CN111952659A - Lithium iron phosphate battery - Google Patents
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- CN111952659A CN111952659A CN202010849710.7A CN202010849710A CN111952659A CN 111952659 A CN111952659 A CN 111952659A CN 202010849710 A CN202010849710 A CN 202010849710A CN 111952659 A CN111952659 A CN 111952659A
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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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
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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
- H01M4/58—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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention provides a lithium iron phosphate battery which is characterized in that a positive electrode material is a lithium iron phosphate material, the concentration range of lithium salt in electrolyte is 0.8-10mol/L, a diaphragm is made of a PE wet-process ceramic coating material, and a positive electrode current collector is a carbon-coated aluminum foil; and the anode material is subjected to nano dispersion by a nano dispersion machine. The battery has stable performance, high safety and low cost.
Description
Technical Field
The invention relates to a lithium ion battery of ferric phosphate, belonging to the technical field of lithium ion batteries.
Background
At present, global energy transformation is imminent, and the market demand of power batteries is continuously and rapidly increased year by year. The lithium iron phosphate battery has development potential in the fields of energy storage, low-speed vehicles, standby power and the like due to the advantages of low cost, high safety, long service life and high rate. However, the existing lithium iron phosphate batteries have the following problems: the performance stability is not high, and potential safety quality hazards occur frequently; the cost is high and the market competitiveness is insufficient.
Disclosure of Invention
The invention provides a lithium iron phosphate battery which can effectively solve the problems.
The invention is realized by the following steps:
a lithium iron phosphate battery is characterized in that a positive electrode material is a lithium iron phosphate material, the concentration range of lithium salt in electrolyte is 0.8-10mol/L, a diaphragm is made of a PE wet-process ceramic coating material, and a positive current collector is a carbon-coated aluminum foil; and the anode material is subjected to nano dispersion by a nano dispersion machine.
As a further improvement, the preparation method of the cathode material comprises the following steps:
s1, mixing the lithium iron phosphate, the carbon nano tube, the conductive carbon black and the polyvinylidene fluoride, and stirring at the speed of 200-800rpm for 50-70 min;
s2, adding 40-80% N-methyl pyrrolidone, and stirring at the speed of 500-2500rpm for 2.5-3.5h under vacuum; then adding the rest N-methyl pyrrolidone, and stirring for 2.5-3.5h at the speed of 200-800rpm under vacuum;
and S3, testing the viscosity and temperature of the slurry, and performing nano-dispersion by using a nano-dispersion machine when the viscosity reaches 14000-16000mPa.s and the temperature is 25-45 ℃.
As a further improvement, the mass ratio of the lithium iron phosphate, the carbon nanotube, the conductive carbon black and the polyvinylidene fluoride is 96:0.5:1.5: 2.0.
as a further improvement, the dispersion speed of the nano dispersion is 1600-2000rpm, the temperature is 40-60 ℃, and the time is 10-50 min.
As a further improvement, the anode material is aged after being subjected to nano-dispersion by a nano-dispersion machine, and the aging process comprises the following steps: and (3) high-temperature aging: the temperature is 40-50 ℃, the time is 8-24h, the humidity is 15-35%, and the low-temperature aging is as follows: the temperature is 20-30 ℃, the time is 8-24h, and the humidity is 15-35%.
As a further improvement, the negative electrode material comprises graphite, conductive carbon black, sodium carboxymethyl cellulose and styrene butadiene rubber, and the mass ratio of the graphite to the conductive carbon black is 96: 0.7: 1.2: 1.8.
as further improvement, the shell of the battery adopts an explosion-proof shell, the winding core adopts a multi-tab structure, and the cover plate leads out the positive electrode to be communicated with the shell.
The invention has the beneficial effects that:
after the nanocrystallization treatment is carried out on the positive electrode material of the lithium iron phosphate battery, slurry aggregates are dispersed, and the uniform distribution of a pole piece active material, a conductive agent and other auxiliary materials on the surface of a current collector is ensured, so that the electrical property consistency of the battery is improved, the pole piece of the battery cell is smooth and has no large particle phenomenon, and the risks of point discharge caused by overlarge particles and micro short circuit caused by diaphragm cracks in the hot-pressing process of the battery cell caused by the overlarge particles are avoided in the charging and discharging process of the battery cell.
The lithium iron phosphate battery core adopts a multi-tab structure, so that the current conduction area is enlarged, the temperature rise of the battery core is reduced, and the reduction of the service life of the battery core caused by lithium salt loss due to electrolyte decomposition and side reaction is prevented.
The shell of the lithium iron phosphate battery adopts an explosion-proof device, and the pressure of an explosion-proof valve is as follows: 0.6 0.2Mpa, inside because temperature rise, short circuit hidden danger take place when electric core, cause electric core internal pressure increase, when reaching explosion-proof valve pressure value, electric core will release the pressure, prevent that bigger harm from taking place.
The lithium iron phosphate battery has the advantages of energy consumption saving and cost reduction in production.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a cycle curve of a lithium iron phosphate battery provided in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings of the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
In the description of the present invention, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
A lithium iron phosphate battery is characterized in that a positive electrode material is a lithium iron phosphate material, the concentration range of lithium salt in electrolyte is 0.8-10mol/L, a diaphragm is made of a PE wet-process ceramic coating material, and a positive current collector is a carbon-coated aluminum foil; and the anode material is subjected to nano dispersion by a nano dispersion machine.
The positive electrode material is subjected to nanocrystallization, intermolecular van der Waals force is eliminated by slurry through high-strength acting forces such as high-speed shearing force, friction and collision, aggregates are opened and dispersed to form uniform, fine and stable particles, meanwhile, in high-speed operation, a central area of equipment forms a negative pressure state, air bubbles in the slurry are instantaneously broken to form a cavity phenomenon, the slurry aggregates are favorably dispersed and dispersed, and the uniform distribution of pole piece active materials, conductive agents and other auxiliary materials on the surface of a current collector is ensured, so that the electrical property consistency of the battery is improved, the consistency of key indexes including alternating current internal resistance, direct current internal resistance, capacity, voltage platform, low-temperature efficiency and the like, and the electrochemical property of.
After the anode material is subjected to nanocrystallization, the battery cell pole piece is smooth and free of large particle phenomenon, so that the battery cell is prevented from point discharge caused by overlarge particulate matters in the charging and discharging process, and risks such as micro short circuit caused by overlarge diaphragm cracks in the hot-pressing process of the battery cell due to the overlarge particulate matters are avoided.
As a further improvement, the preparation method of the cathode material comprises the following steps:
s1, mixing the lithium iron phosphate, the carbon nano tube, the conductive carbon black and the polyvinylidene fluoride, and stirring at the speed of 200-800rpm for 50-70 min;
s2, adding 40-80% solvent N-methyl pyrrolidone, and stirring at the speed of 500-2500rpm for 2.5-3.5h under vacuum; then adding the residual solvent N-methyl pyrrolidone, and stirring for 2.5-3.5h at the speed of 200-; the first addition of the solvent is mainly to fully and uniformly mix the solid-liquid mixture by fully stirring the solid-liquid mixture through a stirrer under the condition of high viscosity; the solvent is added for the second time, so that the LFP and the conductive agent are in a state of micro-voids and intermolecular voids of a self-structure and are fully wet, and a uniform mixture is formed.
And S3, testing the viscosity and temperature of the slurry, and performing nano-dispersion by using a nano-dispersion machine when the viscosity reaches 14000-16000mPa.s and the temperature is 25-45 ℃.
As a further improvement, the dispersion speed of the nano dispersion is 1600-2000rpm, the temperature is 40-60 ℃, and the time is 10-50 min. Within this parameter, the stability of the slurry can be significantly improved. When the dispersion speed is lower than 1600rpm or higher than 2000rpm, the stability of the slurry is lowered.
As a further improvement, after the cathode material is subjected to nano dispersion by a nano dispersion machine, the aging process is as follows: and (3) high-temperature aging: the temperature is 40-50 ℃, the time is 8-24h, the humidity is 15-35%, and the low-temperature aging is as follows: the temperature is 20-30 ℃, the time is 8-24h, and the humidity is 15-35%. The aging process ensures the electrical property consistency of the battery and realizes reliability and safety.
As a further improvement, the mass ratio of the lithium iron phosphate, the carbon nanotube, the conductive carbon black and the polyvinylidene fluoride is 96:0.5:1.5: 2.0. the negative electrode material comprises graphite, conductive carbon black, sodium carboxymethylcellulose and styrene butadiene rubber in a mass ratio of 96: 0.7: 1.2: 1.8. the application of the formula can improve the energy exertion of the active material, reduce the impedance of the battery and improve the capacity.
As a further improvement, the shell of the battery adopts an explosion-proof functional shell, and the pressure of an explosion-proof valve is as follows: 0.6 0.2Mpa, inside because temperature rise, short circuit hidden danger take place when electric core, cause electric core internal pressure increase, when reaching explosion-proof valve pressure value, electric core will release the pressure, prevent that bigger harm from taking place.
The core is of a multi-lug structure, so that the current conduction area is increased, the temperature rise of the battery core is reduced, the lithium salt loss caused by decomposition of electrolyte and side reaction is prevented, and the service life of the battery core is shortened.
The cover plate leads out the anode to be communicated with the shell, so that the shell is prevented from being corroded.
Example 1
Preparation of cathode material
Humidity at a temperature of 25 ± 5 ℃, humidity: mixing lithium iron phosphate LFP serving as a positive electrode main material, conductive carbon black SP, a high-conductivity carbon nano tube CNT and a polyvinylidene fluoride PVDF binder according to the mass ratio of LFP, CNT, SP and PVDF being 96:0.5:1.5:2.0 under the condition of 15 +/-5 percent, stirring at the speed of 600rpm for 1h, adding 60 percent of N-methylpyrrolidone solvent, and stirring at the speed of 2000rpm under the vacuum condition of-0.085 MPa for 3 h; the remaining solvent was added and stirred at 500rpm under vacuum-0.085 MPa for 3 h. When the viscosity is measured to be 15000 +/-1000 mPa.s, the fineness is less than or equal to 15um and the temperature is 30 ℃, a nano-dispersion machine is adopted to carry out nano-dispersion, the dispersion speed is 1800rpm, the dispersion temperature is 50 ℃, and the dispersion time is 40min, so as to prepare the cathode material.
The negative electrode material comprises graphite, conductive carbon black, sodium carboxymethylcellulose and styrene butadiene rubber, and the mass ratio of the graphite to the conductive carbon black is 96: 0.7: 1.2: 1.8. the anode material was prepared according to a conventional method.
The concentration of lithium salt in the electrolyte is 1.0mol/L, the diaphragm is made of PE wet-process coating ceramic materials, and the positive current collector is carbon-coated aluminum foil.
And (3) high-temperature aging: the temperature is 45 ℃, the time is 15h, and the humidity is 20%.
And (3) low-temperature aging: the temperature is 25 ℃, the time is 15h, and the humidity is 20%.
The shell of the battery adopts an explosion-proof shell, the winding core adopts a multi-tab structure, and the cover plate leads out the anode to be communicated with the shell.
Other preparation methods are the same as those of the conventional lithium ion battery.
The test conditions of the cycle test are shown in table 1:
TABLE 1
| Temperature of | 25±5℃ |
| Charging current | 0.5C |
| Discharge current | 0.5C |
The cycle curve is shown in fig. 1, the cycle life of the lithium iron phosphate battery of the embodiment of the invention reaches 5120 times, which is completely higher than the national standard.
Comparative example 1
The comparison of the cathode material prepared by the conventional wet process pulping with the cathode material prepared in example 1 is shown in table 2.
TABLE 2
Therefore, in the production process of the lithium iron phosphate battery, the slurry is uniformly distributed, the stability of the slurry is enhanced, the density of the pole piece surface is stable in the coating process, the coating speed can be increased, the energy consumption is saved, and the cost is reduced.
Comparative example 2
The dispersion speed of the nano dispersion was 600-800rpm, and the other examples were the same as example 1. Tests show that the settled solid content of the slurry is reduced by 1 to 2 percent after 48 hours. In the coating process, the surface density of the pole piece is stable and fluctuates by +/-1%. The pole piece particles are reduced to 3-10 per square meter. The slurry stability was significantly lower than the slurry of example 1. The cycle life of the battery reaches 4000 times.
Comparative example 3
The dispersion rate of the nano dispersion was 2600-. Tests show that the settled solid content of the slurry is reduced by 0.5 to 1.5 percent after 48 hours. In the coating process, the surface density of the pole piece is stable and fluctuates by +/-1%. The pole piece particles are reduced to 2-6 per square meter. The slurry stability was significantly lower than the slurry of example 1. The cycle life of the battery reaches 4300 times.
Comparative example 4
Adding the solvent at one time, and stirring at the speed of 2000rpm for 3h under the vacuum of-0.085 MPa; the mixture was stirred at 500rpm for 3 hours, and the procedure was otherwise the same as in example 1. Tests show that the settled solid content of the slurry is reduced by 1 to 3 percent after 48 hours. In the coating process, the surface density of the pole piece is stable, and the fluctuation is +/-1.5%. The pole piece particles are reduced to 3-15 per square meter. The slurry stability was significantly lower than the slurry of example 1. The cycle life of the battery reaches 3820 times.
Comparative example 5
The mass ratio of the positive electrode material was LFP to CNT to SP to PVDF 95:1.5:1.5:2.0, and the same as in example 1 was performed. Tests show that the settled solid content of the slurry is reduced by 2 to 4 percent after 48 hours. In the coating process, the surface density of the pole piece is stable, and the fluctuation is +/-1.5%. The pole piece particles are reduced to 5-20 per square meter. The slurry stability was significantly lower than the slurry of example 1. The cycle life of the battery reaches 3860 times.
Comparative example 6
The mass ratio of the negative electrode material graphite, the conductive carbon black, the sodium carboxymethyl cellulose and the styrene butadiene rubber is 94: 1.7: 2.2: 1.8, the rest is the same as example 1. The cycle life of the battery reaches 4750 times through testing.
Comparative example 7
The aging process comprises the following steps: and (3) high-temperature aging: the temperature is 60 ℃, the time is 20h, the humidity is 20%, and the low-temperature aging is as follows: the temperature was 40 ℃, the time was 20h, and the humidity was 20%, all other things being equal to example 1. The cycle life of the battery reaches 3950 times through tests.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The lithium iron phosphate battery is characterized in that a positive electrode material is a lithium iron phosphate material, the concentration range of lithium salt in electrolyte is 0.8-10mol/L, a diaphragm is made of a PE wet-process ceramic coating material, and a positive electrode current collector is a carbon-coated aluminum foil; and the anode material is subjected to nano dispersion by a nano dispersion machine.
2. The lithium ion phosphate battery according to claim 1, wherein the preparation method of the cathode material comprises the following steps:
s1, mixing the lithium iron phosphate, the carbon nano tube, the conductive carbon black and the polyvinylidene fluoride, and stirring at the speed of 200-800rpm for 50-70 min;
s2, adding 40-80% N-methyl pyrrolidone, and stirring at the speed of 500-2500rpm for 2.5-3.5h under vacuum; then adding the rest N-methyl pyrrolidone, and stirring for 2.5-3.5h at the speed of 200-800rpm under vacuum;
and S3, testing the viscosity and temperature of the slurry, and performing nano-dispersion by using a nano-dispersion machine when the viscosity reaches 14000-16000mPa.s and the temperature is 25-45 ℃.
3. The lithium ion phosphate battery of claim 2, wherein the mass ratio of the lithium iron phosphate to the carbon nanotubes to the conductive carbon black to the polyvinylidene fluoride is 96:0.5:1.5: 2.0.
4. the lithium iron phosphate battery of claim 2, wherein the nano-dispersion has a dispersion speed of 1600-2000rpm, a temperature of 40-60 ℃, and a time of 10-50 min.
5. The lithium ion phosphate battery of claim 2, wherein the cathode material is aged after being subjected to nano-dispersion by a nano-dispersion machine, and the aging process comprises: and (3) high-temperature aging: the temperature is 40-50 ℃, the time is 8-24h, the humidity is 15-35%, and the low-temperature aging is as follows: the temperature is 20-30 ℃, the time is 8-24h, and the humidity is 15-35%.
6. The lithium ion phosphate battery of claim 2, wherein the negative electrode material comprises graphite, conductive carbon black, sodium carboxymethyl cellulose and styrene butadiene rubber, and the mass ratio of the graphite to the conductive carbon black is 96: 0.7: 1.2: 1.8.
7. the lithium ion iron phosphate battery according to claim 1, wherein the battery shell is an explosion-proof shell, the winding core is a multi-tab structure, and the cover plate leads out the positive electrode to be conducted with the shell.
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