CN108666524B - Battery electrode, preparation method thereof and lithium ion battery - Google Patents
Battery electrode, preparation method thereof and lithium ion battery Download PDFInfo
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- CN108666524B CN108666524B CN201710204488.3A CN201710204488A CN108666524B CN 108666524 B CN108666524 B CN 108666524B CN 201710204488 A CN201710204488 A CN 201710204488A CN 108666524 B CN108666524 B CN 108666524B
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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
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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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
- H01M4/624—Electric conductive fillers
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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 an electrode of a battery, a preparation method thereof and a lithium ion battery using the electrode. The electrode of the battery comprises a conductive base body and a material layer coated on the surface of the conductive base body, wherein the material layer comprises a conductive material layer attached to the conductive base body and an active material layer attached to the conductive material layer, the conductive material layer comprises a conductive substance and a gas generating substance, and the gas generating substance can generate gas when heated, so that the potential safety hazard caused by battery overheating failure can be fundamentally solved, and the safety of a battery pack is remarkably improved.
Description
Technical Field
The invention relates to a lithium ion secondary battery, in particular to an electrode of the battery, a preparation method of the electrode and a lithium ion battery using the electrode.
Background
Due to the rapid development and wide application of portable electronic devices and electric vehicles, the demand for lithium ion batteries with high specific energy, long cycle life and high safety performance is urgent.
Particularly, the safety performance of the battery is always a focus and a hot point of research, and the existing method for improving the safety performance of the battery is mainly solved from the aspects of heat management, the safety structure of a single battery, addition of a flame retardant additive into electrolyte and the like. However, thermal management, whether from the circuit or the cooling system, has certain problems, such as the situation that the circuit has collection failure; the cooling system can only partially reduce the operating temperature of the battery, and has a limited ability to reduce the temperature, and the cooling system is heavy, greatly reducing the energy density of the battery. Although the safety structure of the single battery can control the single battery in time, the current design difficulty is large, the scheme is not complete, and the high-temperature safety problem of the battery cannot be fundamentally solved; the introduction of flame retardant additives brings new problems, such as increased impedance of the battery, and the rate and low temperature performance of the battery are affected to various degrees. Therefore, not only the search for improving the safety performance of the battery is still needed.
Disclosure of Invention
The invention aims to overcome the defect that the safety performance of the existing battery is still not ideal, and provides an electrode of the battery, a preparation method thereof and a lithium ion battery using the electrode, wherein the electrode can radically solve the safety problem of the battery and greatly improve the safety performance of the battery.
The first object of the invention is to provide an electrode of a battery, which comprises a conductive substrate and a material layer coated on the surface of the conductive substrate, wherein the material layer comprises a conductive material layer attached on the conductive substrate and an active material layer attached on the conductive material layer, the conductive material layer comprises a conductive substance and a gas generating substance, and the gas generating substance can generate gas when being heated.
A second object of the present invention is to provide a method for preparing the above electrode, which comprises attaching a conductive material layer containing a conductive substance and a gas-generating substance on a conductive substrate, and then attaching an active material layer on the conductive material layer.
The third purpose of the invention is to provide a lithium ion battery, which comprises a pole core and electrolyte, wherein the pole core and the electrolyte are sealed in a battery shell, the pole core comprises a positive pole, a negative pole and a diaphragm, and the positive pole and/or the negative pole are/is the above-mentioned electrodes.
The material layer of the electrode comprises a conductive material layer attached to a conductive substrate, wherein the conductive material layer contains a gas generating substance, when the battery is abnormal, the temperature inside the battery is increased, the gas generating substance generates gas by heat, so that the active material layer falls off and peels off, the material layer is in an open circuit state, the current of the battery is not conducted, and the battery core is powered off in advance, so that the battery is opened before potential safety hazards are caused by overheating failure of the battery (particularly before a diaphragm is broken, a film is molten and shrunk, if the diaphragm is heated and shrunk, the positive electrode and the negative electrode of the battery can be short-circuited, and safety accidents are easily caused). The potential safety hazard caused by battery overheating failure is fundamentally solved, and the safety of the battery pack is remarkably improved.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides an electrode of a battery, which comprises a conductive substrate and a material layer coated on the surface of the conductive substrate, wherein the material layer comprises a conductive material layer attached on the conductive substrate and an active material layer attached on the conductive material layer, the conductive material layer comprises a conductive substance and a gas generating substance, and the gas generating substance can generate gas when heated, so that the potential safety hazard caused by battery overheating failure is fundamentally solved, and the safety of a battery pack is remarkably improved.
The material layer can be positioned on one side of the conductive base body or positioned on two sides of the conductive base body.
The electrode may be a positive electrode of a battery or a negative electrode of a battery, and the present invention is preferably applied to a positive electrode, that is, an active material layer is a positive active material layer. The positive active material in the positive active material layer can be a positive active material for various lithium ion batteries, and preferably is one or more of lithium cobaltate, nickel cobalt lithium manganate ternary material and nickel cobalt lithium aluminate ternary material. The nickel cobalt lithium manganate ternary material and the nickel cobalt lithium aluminate ternary material are various nickel cobalt lithium manganate ternary materials and nickel cobalt lithium aluminate ternary materials known to those skilled in the art, and for example, the proportion of nickel, cobalt and manganese (aluminum) may be changed, and may also contain doping elements. The scheme of the invention has better interaction with ternary materials of lithium cobaltate, lithium nickel cobalt manganese oxide and lithium nickel cobalt aluminate, has more outstanding effect on the ternary materials of lithium nickel cobalt manganese oxide and lithium nickel cobalt aluminate, and practically solves the difficult problem of the existing ternary materials, the ternary materials have more obvious safety problem due to the thermodynamic stability problem of the ternary materials, and oxygen in the ternary materials is formed in a transition metal-oxygen octahedron form and has a layered structure. The structure determines that the chemical stability of oxygen element in the ternary material is low, and in a charging state (electron losing state), the electron energy level can be reduced to the 2p orbital energy band of oxygen, so that O is generated2-The ions are oxidized. Therefore, the charged ternary material can separate out oxygen in the states of heating, overcharging and the like, and severe combustion and explosion of the battery are caused under the strong combustion supporting effect of the oxygen, and all the safety structures of the battery only aim at the problemThe surface protection can be carried out, large manufacturers adopt multiple safety protection structures as much as possible in order to improve the safety performance of the battery, and spend a large amount of manpower and material resources to develop the protection structures as much as possible, but all take the temporary solution and not take the permanent solution, and all the solutions are not solved from the root. The technical scheme of the invention can well solve the safety performance of the ternary material and fundamentally prevent the ternary battery from generating severe thermal runaway from the electrodes.
The positive active material layer is a mixture of a positive active material, a binder and a conductive agent; the weight ratio of the binder, the positive electrode active material, and the conductive agent in the positive electrode active material layer of the present invention is not particularly limited, and a conventional design may be employed. The type and amount of binder is well known to those skilled in the art, for example, fluorine-containing resins and polyolefin compounds such as polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), and cellulose-based polymers, etc.
The positive conductive substrate may be a conventional positive conductive substrate in a lithium ion battery, such as a stamped metal, a metal foil, a mesh metal, a foam metal, etc., and an aluminum foil is used as the positive conductive substrate in the embodiment of the present invention.
Preferably, the gas production temperature of the gas production substance is lower than the decomposition temperature of the positive electrode active material, so that the positive electrode active material can be stripped before the battery reaches the thermal runaway temperature, the connection between the positive electrode active material and the conductive substrate is cut off or the impedance of the electrode is greatly increased, and the effects of preventing short circuit and thermal runaway in the battery are better achieved.
Preferably, the gas generating temperature of the gas generating substance is lower than the melting point of the battery separator. The active material can fall off before the membrane rupture, melting and shrinkage of the membrane, so that the membrane is prevented from being heated and shrunk, the short circuit between the anode and the cathode of the battery is prevented, serious safety problems such as fire explosion and the like are avoided, and the safety problem of the battery is fundamentally solved.
The invention further preferably selects the gas production temperature of the gas production substance to be 80-180 ℃, and further preferably selects 120-180 ℃, so that the failure of the battery under the conventional high-temperature use can be further prevented, the thermal failure of the battery can be more accurately prevented, and the situations of false triggering, triggering delay and the like can be prevented.
According to the invention, preferably, the gas generating substance is one or more selected from diammonium hydrogen phosphate, ammonium bicarbonate, ammonium carbonate, ammonium nitrate or ammonium chloride, a large amount of gas can be rapidly released under the heated condition, the current collector and the battery active substance are isolated, and the generated gas is a non-combustible gas, so that the combustion and explosion of the battery can be further prevented, and the safety performance of the battery can be further improved. Further, according to the invention, the gas generating substance is preferably selected from diammonium hydrogen phosphate, is more matched with the positive active material and the diaphragm of the battery, and can more accurately prevent the thermal failure of the battery.
The conductive material is not limited in the present invention, and may be, for example, a conductive polymer or an inorganic conductive agent, and if the conductive polymer is a conductive polymer, a conductive polymer having adhesive properties may be directly selected. The conductive substance is preferably selected from one or more of conductive graphite, carbon nanotubes and graphene. Generally, when an inorganic conductive agent is selected, the conductive material layer may further contain a binder, that is, the conductive material layer contains a conductive substance, a binder and a gas generating substance.
It is preferred that the layer of conductive material of the present invention further comprises a binder. More preferably, based on the weight percentage of the conductive material layer, the content of the conductive substance is 60 wt% to 85 wt%, the content of the binder is 15 wt% to 40 wt%, and the content of the gas generating substance is 1 wt% to 5 wt%.
Preferably, the thickness of the conductive material layer is 0.5-10 μm.
The invention also provides a preparation method of the electrode, which comprises the steps of firstly attaching a conductive material layer containing a conductive substance and a gas generating substance on a conductive substrate, and then attaching an active material layer on the conductive material layer.
The method of attaching the conductive material layer to the conductive substrate and then attaching the active material layer may employ various coating methods that are conventional in the art, for example, the method includes first coating a slurry containing a conductive substance, a gas generating substance, and a solvent on the surface of the conductive substrate, drying, rolling or not, to form the conductive material layer, then coating a slurry containing an active material and a solvent on the conductive material layer, drying, rolling or not, to form the active material layer. According to the present invention, a plurality of conductive material layers and a plurality of active material layers may be formed on a conductive substrate according to different needs of different batteries. The specific preparation process can be as follows: (1) when the binder is selected, the binder is uniformly mixed in a solvent to form stable binder slurry; (2) adding a conductive substance and a gas generating substance into the binder slurry, and uniformly mixing to form slurry of a conductive material layer; (3) and uniformly and finely coating the slurry of the conductive material layer on the conductive substrate aluminum foil to form a uniform conductive material layer with the thickness of 0.5-10 mu m approximately.
The amount of the solvent in the above-mentioned slurry containing a conductive material, a gas generating material and a solvent for forming a conductive material layer and the slurry containing an active material and a solvent is not particularly limited, and the amount of the solvent may be such that the slurry has viscosity and fluidity and can be applied to the conductive substrate or the conductive material layer. The solvent can be one or more selected from N-methylpyrrolidone (NMP), Dimethylformamide (DMF), Diethylformamide (DEF), dimethyl sulfoxide (DMSO), Tetrahydrofuran (THF) and water and alcohol; the solvent is preferably water.
The invention also provides a lithium ion battery, which comprises a pole core and electrolyte, wherein the pole core and the electrolyte are sealed in a battery shell, the pole core comprises a positive pole, a negative pole and a diaphragm, and the positive pole and/or the negative pole are/is the above-mentioned electrodes.
The positive electrode and the negative electrode of the lithium ion battery can adopt the scheme, and the positive electrode is preferably the electrode, so that the response is quicker, and the safety performance of the battery is better solved.
The improvement of the present invention relates only to the electrode, and therefore, in the lithium ion battery provided by the present invention, there is no particular limitation on the separator and the electrolyte of the battery, and all types of separators and electrolytes that can be used in the lithium ion battery can be used.
For the technical scheme that the electrode is the anode, the cathode may adopt a conventional cathode, that is, the cathode includes a cathode conductive substrate and a cathode active material layer attached on the cathode conductive substrate, wherein the cathode conductive substrate may be a conventional cathode conductive substrate in a lithium ion battery, such as a stamped metal, a metal foil, a net metal, a foam metal, etc., and in a specific embodiment of the present invention, a copper foil is used as the cathode conductive substrate. The negative active material layer is not particularly limited and may be a negative active material layer that is conventional in the art, the negative active material in the negative active material layer may be a graphite-based material, a silicon-based material, lithium titanate, or the like, the negative active material layer may or may not contain a conductive agent, and the type and content of a binder in the negative active material layer are well known to those skilled in the art, for example, one or more of fluorine-containing resin and polyolefin compounds such as polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), Styrene Butadiene Rubber (SBR).
The electrolyte solution of the lithium ion battery may be a mixed solution of an electrolyte lithium salt and a nonaqueous solvent, and is not particularly limited, and a nonaqueous electrolyte solution that is conventional in the art may be used. For example, the electrolyte lithium salt is selected from lithium hexafluorophosphate (LiPF)6) One or more of lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium halide, lithium chloroaluminate and lithium fluoro alkyl sulfonate. The organic solvent is a mixed solution of chain acid ester and cyclic acid ester, wherein the chain acid ester can be at least one of dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), Methyl Propyl Carbonate (MPC), dipropyl carbonate (DPC) and other chain organic esters containing fluorine, sulfur or unsaturated bonds, and the cyclic acid ester can be at least one of Ethylene Carbonate (EC), Propylene Carbonate (PC), Vinylene Carbonate (VC), gamma-butyrolactone (gamma-BL), sultone and other cyclic organic esters containing fluorine, sulfur or unsaturated bonds. The injection amount of the electrolyte is generally 1.5 to 4.9g/Ah, and the concentration of the electrolyte is generally 0.5 to 2.9 mol/L.
The separator of a lithium ion battery is disposed between a positive electrode and a negative electrode, has electrical insulating properties and liquid retaining properties, and allows the electrode core to be contained in a battery case together with an electrolyte. The separator may be selected from various separators used in lithium ion batteries, such as polyolefin microporous membranes. The location, nature and kind of the diaphragm are well known to those skilled in the art.
The present invention will be further specifically described below by way of specific examples, but it should not be construed as limiting the scope of the present invention.
Example 1
(1) Preparation of the Positive electrode
Mixing carboxymethyl cellulose, styrene-butadiene rubber and water according to the weight ratio of 1: 1: 90 weight ratio, mixing and stirring to obtain uniform binder slurry, mixing nanometer conductive graphite and diammonium hydrogen phosphate (chemical formula is (NH)4)2HPO4Gas generation begins at 120 ℃) and the binder slurry are added into the binder slurry according to the weight ratio of 10:10:105, the mixture is fully mixed and stirred evenly, the slurry is evenly coated on the two sides of a conductive matrix aluminum foil with the thickness of 0.008 mm, and the conductive material layer with the thickness of 3 microns is obtained after drying at 100 ℃; then NCM111 (LiNi)1/3Mn1/3Co1/3O2) (oxygen is generated by starting thermal decomposition at 290 ℃ in a charged state), acetylene black, polytetrafluoroethylene and N-methylpyrrolidone according to the weight ratio of 100: 3: 2: 50 into slurry, uniformly coating the slurry on a conductive material layer, drying at 110 ℃, rolling and cutting to obtain the positive plate A1 with the dimensions of 485 mm × 44 mm × 0.140 mm.
(2) Preparation of the negative electrode
Mixing natural graphite, carboxymethyl cellulose, styrene butadiene rubber and water according to the weight ratio of 100: 2: 2: 180 to obtain uniform slurry, uniformly coating the slurry on two sides of a conductive base copper foil with the thickness of 0.008 mm, drying at 100 ℃, and finally cutting to obtain a negative plate with the size of 480 mm multiplied by 45 mm multiplied by 0.156 mm.
(3) Assembly of a battery
Winding the positive plate, the negative plate and the polypropylene film (with the melting point of 170 ℃) into a pole core of a square lithium ion battery, and then winding LiPF6The electrolyte was dissolved in a mixed solvent of EC/DMC 1:1 at a concentration of 1 mol/l to prepare an electrolyte, and the electrolyte was injected into an aluminum plastic film at an amount of 3.6g/Ah, followed by sealing to prepare a soft package lithium ion battery S1.
Example 2
A positive electrode sheet a2 and a lithium ion battery S2 were prepared by the same method steps as in example 1, except that the gas-generating substance was ammonium carbonate (chemical formula (NH)4)2CO3And the gas production temperature is 80 ℃).
Example 3
A positive electrode sheet a3 and a lithium ion battery S3 were prepared by the same method steps as in example 1, except that nano conductive graphite and diammonium hydrogen phosphate (chemical formula is (NH)4)2HPO4) The weight ratio of the binder slurry to the binder slurry is 10: 5: 105.
example 4
A positive electrode sheet a4 and a lithium ion battery S4 were prepared by the same method steps as in example 1, except that nano conductive graphite and diammonium hydrogen phosphate (chemical formula is (NH)4)2HPO4) The weight ratio of the binder slurry to the binder slurry is 10: 20: 105.
example 5
A positive electrode sheet a5 and a lithium ion battery S5 were prepared by the same method steps as in example 1, except that nano conductive graphite and diammonium hydrogen phosphate (chemical formula is (NH)4)2HPO4) The weight ratio of the binder slurry to the binder slurry is 10: 2: 105.
example 6
A positive electrode sheet a6 and a lithium ion battery S6 were prepared by the same process steps as in example 1, except that ammonium hydrogen phosphate (chemical formula (NH)4)2HPO4)。
Example 7
A lithium ion battery S7 was prepared using the same process steps as in example 2, except that a high melting aramid separator (melting point > 300 ℃ C.) was used
Comparative example 1
(1) Preparation of the Positive electrode
NCM111 (beginning to thermally decompose at 290 ℃ in a charged state to generate oxygen), acetylene black, polytetrafluoroethylene and N-methylpyrrolidone in a weight ratio of 100: 3: 2: 50 into slurry, evenly coating the slurry on an aluminum foil of a conductive matrix, drying at 110 ℃, rolling and cutting to obtain the positive plate DA1 with the size of 485 mm multiplied by 44 mm multiplied by 0.140 mm.
(2) Preparation of the negative electrode
Mixing natural graphite, carboxymethyl cellulose, styrene butadiene rubber and water according to the weight ratio of 100: 2: 2: 180 to obtain uniform slurry, uniformly coating the slurry on two sides of a conductive base copper foil with the thickness of 0.008 mm, drying at 100 ℃, and finally cutting to obtain a negative plate with the size of 480 mm multiplied by 45 mm multiplied by 0.156 mm.
(3) Assembly of a battery
Winding the positive plate, the negative plate and the polypropylene film (with the melting point of 170 ℃) into a pole core of a square lithium ion battery, and then winding LiPF6The electrolyte solution was dissolved in a mixed solvent of EC/DMC 1:1 at a concentration of 1 mol/l to give an electrolyte solution, and the electrolyte solution was injected into an aluminum plastic film at a rate of 3.6g/Ah, followed by sealing to give a soft pack lithium ion battery DS 1.
Performance testing
1. Testing the thermal safety of the battery at 150 ℃: the batteries S1 to S7 and DS1 prepared in the above examples 1 to 7 and comparative example 1 were subjected to a 150 ℃ furnace thermal safety test; the test method comprises the following steps: the furnace was heated at 150 ℃ for 2 hours, and the results are shown in Table 1.
TABLE 1
| Battery with a battery cell | Safety performance |
| S1 | Through, no phenomenon |
| S2 | Smoking with a certain risk of fire |
| S3 | By smoking |
| S4 | Through, no phenomenon |
| S5 | Smoking with a certain risk of fire |
| S6 | By smoking |
| S7 | Through, no phenomenon |
| DS1 | Fire and explosion |
As can be seen from the results in Table 1, the technical scheme of the invention can obviously improve the safety performance of the battery.
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 and improvements made within the spirit and principle of the present invention are intended to be included therein.
It will be understood by those skilled in the art that the foregoing is merely exemplary of the present invention, and is not intended to limit the invention to the particular forms disclosed herein, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims. The scope of the invention is defined by the claims.
Claims (11)
1. The electrode of a battery comprises a conductive base body and a material layer coated on the surface of the conductive base body, and is characterized in that the material layer comprises a conductive material layer attached to the conductive base body and an active material layer attached to the conductive material layer, and the conductive material layer comprises a conductive substance and a gas generating substance;
the gas generating substance can generate gas by heating, so that the active material layer falls off and peels off, and the material layer is in an open circuit state; the gas production temperature of the gas production substance is lower than the diaphragm melting point of the battery; the gas production substance is selected from one or more of diammonium hydrogen phosphate, ammonium bicarbonate, ammonium carbonate, ammonium nitrate or ammonium chloride.
2. The electrode according to claim 1, wherein the active material layer is a positive electrode active material layer.
3. The electrode according to claim 2, wherein the positive electrode active material in the positive electrode active material layer is one or more of lithium cobaltate, lithium nickel cobalt manganese oxide ternary material and lithium nickel cobalt aluminate ternary material.
4. The electrode of claim 2, wherein the gas generating substance has a gas generating temperature lower than a decomposition temperature of the positive electrode active material.
5. The electrode of claim 1, wherein the gas generating species is selected from diammonium phosphate.
6. The electrode according to claim 1, wherein the conductive material is selected from one or more of conductive graphite, carbon nanotubes and graphene.
7. The electrode of claim 1, wherein the layer of conductive material further comprises a binder.
8. The electrode according to claim 1, wherein the thickness of the conductive material layer is 0.5 to 10 μm.
9. A method of manufacturing an electrode according to any one of claims 1 to 8, comprising attaching a layer of conductive material comprising a conductive substance and a gas-generating substance to a conductive substrate and then attaching a layer of active material to the layer of conductive material.
10. A lithium ion battery comprising a core and an electrolyte, the core and the electrolyte being sealed in a battery housing, the core comprising a positive electrode, a negative electrode and a separator, wherein the positive and/or negative electrode is an electrode according to any one of claims 1 to 8.
11. The lithium ion battery of claim 10, wherein the positive electrode is the electrode of any one of claims 1-8.
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| CN201710204488.3A CN108666524B (en) | 2017-03-31 | 2017-03-31 | Battery electrode, preparation method thereof and lithium ion battery |
| PCT/CN2018/071492 WO2018176979A1 (en) | 2017-03-31 | 2018-01-05 | Battery electrode and method for fabricating same, and lithium-ion battery |
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| CN201710204488.3A CN108666524B (en) | 2017-03-31 | 2017-03-31 | Battery electrode, preparation method thereof and lithium ion battery |
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| CN111628218B (en) * | 2020-05-18 | 2021-08-31 | 珠海冠宇电池股份有限公司 | Lithium ion battery and preparation method thereof |
| CN112490407B (en) * | 2020-12-02 | 2023-12-01 | 欣旺达动力科技股份有限公司 | Electrode plate, preparation method thereof and lithium ion battery |
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| JP2005011540A (en) * | 2003-06-16 | 2005-01-13 | Toshiba Corp | Nonaqueous electrolyte secondary battery |
| CN101752544A (en) * | 2008-12-01 | 2010-06-23 | 比亚迪股份有限公司 | Silicon cathode and preparation method thereof and Li-ion secondary battery comprising silicon cathode |
| CN104137306A (en) * | 2012-02-23 | 2014-11-05 | 丰田自动车株式会社 | Sealed nonaqueous electrolyte secondary battery |
| CN104488118A (en) * | 2012-09-27 | 2015-04-01 | 东洋铝株式会社 | Conductive member, electrode, secondary battery, capacitor, method for producing conductive member, and method for producing electrode |
| CN105810885A (en) * | 2016-04-27 | 2016-07-27 | 宁德时代新能源科技股份有限公司 | Positive pole piece and lithium ion battery |
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| JP2000195523A (en) * | 1998-12-24 | 2000-07-14 | Kao Corp | Nonaqueous secondary battery |
| JP6777388B2 (en) * | 2015-02-27 | 2020-10-28 | パナソニック株式会社 | Non-aqueous electrolyte secondary battery |
| CN205542964U (en) * | 2016-02-22 | 2016-08-31 | 宁德时代新能源科技股份有限公司 | Battery box body |
| CN106450156A (en) * | 2016-09-28 | 2017-02-22 | 湖南立方新能源科技有限责任公司 | Electrode plate and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005011540A (en) * | 2003-06-16 | 2005-01-13 | Toshiba Corp | Nonaqueous electrolyte secondary battery |
| CN101752544A (en) * | 2008-12-01 | 2010-06-23 | 比亚迪股份有限公司 | Silicon cathode and preparation method thereof and Li-ion secondary battery comprising silicon cathode |
| CN104137306A (en) * | 2012-02-23 | 2014-11-05 | 丰田自动车株式会社 | Sealed nonaqueous electrolyte secondary battery |
| CN104488118A (en) * | 2012-09-27 | 2015-04-01 | 东洋铝株式会社 | Conductive member, electrode, secondary battery, capacitor, method for producing conductive member, and method for producing electrode |
| CN105810885A (en) * | 2016-04-27 | 2016-07-27 | 宁德时代新能源科技股份有限公司 | Positive pole piece and lithium ion battery |
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| CN108666524A (en) | 2018-10-16 |
| WO2018176979A1 (en) | 2018-10-04 |
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