, and a large amount of heat is generated. The overall temperature of the self-destructing structure increases. The temperature of the chemical inhibitor inside the destruct structure increases and the vaporized volume expands. The chemical inhibitor breaks through the first casing and diffuses into the battery electrolyte. The chemical inhibitor is used for blocking the redox reaction when the battery is in thermal runaway, so that the thermal runaway of the battery is restrained, and the safety of the battery is improved. The self-destruction structure has important value for the safety design of the lithium ion battery with high specific energy.
Description
Technical Field
The application relates to the technical field of batteries, in particular to a self-destruction structure, electrolyte, an electrode, a diaphragm and a battery.
Background
When a lithium ion battery is charged, lithium ions are generated on the positive electrode of the battery, and the generated lithium ions move to the negative electrode through the electrolyte. The carbon as the negative electrode has a layered structure having many pores, and lithium ions reaching the negative electrode are inserted into the pores of the carbon layer, and the more lithium ions are inserted, the higher the charge capacity is. Also, when the battery is discharged (i.e., our process of using the battery), lithium ions embedded in the negative carbon layer are extracted. The lithium ions move back to the positive electrode. The more lithium ions returned to the positive electrode, the higher the discharge capacity.
The safety of lithium batteries is one of the most concerned issues for power batteries. The safety of the battery is greatly related to the design of the battery pack and the conditions of abuse. For a single cell, safety is greatly related to a negative electrode, a separator and an electrolyte in addition to a positive electrode material. The thermal runaway of lithium batteries is due to the fact that the rate of heat generation by the redox reaction inside the battery is much greater than the rate of heat dissipation. Thermal runaway of lithium batteries can lead to explosion and even life safety hazards.
The safety problem of the lithium ion battery prevents the lithium ion battery from further developing to low cost and high specific energy, and becomes a technical bottleneck in the application of a large-scale energy storage system. How to improve the safety of the lithium ion battery is an urgent problem to be solved.
Disclosure of Invention
In view of this, it is necessary to provide a self-destruction structure, an electrolyte, an electrode, a separator, and a battery, in order to improve the safety of a lithium ion battery.
A self-destruction structure is used for being contained in a battery. The self-destructive structure includes a first housing and a chemical inhibitor. The first housing encloses a first space. The chemical inhibitor is received in the first space. The chemical inhibitor is used for inhibiting oxidation-reduction reaction when the battery is in thermal runaway, and the gasification temperature of the chemical inhibitor is lower than the trigger temperature of the thermal runaway of the battery.
In one embodiment, the chemical inhibitor comprises a poisoning agent. The poisoning agent includes a group that polymerizes the carbonate electrolyte.
In one embodiment, the poisoning agent includes a group that inerts the negative electrode of the battery.
In one embodiment, the poisoning agent includes a group that binds to a reactive oxygen species or a free radical.
In one embodiment, the poisoning agent includes at least one of an amine poisoning agent or a carbonate poisoning agent.
In one embodiment, the chemical inhibitor further comprises a dispersant. The vaporization temperature of the dispersant is lower than the trigger temperature of thermal runaway of the battery.
In one embodiment, the self-destruct structure further comprises a spacer. The interlayer is arranged in the first space. The partition separates a second space from the first space. The poisoning agent is received in the first space. The dispersant is contained in the second space.
In one embodiment, the self-destruct structure further comprises a trigger. The trigger is contacted with the chemical inhibitor. The trigger is used for triggering the chemical inhibitor to gasify, and the trigger temperature of the trigger is lower than the trigger temperature of the battery thermal runaway.
In one embodiment, the first housing is an electrode housing or a membrane housing.
An electrolyte having the self-destruct structure of any of the embodiments described above.
An electrode comprising an electrode casing and a self-destruct structure as described in any of the above embodiments, the self-destruct structure being disposed on an outer surface of the electrode casing.
A septum comprising a septum housing and a self-destruct structure as described in any of the above embodiments, the self-destruct structure disposed on an outer surface of the septum housing.
A battery comprising a battery housing and a self-destruct structure as in any one of the above embodiments, the battery housing defining a third space, the self-destruct structure being received in the third space.
The self-destruction structure provided by the embodiment of the application is used for being contained in a battery. The self-destructive structure includes a first housing and a chemical inhibitor. The first housing encloses a first space. The chemical inhibitor is received in the first space. The chemical inhibitor is used for inhibiting oxidation-reduction reaction when the battery is in thermal runaway. The chemical inhibitor has a vaporization temperature below a trigger temperature for thermal runaway of the battery. When the battery is overcharged, overheated, and short-circuited, the redox reaction inside the battery is accelerated, and a large amount of heat is generated. The temperature of the self-destructing structure increases. The temperature of the chemical inhibitor increases. The chemical inhibitor vaporizes volume expansion. The chemical inhibitor breaches the first housing. The chemical inhibitor diffuses into the battery electrolyte. The chemical inhibitor is used for blocking the redox reaction when the battery is in thermal runaway, so that the thermal runaway of the battery is restrained, and the safety of the battery is improved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments or the conventional technologies of the present application, the drawings used in the descriptions of the embodiments or the conventional technologies will be briefly introduced below, it is obvious that the drawings in the following descriptions are only some embodiments of the present application, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic structural view of the self-destruct structure provided in an embodiment of the present application;
FIG. 2 is a schematic structural diagram of the self-destruct structure provided in yet another embodiment of the present application;
FIG. 3 is a schematic structural view of the self-destruct structure provided in another embodiment of the present application;
FIG. 4 is a schematic structural view of the electrode provided in one embodiment of the present application;
FIG. 5 is a schematic diagram of the structure of the diaphragm provided in one embodiment of the present application;
FIG. 6 is a schematic diagram of the structure of the battery provided in one embodiment of the present application;
fig. 7 is a schematic structural diagram of the battery provided in another embodiment of the present application.
Reference numerals:
self-destructive structure 10
Detailed Description
In order to make the aforementioned objects, features and advantages of the present application more comprehensible, embodiments accompanying the present application are described in detail below with reference to the accompanying drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application. This application is capable of embodiments in many different forms than those described herein and those skilled in the art will be able to make similar modifications without departing from the spirit of the application and it is therefore not intended to be limited to the embodiments disclosed below.
The numbering of the components as such, e.g., "first", "second", etc., is used herein for the purpose of describing the objects only, and does not have any sequential or technical meaning. The term "connected" and "coupled" when used in this application, unless otherwise indicated, includes both direct and indirect connections (couplings). In the description of the present application, it is to be understood that the terms "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", and the like, indicate orientations or positional relationships based on those shown in the drawings, and are used only for convenience in describing the present application and for simplicity in description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed in a particular orientation, and be operated, and thus, are not to be considered as limiting the present application.
In this application, unless expressly stated or limited otherwise, the first feature "on" or "under" the second feature may be directly contacting the first and second features or indirectly contacting the first and second features through intervening media. Also, a first feature "on," "over," and "above" a second feature may be directly or diagonally above the second feature, or may simply indicate that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature may be directly under or obliquely under the first feature, or may simply mean that the first feature is at a lesser elevation than the second feature.
A lithium ion battery is a secondary battery (rechargeable battery) that mainly operates by movement of lithium ions between a positive electrode and a negative electrode. When the battery is charged, lithium ions are generated on the positive electrode of the battery, and the generated lithium ions move to the negative electrode through the electrolyte. The carbon as the negative electrode has a layered structure having many pores, and lithium ions reaching the negative electrode are inserted into the pores of the carbon layer, and the more lithium ions are inserted, the higher the charge capacity is. Also, when the battery is discharged (i.e., the process we are using the battery), lithium ions embedded in the negative carbon layer are extracted and move back to the positive electrode. The more lithium ions returned to the positive electrode, the higher the discharge capacity.
Lithium ion batteries also consist of three parts: a positive electrode, a negative electrode and an electrolyte. And (3) anode material: graphite is mostly used. New studies found that titanate may be a better material. And (3) cathode reaction: lithium ions are deintercalated during discharge and are intercalated during charge. During charging: xLi + xe +6C → LixC6. During discharging: lixC6→xLi+xe+6C。
The electrolyte includes a solute and a solvent. Lithium salts such as lithium perchlorate (LiClO4), lithium hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4) are commonly used as solutes. Solvent: since the operating voltage of the battery is much higher than the decomposition voltage of water, organic solvents such as diethyl ether, ethylene carbonate, propylene carbonate, diethyl carbonate, etc. are commonly used in lithium ion batteries.
The organic carbonate compounds of the electrolyte have high activity and are extremely easy to burn. The battery anode material in the charged state is a strong oxidizing compound, while the battery cathode material in the charged state is a strong reducing compound. Strongly oxidizing positive electrode materials are generally less stable and prone to oxygen evolution under abusive conditions, such as overcharge, overheating, and short circuits. Carbonate is very easy to react with oxygen and releases a large amount of heat and gas; the generated heat can further accelerate the decomposition of the positive electrode, generate more oxygen and promote the progress of more exothermic reactions; meanwhile, the activity of the negative electrode with strong reducibility is close to that of metal lithium, and the negative electrode can be immediately burnt and ignite electrolyte, a diaphragm and the like when being contacted with oxygen, so that thermal runaway of the battery is caused, and the battery can be burnt and exploded.
Referring to fig. 1, the present embodiment provides a self-destruct structure 10 for being housed in a battery 100. The self-destruct structure 10 includes a first housing 20 and a chemical inhibitor 30. The first housing 20 defines a first space 201. The chemical inhibitor 30 is received in the first space 201. The chemical inhibitor 30 is used for inhibiting oxidation-reduction reaction when the battery is in thermal runaway, and the gasification temperature of the chemical inhibitor 30 is lower than the trigger temperature of the thermal runaway of the battery.
When the battery is overcharged, overheated, and short-circuited, the redox reaction inside the battery is accelerated, and a large amount of heat is generated. The overall temperature of the self-destruct structure 10 provided by the embodiments of the present application is increased. The temperature of the chemical inhibitor 30 inside the self-destructing structure 10 is increased. The chemical inhibitor 30 vaporizes the volume expansion. The chemical inhibitor 30 breaks through the first housing 20. The chemical inhibitor 30 diffuses into the battery electrolyte. The chemical inhibitor 30 serves to block an oxidation-reduction reaction when the battery thermally runaway, thereby suppressing the thermal runaway of the battery 100 and improving the safety of the battery 100. The self-destruct structure 10 is of significant value to the safety design of high specific energy lithium ion batteries.
Due to the protection of the structure of the first housing 20, the chemical inhibitor 30 is not released at ordinary times, and does not affect the basic performance of the battery 100. The self-destructive structure 10 can be designed and manufactured independently, with little change to the design of the galvanic cell 100, which saves costs. The scheme has important value for the safety design of the high-specific-energy lithium ion battery.
The material of the first housing 20 may be a flexible material or a rigid material.
In one embodiment, the material of the first housing 20 is compatible with the electrochemical system of the primary battery system, i.e., does not induce electrochemical or chemical side reactions. The material of the first housing 20 is aluminum. The material of the first housing 20 is copper.
Referring also to fig. 2, in one embodiment, the first housing 20 is made of fibers of a diaphragm. The use of separator fibers as the first shell 20 may be accomplished by a double layer electrospinning technique. In one embodiment, the shape of the first housing 20 may be a regular shape such as a rectangular parallelepiped, a cube, or a cylinder. The shape of the first housing 20 may be irregular such as a wave shape, a semi-arc shape, or a cone shape.
In one embodiment, the shape of the first space 201 may be a regular shape such as a rectangular parallelepiped, a cube, or a cylinder. The shape of the first space 201 may also be irregular such as a wave shape, a semi-arc shape, or a cone shape.
The first space 201 functions to accommodate the chemical inhibitor 30.
The wall thickness of the first housing 20 may be the same or different.
The self-destructing structure 10 can be disposed within the electrolyte, interior space, electrode or membrane of the battery. The self-destruction structure 10 is disposed according to the degree of heat release inside the battery and the position where heat is easily accumulated.
The self-destruct structure 10 may be disposed on the inner surface of the battery case, the outer surface of the electrode or the outer surface of the separator.
In one embodiment, the chemical inhibitor 30 includes a poisoning agent 310. The poisoning agent 310 includes a group that polymerizes the carbonate electrolyte.
The carbonate electrolyte has high ionic conductivity, and can be generally 10-3S/cm to 2X 10-3S/cm. The transference number of lithium ions should be close to 1.
The carbonate compounds are extremely easy to burn due to high activity. Strongly oxidizing positive electrode materials are generally less stable and prone to oxygen evolution under cell abuse conditions, such as overcharge, overheating, and short circuits. Carbonate is very easy to react with oxygen and releases a large amount of heat and gas; the generated heat can further accelerate the decomposition of the positive electrode, generate more oxygen and promote more exothermic reactions. The poisoning agent 310 includes a group that polymerizes the carbonate electrolyte. The group abstracts electrons from the cyclic carbonate such that the carbonate undergoes ring opening. The ring-opened carbonate is then mixed with the said groups for polymerization. The poisoning agent 310 reduces the reactivity of the carbonate, which in turn reduces the redox reaction rate of the carbonate with oxygen. The self-destruction structure 10 thus suppresses thermal runaway of the battery 100, and improves the safety of the battery 100.
In one embodiment, the poisoning agent 310 is an amine poisoning agent. The radical comprising NH3(amino/amine compounds). The NH3(amino/amine compound) abstracts electrons of cyclic carbonate to cause ring opening of carbonate, and then the ring is openedThe carbonate and the amino group are mixed and polymerized. The amine poisoning agent reduces the reactivity of the carbonate, thereby reducing the redox reaction rate of the carbonate with oxygen. The self-destruction structure 10 thus suppresses thermal runaway of the battery 100, and improves the safety of the battery 100.
In one embodiment, the poisoning agent 310 includes a group that inerts the negative electrode of the battery.
When the battery is charged, lithium ions reaching the negative electrode are inserted into micropores of the carbon layer to form LixC6。LixC6Is a strong reducing compound. In the process of thermal runaway, the cathode Li with strong reducibilityxC6Is close to metallic lithium in reactivity. LixC6Contact with oxygen causes immediate combustion (redox reaction) and ignition of electrolyte, separator, etc., thereby causing thermal runaway of the battery, resulting in combustion and explosion of the battery.
The poisoning agent 310 includes a group that renders the negative electrode of the battery inert. The poisoning agent 310 and the strong reducing cathode LixC6Reaction is carried out to ensure that Li of the cathode releases oxygen when the anode or the organic solvent releases oxygenxC6The reaction was complete. Oxygen cannot react with LixC6A severe redox reaction occurs, thereby reducing thermal runaway energy.
The poisoning agent 310 comprises hydrogel or dilute hydrochloric acid, hydrogel or dilute hydrochloric acid and LixC6Reaction is carried out to avoid oxygen and LixC6A severe redox reaction occurs, reducing the ability of thermal runaway to emit heat.
In one embodiment, the poisoning agent 310 includes a group that binds to a reactive oxygen species or a free radical.
When thermal runaway of a battery occurs, C radicals or H radicals are present in an electrolyte of the battery. And the C radical or the H radical participates in the redox reaction. The poisoning agent 310 includes a group that binds to a radical, reducing the concentration of C or H radicals in the electrolyte, which in turn reduces the rate of the redox reaction. The self-destruction structure 10 thus suppresses thermal runaway of the battery 100, and improves the safety of the battery 100.
In one embodiment, the poisoning agent 310 includes (CO)3)2-Or (HCO)3)-One or two of them. (CO)3)2-Or (HCO)3)-Reacting with C free radical or H free radical under specific conditions to generate CO2The concentration of C radicals or H radicals in the electrolyte is reduced.
In one embodiment, the poisoning agent 310 is NaHCO3Or KHCO3One or two of them. NaHCO 23Or KHCO3CO production in the mid-temperature range2Blocking C and H radicals. NaHCO 23Or KHCO3At the same time, a more stable intermediate product Li is generated in a medium temperature range2CO3The concentration of C radicals or H radicals in the electrolyte is reduced. The self-destruction structure 10 thus suppresses thermal runaway of the battery 100, and improves the safety of the battery 100.
In one embodiment, the poisoning agent 310 is a capture agent that contains reactive oxygen species. The poisoning agent 310 inhibits the migration of active oxygen inside the battery.
In one embodiment, the poisoning agent 310 serves a dual function of trapping both reactive oxygen species and C and H radicals, reducing the flammability of the spray after electrolyte failure.
In one embodiment, the poisoning agent 310 includes at least one of an amine-based poisoning agent, a carbonate-based poisoning agent, or a water-based poisoning agent, ensuring that the poisoning agent 310 blocks thermal runaway. The water-based poisoning agent includes a hydrosol.
In one embodiment, the chemical inhibitor 30 further comprises a dispersant 320. The vaporization temperature of the dispersant 320 is lower than the trigger temperature for thermal runaway of the battery. The dispersant 320 is used to accelerate the diffusion rate of the poisoning agent 310.
Since the vaporization temperature of the dispersion agent 320 is lower than the trigger temperature of the thermal runaway of the battery, the dispersion agent 320 expands in volume before the thermal runaway of the battery occurs. The volume of the dispersant 320 is expanded, the pressure of the first space 201 is greater than the strength of the first case 20, and the dispersant 320 breaks through the first case 20 and diffuses into the battery internal space. The poisoning agent 310 also diffuses into the electrolyte 150 rapidly with the air wave.
In one embodiment, the dispersant 320 has a better wettability with the electrolyte 150. The dispersant 320 wraps the poisoning agent 310 and infiltrates into the electrolyte 150, promotes the action of the poisoning agent 310 with radicals in the electrolyte 150, and inhibits a chemical reaction that generates electric energy.
The poisoning agent 310 and the dispersant 320 may be placed in a mixed state or may be placed separately.
In one embodiment, the destruct structure 10 further comprises a barrier 40. The partition 40 is disposed in the first space 201. The partition 40 separates a second space 202 from the first space 201. The poisoning agent 310 is received in the first space 201. The dispersant 320 is received in the second space 202.
The poisoning agent 310 and the dispersing agent 320 are respectively placed in different accommodating spaces, so that the poisoning agent 310 and the dispersing agent 320 are prevented from being in contact with each other for a long time to generate a chemical reaction, and the functions of the poisoning agent 310 and the dispersing agent 320 are prevented from being influenced.
The first space 201 and the second space 202 may have the same shape or different shapes. The first space 202 may also be arranged to surround the second space 202.
The first space 201 and the second space 202 may have the same size or different sizes. The positions, shapes and sizes of the first space 201 and the second space 202 are set according to the chemical properties and the dosage of the poisoning agent 310 and the dispersant 320.
In one embodiment, the strength of the barrier 40 is not greater than the strength of the first housing 20 to ensure that when the first housing 20 is ruptured, the barrier 40 is also ruptured to allow the poisoning agent 310 and the dispersant 320 to diffuse into the electrolyte 150.
The material of the partition 40 may be the same as or different from the material of the first housing 20.
In one embodiment, the material of the first housing 20 is the same as the material of the barrier 40 to ensure that when the first housing 20 is ruptured, the barrier 40 is ruptured to release the poisoning agent 310.
In one embodiment, the self-destruct structure 10 further comprises a trigger 400. The trigger 400 is in contact with the chemical inhibitor 30. The trigger 400 is used to trigger the chemical inhibitor 30 to vaporize, and the trigger temperature of the trigger 400 is lower than the trigger temperature of the battery thermal runaway.
In one embodiment, the trigger body 400 is a lead. When the temperature inside the battery rises and the environment in which the lead is placed satisfies the autoignition condition, the autoignition of the lead causes the chemical inhibitor 30 to vaporize. The chemical inhibitor 30 vaporizes the volume expansion. The chemical inhibitor 30 breaks through the first housing 20. The chemical inhibitor 30 diffuses into the battery electrolyte. The chemical inhibitor 30 serves to block an oxidation-reduction reaction when the battery thermally runaway, thereby suppressing the thermal runaway of the battery 100 and improving the safety of the battery 100.
The trigger 400 may be received only in the first space 201 or the second space 202.
The trigger 400 may be partially received in the first space 201 or the second space 202, and the rest of the trigger 400 is outside the first housing 20.
The shape of the trigger body 400 is not limited. The trigger body 400 may be a tubular structure or a wire-like structure.
In one embodiment, the trigger body 400 is a wire-like structure. The trigger body 400 includes a first end and a second end. The first end is received in the first space 201 or the second space 202. The second end extends to the outside of the first housing 20. The second end is placed at the contact part of the outermost side of the battery and other batteries.
When the poisoning agent 310 and the dispersor 320 are mixed, the first end is in contact with the poisoning agent 310 and the dispersor 320.
In one embodiment, when the poisoning agent 310 and the dispersant 320 are separately placed, the first end is only in contact with the dispersant 320 and not in contact with the poisoning agent 310, so as to ensure that the poisoning agent 310 is not contaminated.
Referring also to fig. 3, in one embodiment, the first casing 20 is an electrode casing 501 or a diaphragm casing 141.
When the first case 20 is the electrode case 501, the chemical inhibitor 30 is accommodated in the internal space of the electrode case 501, thereby forming a sandwich electrode. When the first casing 20 is the diaphragm casing 141, the chemical inhibitor 30 is accommodated in the internal space of the diaphragm casing 141 to form a sandwich diaphragm.
The embodiment of the present application provides an electrolyte 150, and the electrolyte 150 has the self-destruction structure 10 as described in any of the above embodiments. When heat builds up inside the battery 100, the temperature of the chemical inhibitor 30 inside the self-destruct structure 10 increases. The chemical inhibitor 30 vaporizes the volume expansion. The chemical inhibitor 30 breaks through the first housing 20. The chemical inhibitor 30 diffuses into the battery electrolyte 150. The chemical inhibitor 30 serves to block an oxidation-reduction reaction when the battery thermally runaway, thereby suppressing the thermal runaway of the battery 100 and improving the safety of the battery 100.
The self-destructive structure 10 may be a particulate structure.
Referring to fig. 4, an electrode 500 according to an embodiment of the present application includes an electrode housing 501 and a self-destruction structure 10 according to any of the embodiments, where the self-destruction structure 10 is disposed on an outer surface of the electrode housing 501. The self-destructive structure 10 is disposed on the outer surface of the electrode 500, and the self-destructive structure 10 may be coated. As heat builds up inside the cell 100 and the temperature rises, the chemical inhibitor 30 vaporizes, expands in volume and diffuses into the cell's electrolyte 150. The chemical inhibitor 30 serves to block an oxidation-reduction reaction when the battery thermally runaway, thereby suppressing the thermal runaway of the battery 100 and improving the safety of the battery 100.
Referring to fig. 5, the present embodiment provides a diaphragm 140, which includes a diaphragm casing 141 and the self-destruct structure 10 according to any of the above embodiments, wherein the self-destruct structure 10 is disposed on an outer surface of the diaphragm casing 141. The outer surface of the membrane 140 is provided with the self-destruct structure 10, and the self-destruct structure 10 may form a coating. As heat builds up inside the cell 100 and the temperature rises, the chemical inhibitor 30 vaporizes, expands in volume and diffuses into the cell's electrolyte 150. The chemical inhibitor 30 serves to block an oxidation-reduction reaction when the battery thermally runaway, thereby suppressing the thermal runaway of the battery 100 and improving the safety of the battery 100.
Referring to fig. 6, the present embodiment provides a battery 100, which includes a battery housing 110 and a self-destruction structure 10 according to any of the above embodiments, wherein the battery housing 110 forms a third space 111 around the battery housing, and the self-destruction structure 10 is received in the third space 111.
In one embodiment, the battery 100 includes a battery case 110, a positive electrode 120, a positive electrode coating 121, a negative electrode 130, a negative electrode coating 131, a separator 140, and an electrolyte 150. The battery case 110 defines a third space 111. The positive electrode 120, the positive electrode coating layer 121, the negative electrode 130, the negative electrode coating layer 131, the separator 140, and the electrolyte 150 are all accommodated in the third space 111. The positive electrode 120 is disposed opposite to the negative electrode 130 at an interval. The positive electrode coating 121 is attached to the surface of the positive electrode 120 close to the negative electrode 130. The negative electrode coating 131 is attached to the surface of the negative electrode 130 close to the positive electrode 120. The separator 140 is disposed between the positive electrode coating 121 and the negative electrode coating 131. The electrolyte 150 is filled in the third space 111.
When the battery 100 is charged, lithium ions are generated on the positive electrode coating 121 of the battery 100, and the generated lithium ions move to the negative electrode through the electrolyte 150. The negative electrode coating 131 has a carbon layer structure. The carbon layered structure has many micropores, so that lithium ions reaching the negative electrode are inserted into the micropores of the carbon layer, and the more lithium ions are inserted, the higher the charge capacity is. Also, when the battery 100 is discharged (i.e., our process of using the battery), lithium ions embedded in the carbon layer structure are extracted and move back to the positive electrode coating 121. The more lithium ions returned to the positive electrode, the higher the discharge capacity.
The self-destruct structure 10 may be disposed within the electrolyte 150, within an interior space, within the electrode 500, or within the separator 140 of the battery 100. The self-destruction structure 10 is disposed according to the degree of heat release inside the battery and the position where heat is easily accumulated.
The self-destruct structure 10 may be disposed on the inner surface of the battery case 110, the outer surface of the electrode 500 or the outer surface of the separator 140. The self-destruct structure 10 includes the first housing 20 and the chemical inhibitor 30. The chemical inhibitor 30 includes the poisoning agent 310 and a dispersant 320.
The vaporization temperature of the dispersant 320 is lower than the trigger temperature for thermal runaway of the battery. The dispersant 320 expands in volume before thermal runaway of the battery occurs. The volume of the dispersant 320 is expanded, the pressure of the first space 201 is greater than the strength of the first case 20, and the dispersant 320 breaks through the first case 20 and diffuses into the battery internal space. The poisoning agent 310 also diffuses into the electrolyte 150 rapidly with the air wave.
The organic carbonate compounds of the electrolyte 150 have high activity and are extremely easy to burn. The battery anode material in the charged state is a strong oxidizing compound, while the battery cathode material in the charged state is a strong reducing compound. Strongly oxidizing positive electrode materials are generally less stable and prone to oxygen evolution under abusive conditions, such as overcharge, overheating, and short circuits. Carbonates, however, react very readily with oxygen, releasing large amounts of heat and gases. The generated heat can further accelerate the decomposition of the positive electrode, generate more oxygen and promote more exothermic reactions. Meanwhile, the activity of the negative electrode with strong reducibility is close to that of metal lithium, and the negative electrode can be immediately burnt and ignite electrolyte, a diaphragm and the like when being contacted with oxygen, so that thermal runaway of the battery is caused, and the battery can be burnt and exploded.
The poisoning agent 310 suppresses an oxidation-reduction reaction for blocking thermal runaway of the battery, thereby reducing energy released from the thermal runaway of the battery. The poisoning agent 310 reduces the rate of heat generated inside the battery, prevents heat from being accumulated, and improves the safety of the battery 100.
The poisoning agent 310 can be used for three ways of restraining thermal runaway, which are respectively:
the first method comprises the following steps: the poisoning agent 310 includes a group that polymerizes the carbonate electrolyte. The group abstracts electrons from the cyclic carbonate such that the carbonate undergoes ring opening. The ring-opened carbonate is then mixed with the said groups for polymerization. The poisoning agent 310 reduces the concentration of the carbonate, which in turn reduces the rate of the redox reaction of the carbonate with oxygen. The self-destruction structure 10 thus suppresses thermal runaway of the battery 100, and improves the safety of the battery 100.
And the second method comprises the following steps: the poisoning agent 310 includes a group that renders the negative electrode of the battery inert. The poisoning agent 310 and the strong reducing cathode LixC6Reaction is carried out to ensure that Li of the cathode releases oxygen when the anode or the organic solvent releases oxygenxC6The reaction was complete. Oxygen cannot react with LixC6A severe redox reaction occurs, thereby reducing thermal runaway energy.
And the third is that: the poisoning agent 310 includes a group that binds to a reactive oxygen species or a free radical. The concentration of C radicals or H radicals in the electrolyte is reduced, and the rate of redox reaction is reduced. The self-destruction structure 10 thus suppresses thermal runaway of the battery 100, and improves the safety of the battery 100.
In one embodiment, the self-destruction structure 10 is disposed in the third space 111 and is not in contact with the electrolyte 150. The second end of the trigger 400 is disposed at a position where the electrolyte 150 is close to the inner wall of the battery 100. The temperature of the inner wall of the battery 100 is higher than that of other parts, and the second end of the trigger 400 can sense the temperature change in time, so that the trigger 400 can timely trigger the gasification of the chemical inhibitor 30.
In one embodiment, the battery 100 includes a plurality of jelly rolls 600. Each of the jelly rolls 600 includes one of the positive electrode 120 and the positive electrode coating 121, one of the negative electrode 130 and the negative electrode coating 131, and one of the separators 140. The self-destruction structure 10 is disposed between two adjacent winding cores 600. When the temperature of the winding core 600 adjacent to the self-destruction structure 10 is increased to a set temperature, the second end of the trigger 400 can sense the temperature change in time. The trigger 400 triggers the chemical inhibitor 30 to vaporize in time. The chemical inhibitor 30 vaporizes the volume expansion. The chemical inhibitor 30 breaks through the first housing 20. The chemical inhibitor 30 diffuses into the battery electrolyte. The chemical inhibitor 30 serves to block the redox reaction upon thermal runaway of the battery. Since the self-destruction structure 10 is disposed between two adjacent winding cores 600, the self-destruction structure 10 can prevent thermal runaway from spreading to the adjacent winding cores 600. The self-destruction structure 10 suppresses thermal runaway of the battery 100, and improves the safety of the battery 100. The self-destruct structure 10 is of significant value to the safety design of high specific energy lithium ion batteries.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-described examples merely represent several embodiments of the present application and are not to be construed as limiting the scope of the claims. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (13)
1. A self-destruct structure, characterized in that said self-destruct structure (10) is intended to be housed within a battery (100), said self-destruct structure (10) comprising:
a first housing (20) enclosing a first space (201);
and a chemical inhibitor (30) housed in the first space (201), wherein the chemical inhibitor (30) is used for inhibiting an oxidation-reduction reaction when the battery is in thermal runaway, and the gasification temperature of the chemical inhibitor (30) is lower than a trigger temperature of the battery in thermal runaway.
2. The self-destructive structure according to claim 1, wherein said chemical inhibitor (30) comprises:
a poisoning agent (310), the poisoning agent (310) including a group that polymerizes a carbonate electrolyte.
3. The self-destruct structure according to claim 2, wherein said poisoning agent (310) comprises a group that renders the negative electrode of the battery inert.
4. The self-destructing structure according to claim 2, wherein the poisoning agent (310) comprises a group that binds to a reactive oxygen species or a free radical.
5. The self-destruct structure according to claim 2, wherein said poisoning agent (310) comprises at least one of an amine-based poisoning agent or a carbonate-based poisoning agent.
6. The self-destruct structure according to claim 2, characterized in that said chemical inhibitor (30) further comprises:
a dispersant (320), the vaporization temperature of the dispersant (320) being below a trigger temperature for thermal runaway of the battery.
7. The self-destruct structure of claim 6, further comprising:
a partition (40) disposed in the first space (201), wherein the partition (40) partitions the first space (201) into a second space (202), the poisoning agent (310) is contained in the first space (201), and the dispersant (320) is contained in the second space (202).
8. The self-destruct structure of claim 1, further comprising:
a trigger body (400) in contact with the chemical inhibitor (30), the trigger body (400) being configured to initiate vaporization of the chemical inhibitor (30), and a trigger temperature of the trigger body (400) being lower than a trigger temperature of the battery thermal runaway.
9. Self-destructing structure according to any one of claims 1 to 8, characterised in that the first housing (20) is an electrode housing (501) or a membrane housing (141).
10. An electrolyte, characterized in that the electrolyte has a self-destructing structure (10) according to any one of claims 1 to 9.
11. An electrode, characterized in that it comprises an electrode housing (501) and a self-destructing structure (10) according to any one of claims 1-9, said self-destructing structure (10) being arranged on an outer surface of said electrode housing (501).
12. A membrane, comprising a membrane housing (141) and a self-destruct structure (10) according to any one of claims 1-9, said self-destruct structure (10) being disposed on an outer surface of said membrane housing (141).
13. A battery, characterized in that it comprises a battery case (110) and a self-destructive structure (10) according to any one of claims 1 to 9, said battery case (110) enclosing a third space (111), said self-destructive structure (10) being received in said third space (111).
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| CN202010690360.4A CN112018445A (en) | 2020-07-17 | 2020-07-17 | Self-destruction structure, electrolyte, electrode, diaphragm and battery |
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| CN202010690360.4A CN112018445A (en) | 2020-07-17 | 2020-07-17 | Self-destruction structure, electrolyte, electrode, diaphragm and battery |
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