CN113451556A - Low-temperature lithium ion battery - Google Patents
Low-temperature lithium ion battery Download PDFInfo
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- CN113451556A CN113451556A CN202110539884.8A CN202110539884A CN113451556A CN 113451556 A CN113451556 A CN 113451556A CN 202110539884 A CN202110539884 A CN 202110539884A CN 113451556 A CN113451556 A CN 113451556A
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
-
- 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
- H01M10/0569—Liquid materials characterised by the solvents
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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
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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 invention discloses a low-temperature lithium ion battery, which belongs to the technical field of lithium ion batteries and is characterized in that: the positive plate comprises an aluminum foil current collector, and a positive active material, a binder and a conductive agent coated on the aluminum foil current collector; the negative plate comprises a copper foil current collector, and a negative active material, a binder and a conductive agent coated on the copper foil current collector; the electrolyte comprises a fluorine-containing solvent, a lithium salt and a cosolvent; the fluorine-containing solvent is one or a compound of more of 1,1,1,3,3, 3-hexafluoropropane, 1,1,1,2,3,3, 3-heptafluoropropane, 1-methoxy heptafluoropropane and 1,1,2,2,3,3, 4-heptafluorocyclopentane; the lithium salt is one or more of LiTFSI and LiFSI; the cosolvent is methylal. According to the invention, the multi-layer graphitized carbon compounded by the carbon nano tubes is used as the negative electrode and the low-boiling-point fluorine-containing non-combustible solvent, so that the migration rate of lithium ions can be greatly improved, and the low-temperature performance and the safety of the battery can be improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a low-temperature lithium ion battery.
Background
Currently, lithium ion batteries are widely used due to their high energy density, good cycle performance and rate capability. However, there are no mature products and technologies for lithium ion batteries that can achieve both high energy density and high safety in a low-temperature environment. Under a low-temperature environment, the viscosity of the electrolyte is increased, so that the migration rate of lithium ions in the lithium ion battery is reduced, and the discharge performance of the lithium ion battery is greatly reduced at a low temperature. Therefore, improving the transmission rate of lithium ions in the lithium ion battery is the key to solve the deterioration of the low-temperature performance of the lithium ion battery. The prior art mainly focuses on the use of low-boiling point solvents to improve the migration performance of lithium ions at low temperature (for example, patent CN111525089B), but uncertain factors are brought to the safety of lithium ion batteries due to the flammable characteristics of low-boiling point organic solvents. Therefore, it is required to develop a high safety lithium ion battery having good low temperature performance and non-flammability.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides a low-temperature lithium ion battery which has good charge and discharge performance, higher energy density and better safety performance under the low-temperature condition.
The invention aims to provide a low-temperature lithium ion battery, which comprises a positive plate, a negative plate, a diaphragm and electrolyte;
the positive plate comprises an aluminum foil current collector, and a positive active material, a binder and a conductive agent coated on the aluminum foil current collector;
the negative plate comprises a copper foil current collector, and a negative active material, a binder and a conductive agent coated on the copper foil current collector;
the electrolyte comprises a fluorine-containing solvent, a lithium salt and a cosolvent; wherein the fluorine-containing solvent is a compound of one or more components of 1,1,1,3,3, 3-hexafluoropropane, 1,1,1,2,3,3, 3-heptafluoropropane, 1-methoxy heptafluoropropane and 1,1,2,2,3,3, 4-heptafluorocyclopentane; the lithium salt is one or more of LiTFSI and LiFSI; the cosolvent is methylal.
Preferably, the positive electrode active material is lithium cobaltate.
Preferably, the negative active material is Co @ Al-MOF (1, 4-H)2NDC) is a carbon material prepared from a precursor.
Preferably, the method for preparing the negative active material comprises:
s1, loading the load with 1 percent～6％CoNO3Al-MOF (1, 4-H) of2NDC) carbonizing at 900-1200 ℃ for 3-6 hours in a nitrogen atmosphere;
and S2, washing the carbonized material with hydrochloric acid aqueous solution to remove residual metal elements, and drying to obtain the negative electrode active material.
Preferably, the preparation method of the positive plate comprises the following steps: the method comprises the steps of taking N-methyl pyrrolidone as a solvent, mixing and homogenizing a positive electrode active material, a conductive agent and a binder according to the mass ratio of 95.5:3:1.5, coating positive electrode slurry on an aluminum foil current collector, drying and rolling to obtain a positive electrode sheet.
Preferably, the preparation method of the negative electrode plate comprises the following steps: firstly, preparing a negative active material; and then mixing and homogenizing the negative active material, the conductive carbon black, SBR and CMC according to the mass ratio of 94.5:2.5:1.5:1.5 by taking water as a solvent, coating the negative slurry on a copper foil current collector, drying and rolling to obtain a negative plate.
Preferably, the preparation method of the electrolyte comprises the following steps: in a low-temperature drying environment, dissolving LiFSI in a mixed solvent of 1-methoxy heptafluoropropane and methylal, wherein the mass ratio of the 1-methoxy heptafluoropropane to the methylal is 9: 1; the concentration of the electrolyte is 1.0 mol/L.
The invention has the advantages and positive effects that:
(1) the cathode of the invention adopts Co @ Al-MOF (1, 4-H)2NDC) is a carbon material prepared by a precursor, the material is a carbon nanotube composite multilayer carbon material, and the lithium ion transmission rate can be improved while the electron conductivity is improved;
(2) the electrolyte solvent adopts a fluorine-containing solvent with a low boiling point, so that the viscosity of the electrolyte can be reduced, and the solvation effect of the solvent on lithium ions can be reduced, so that the lithium ion conducting capacity of the electrolyte is greatly improved, meanwhile, the fluorine-containing solvent is non-combustible and has better fire extinguishing capacity, the safety of the lithium ion battery can be effectively guaranteed, and in addition, the solubility of the electrolyte in the fluorine-containing solvent can be increased by adding a cosolvent;
(3) the invention carries out comprehensive optimization and improvement on the low-temperature performance and the safety of the lithium ion battery through three dimensions of the anode material, the cathode material and the electrolyte, can realize the low-temperature and high-safety lithium ion battery, and has very good application prospect.
Detailed Description
In order to further understand the contents, features and effects of the present invention, the following examples are illustrated, and the following detailed descriptions are given:
the technical scheme of the invention is as follows:
a low temperature lithium ion battery comprising: the positive plate, the negative plate, the diaphragm and the electrolyte;
the positive plate comprises an aluminum foil current collector, and a positive active substance, a binder and a conductive agent coated on the aluminum foil current collector, wherein the positive active substance is lithium cobaltate;
the negative plate comprises a copper foil current collector and a mixture consisting of a negative active material, a binder and a conductive agent coated on the copper foil current collector; wherein the negative active substance adopts Co @ Al-MOF (1, 4-H)2NDC) is a carbon material prepared by a precursor, and the preparation method comprises the following steps: loading 1% -6% CoNO3Al-MOF (1, 4-H) of2NDC) is carbonized at a high temperature of 900-1200 ℃ for 3-6 hours in a nitrogen atmosphere, then the carbonized material is thoroughly cleaned by hydrochloric acid aqueous solution to remove residual metal elements, and the negative active material is obtained after drying.
The electrolyte comprises a fluorine-containing solvent, a lithium salt and a cosolvent; wherein the fluorine-containing solvent is a compound of one or more components of 1,1,1,3,3, 3-hexafluoropropane, 1,1,1,2,3,3, 3-heptafluoropropane, 1-methoxy heptafluoropropane and 1,1,2,2,3,3, 4-heptafluorocyclopentane; the lithium salt is one or more of LiTFSI and LiFSI; the cosolvent is methylal.
Example 1
The preparation method of the low-temperature high-safety lithium ion battery provided by the embodiment comprises the following steps:
preparing a positive plate: mixing and homogenizing a positive electrode active material (lithium cobaltate), a conductive agent (conductive carbon black) and a binder (polyvinylidene fluoride) according to a mass ratio of 95.5:3:1.5 by taking N-methyl pyrrolidone as a solvent, coating the positive electrode slurry on an aluminum foil, drying and rolling to obtain a positive electrode sheet;
preparation of negative plate: will load 2% CoNO3Al-MOF (1, 4-H) of2NDC) is carbonized at a high temperature of 1000 ℃ for 3 hours in a nitrogen atmosphere, then the carbonized material is thoroughly cleaned by hydrochloric acid aqueous solution to remove residual metal elements, and the negative active material is obtained after drying. Taking water as a solvent, mixing and homogenizing a negative active material, a conductive agent (conductive carbon black) and a binder (SBR and CMC) according to a mass ratio of 94.5:2.5:1.5:1.5, coating a negative slurry on a copper foil, drying and rolling to obtain a negative plate;
preparing an electrolyte: in a low-temperature drying environment, LiFSI is dissolved in a mixed solvent of 1-methoxy heptafluoropropane and methylal (the mass ratio is 9: 1), and the concentration of the electrolyte is 1.0 mol/L.
The positive plate, the negative plate and the diaphragm are prepared into a battery with a required model in a winding mode, and the battery is manufactured into the low-temperature lithium ion battery through the working procedures of casing, vacuum drying, electrolyte injection, formation, capacity grading and the like.
Example 2
The difference from example 1 is: the electrolyte is prepared by dissolving LiFSI in a mixed solvent of 1,1,2,2,3,3, 4-heptafluorocyclopentane and methylal (mass ratio is 8.5: 1.5), and the concentration of the electrolyte is 1.0 mol/L.
The remaining process steps were the same as in example 1.
Example 3
The difference from example 1 is: the electrolyte is prepared by dissolving LiFSI in a mixed solvent of 1,1,1,2,3,3, 3-heptafluoropropane and methylal (mass ratio is 8.5: 1.5), and the concentration of the electrolyte is 1.0 mol/L.
The remaining process steps were the same as in example 1.
Example 4
The difference from example 1 is: the electrolyte is prepared by dissolving LiFSI in a mixed solvent of 1,1,1,3,3, 3-hexafluoropropane and methylal (mass ratio of 8.5: 1.5), and the concentration of the electrolyte is 1.0 mol/L.
The remaining process steps were the same as in example 1.
Comparative example 1
Comparative example 1 provides a lithium ion battery in which the negative electrode active material is graphite and the electrolyte is 1.0mol/L LiFSI (EC/DMC/EMC 15:37:48), the rest being the same as in example 1.
The technical principle of the technical scheme of the invention is as follows: the lithium cobaltate adopted as the positive active material improves the energy density and the safety of the lithium ion battery; the negative electrode adopts Co @ Al-MOF (1, 4-H)2NDC) is a carbon material prepared by a precursor, the material is a carbon nanotube composite multilayer carbon material, and the transmission rate of lithium ions can be greatly improved; the electrolyte solvent adopts a fluorine-containing solvent with a low boiling point, so that the viscosity of the electrolyte can be reduced, the solvation effect of the solvent on lithium ions is reduced, the lithium ion conducting capacity of the electrolyte is greatly improved, meanwhile, the fluorine-containing solvent is non-combustible and has better fire extinguishing capacity, the safety of the lithium ion battery can be effectively guaranteed, and in addition, the solubility of the electrolyte in the fluorine-containing solvent can be increased by adding a cosolvent. The invention carries out comprehensive optimization and improvement on the low-temperature performance and the safety of the lithium ion battery through three dimensions of the anode material, the cathode material and the electrolyte, and can realize the low-temperature and high-safety lithium ion battery.
Performance testing
The lithium ion battery prepared above was subjected to a performance test, and the test results are shown in table 1.
TABLE 1 results of cell Performance test
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications, equivalent changes and modifications made to the above embodiment according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (7)
1. A low-temperature lithium ion battery comprises a positive plate, a negative plate, a diaphragm and electrolyte; the method is characterized in that:
the positive plate comprises an aluminum foil current collector, and a positive active material, a binder and a conductive agent coated on the aluminum foil current collector;
the negative plate comprises a copper foil current collector, and a negative active material, a binder and a conductive agent coated on the copper foil current collector;
the electrolyte comprises a fluorine-containing solvent, a lithium salt and a cosolvent; wherein the fluorine-containing solvent is a compound of one or more components of 1,1,1,3,3, 3-hexafluoropropane, 1,1,1,2,3,3, 3-heptafluoropropane, 1-methoxy heptafluoropropane and 1,1,2,2,3,3, 4-heptafluorocyclopentane; the lithium salt is one or more of LiTFSI and LiFSI; the cosolvent is methylal.
2. The low temperature lithium ion battery of claim 1, wherein the positive electrode active material is lithium cobaltate.
3. The low-temperature lithium ion battery as claimed in claim 1, wherein the negative active material is Co @ Al-MOF (1, 4-H)2NDC) is a carbon material prepared from a precursor.
4. The low-temperature lithium ion battery according to any one of claims 1 to 3, wherein the preparation method of the negative electrode active material comprises the following steps:
s1, loading 1% -6% CoNO3Al-MOF (1, 4-H) of2NDC) carbonizing at 900-1200 ℃ for 3-6 hours in a nitrogen atmosphere;
and S2, washing the carbonized material with hydrochloric acid aqueous solution to remove residual metal elements, and drying to obtain the negative electrode active material.
5. The low-temperature lithium ion battery according to any one of claims 1 to 3, wherein the preparation method of the positive plate comprises the following steps: the method comprises the steps of taking N-methyl pyrrolidone as a solvent, mixing and homogenizing a positive electrode active material, a conductive agent and a binder according to the mass ratio of 95.5:3:1.5, coating positive electrode slurry on an aluminum foil current collector, drying and rolling to obtain a positive electrode sheet.
6. The low-temperature lithium ion battery according to any one of claims 1 to 3, wherein the preparation method of the negative electrode sheet comprises the following steps: firstly, preparing a negative active material; and then mixing and homogenizing the negative active material, the conductive carbon black, SBR and CMC according to the mass ratio of 94.5:2.5:1.5:1.5 by taking water as a solvent, coating the negative slurry on a copper foil current collector, drying and rolling to obtain a negative plate.
7. The low-temperature lithium ion battery according to any one of claims 1 to 3, wherein the preparation method of the electrolyte comprises the following steps: in a low-temperature drying environment, dissolving LiFSI in a mixed solvent of 1-methoxy heptafluoropropane and methylal, wherein the mass ratio of the 1-methoxy heptafluoropropane to the methylal is 9: 1; the concentration of the electrolyte is 1.0 mol/L.
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