CN114865219A - Aramid fiber diaphragm and preparation method thereof, and aramid fiber diaphragm battery and preparation method thereof - Google Patents
Aramid fiber diaphragm and preparation method thereof, and aramid fiber diaphragm battery and preparation method thereof Download PDFInfo
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- CN114865219A CN114865219A CN202210581052.7A CN202210581052A CN114865219A CN 114865219 A CN114865219 A CN 114865219A CN 202210581052 A CN202210581052 A CN 202210581052A CN 114865219 A CN114865219 A CN 114865219A
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/423—Polyamide resins
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses an aramid fiber diaphragm and a preparation method thereof, and an aramid fiber diaphragm battery and a preparation method thereof, wherein the method comprises the following steps: grinding aramid fibers, aluminum oxide and lithium glycerol to 10-50 microns in a preset mass ratio, and uniformly mixing the ground particles in a water-ethanol mixed solvent with a volume ratio of 1:1 to obtain aramid fiber composite slurry; and coating the aramid fiber composite slurry on a polypropylene or polyethylene diaphragm to obtain the aramid fiber diaphragm. The invention aims to improve the high-temperature resistance of the battery.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to an aramid fiber diaphragm and a preparation method thereof, and an aramid fiber diaphragm battery and a preparation method thereof.
Background
The existing lithium battery mostly adopts ternary materials and lithium cobaltate as main anode materials, but has the defects of short service life, poor high-temperature resistance, easy ignition and poor safety coefficient. The prior art CN110931801A discloses a high-safety aramid fiber lithium ion battery and a preparation method thereof, wherein aramid fiber is coated on the surface of a positive electrode or a negative electrode, specifically, the aramid fiber slurry is coated on the surface of a pole piece in a spraying mode, the spraying speed is 10m/min, the aramid fiber slurry is soaked in water for 10s, a three-stage oven is used for drying, the temperatures of all stages are respectively 50 ℃, 60 ℃ and 55 ℃, and the aramid fiber coated pole piece is obtained after drying.
Disclosure of Invention
The invention mainly aims to provide an aramid fiber diaphragm and a preparation method thereof, and an aramid fiber diaphragm battery and a preparation method thereof, and aims to solve the technical problem of poor high-temperature resistance of the conventional battery.
In order to achieve the purpose, the invention provides a preparation method of an aramid fiber membrane, which comprises the following steps:
(1) grinding aramid fibers, aluminum oxide and lithium glycerol to 10-50 microns in a preset mass ratio, and uniformly mixing the ground particles in a water-ethanol mixed solvent with a volume ratio of 1:1 to obtain aramid fiber composite slurry;
(2) and coating the aramid fiber composite slurry on a polypropylene or polyethylene diaphragm to obtain the aramid fiber diaphragm.
Optionally, the step (2) comprises:
and (3) coating the aramid fiber composite slurry on the surfaces of two sides of a polypropylene or polyethylene diaphragm in a spraying manner, wherein the coating thickness is 0.5-4 microns.
Optionally, the step (1) comprises: the mass ratio of the aramid fiber to the aluminum oxide to the lithium glycerol is (0.5-1.8): 1.2: (1.1-3.5).
In addition, in order to achieve the purpose, the invention also provides an aramid fiber membrane which is prepared by the preparation method of the aramid fiber membrane.
In addition, in order to achieve the purpose, the invention also provides a preparation method of the aramid fiber diaphragm battery, which adopts the aramid fiber diaphragm and comprises the following steps:
cutting the aramid fiber diaphragm to a target size according to a preset requirement;
laminating a positive plate, a negative plate and the cut aramid fiber diaphragm and performing winding operation to obtain a target winding core, wherein the positive plate comprises a lithium iron manganese phosphate material;
carrying out microwave treatment on the target winding core under vacuum;
and (5) putting the dried roll core into a preset shell, and assembling into the target battery.
Optionally, the step of laminating the positive electrode sheet, the negative electrode sheet and the slit aramid fiber membrane and performing a winding operation includes:
stacking according to the sequence from the positive plate, the cut aramid fiber diaphragm to the negative plate;
and winding the laminated composite material from one end or the middle part under the pressure of 6-10 kg.
Optionally, the step of baking the target winding core under vacuum includes:
and carrying out microwave treatment on the target winding core under vacuum for a preset time, wherein the temperature of the microwave treatment is 60-80 ℃, and the preset time is 30-40 hours.
Optionally, the step of baking the target winding core under vacuum further includes:
the target core was microwaved at 80 ℃ for 32 hours under vacuum.
In addition, in order to achieve the purpose, the invention also provides an aramid fiber diaphragm battery, and the aramid fiber diaphragm battery is prepared by the preparation method of any one of the aramid fiber diaphragm batteries.
The invention provides an aramid fiber diaphragm and a preparation method thereof, and an aramid fiber diaphragm battery and a preparation method thereof, wherein the aramid fiber diaphragm is obtained by coating aramid fiber composite slurry on a polypropylene or polyethylene diaphragm in a spraying manner; the obtained aramid diaphragm is used for preparing an aramid diaphragm battery, a target winding core is obtained by sequentially laminating a positive plate, the aramid diaphragm and a negative plate and winding, the target winding core is baked in vacuum, the dried winding core is arranged in a preset shell, and the target battery is obtained by assembling. The aramid fiber composite slurry is coated on the surface of the polypropylene or polyethylene diaphragm, so that the insulativity, the ductility and the chemical resistance stability of the diaphragm are improved, the preparation process is simple, and the preparation cost is low; and the lithium iron phosphate material is adopted as the anode material, so that the prepared battery has long service life, good safety and long storage time, and the maintenance cost is reduced. In addition, carry out the microwave baking treatment with rolling up the core, reduced the damage of traditional infrared ray baking to electric core material effective chemical composition.
Drawings
FIG. 1 is a schematic flow chart of an embodiment of a method for preparing an aramid fiber membrane battery according to the invention;
fig. 2 is a graph comparing the cycling performance of the cells of the present invention with that of the prior art cells.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, a flow diagram of an embodiment of a preparation method of an aramid fiber membrane battery of the invention is shown, and the method comprises the following steps:
step S10, cutting the aramid fiber membrane to a target size according to preset requirements;
specifically, the aramid fiber diaphragm is prepared by grinding aramid fiber and auxiliary materials to a preset size, and uniformly mixing grinding particles in a water-ethanol solvent to obtain aramid fiber composite slurry; coating the aramid fiber composite slurry on a polypropylene or polyethylene diaphragm in a spraying manner to obtain an aramid fiber diaphragm; wherein the auxiliary material comprises aluminum oxide and glycerol lithium mixed particles, and the mass ratio of aramid fiber, aluminum oxide and glycerol lithium is (0.5-1.8): 1.2: (1.1-3.5), the aramid fiber and the auxiliary materials are generally ground to 10-50 microns.
Furthermore, the aramid fiber composite slurry is coated on the surfaces of two sides of a polypropylene or polyethylene diaphragm through a photoelectric all-in-one machine. In the specific coating process, the aramid fiber composite slurry is coated on the surfaces of two sides of a polypropylene or polyethylene diaphragm in a spraying mode by a concave photoelectric all-in-one machine, and the coating thickness is 0.5-4 microns.
Step S20, laminating a positive plate, a negative plate and the cut aramid fiber diaphragm and performing winding operation to obtain a target winding core, wherein the positive plate comprises a lithium iron manganese phosphate material;
specifically, lamination is performed from the positive electrode sheet, the slit aramid separator to the negative electrode sheet, and pressure winding is performed under a pressure of 6 to 10kg, and the winding operation is performed from one end or the middle of the laminated material. The positive pole piece further comprises a metal base layer, and each lithium iron manganese phosphate layer is uniformly coated on the upper surface and the lower surface of the corresponding metal base layer.
Furthermore, the thickness range of each positive pole piece is 0.05-10 mm.
Step S30, baking the target winding core under vacuum;
specifically, the obtained target winding core is subjected to microwave baking in a vacuum environment for a preset time, the temperature of microwave treatment is controlled to be 60-80 ℃, and the preset time is 30-40 hours. Preferably, the jellyroll is baked at 80 ℃ for 32 hours. The energy can be saved by 45% by microwave baking of the battery cell, the damage to the effective chemical components of the anode and cathode materials is much smaller than that of the traditional infrared baking, the damage to the effective chemical components by the traditional baking is 8%, and the damage to the effective chemical components by the microwave baking is only 0.2%.
And step S40, the dried winding core is put into a preset shell and assembled into the target battery.
Specifically, the dried target winding core is put into an aluminum shell or a shell of an aluminum plastic film with a certain shape to assemble the aramid diaphragm battery. The obtained aramid fiber diaphragm battery further comprises: positive pole piece, aramid fiber diaphragm and the negative pole piece that interval distribution in proper order, each aramid fiber diaphragm setting be in the positive pole piece that corresponds with between the negative pole piece, the upper and lower both sides surface coating of each diaphragm has the compound thick liquids layer of aramid fiber, and each positive pole piece includes manganese iron lithium phosphate layer, and each negative pole piece is graphite negative pole piece.
In the battery preparation process, the aramid fiber composite slurry is coated on the surface of the polypropylene or polyethylene diaphragm, so that the insulativity, the ductility and the chemical stability resistance of the diaphragm are improved, the high-temperature resistance of the lithium battery is further improved, and compared with the process of coating the aramid fiber composite slurry on the positive electrode and the negative electrode, the process is more convenient, more energy-saving and more environment-friendly, and the production process is simpler and more convenient; and the main equipment produced by the traditional lithium battery process can be utilized, the equipment of the traditional lithium battery can be utilized by more than 90 percent, and the investment of production equipment can be saved to the maximum extent. Meanwhile, the coiled core is subjected to microwave baking treatment, so that the damage of the traditional infrared baking to the effective chemical components of the battery core material is reduced, the using effect of the anode material is improved, and the lithium iron phosphate material is used as the anode, so that the effects of long service life, good safety and long storage time of the prepared battery are realized.
Examples 1-3 for preparing aramid separator batteries obtained by the above preparation method were as follows:
example 1
step 2, stacking the anode plate, the cut aramid fiber diaphragm plate and the cathode plate in a sequencing mode, performing pressure winding under the pressure of 6kg, and performing winding operation from one end of the stacked material to obtain a target winding core;
step 3, performing microwave baking on the target winding core for 30 hours in a vacuum environment, and controlling the baking temperature to be 80 ℃;
and 4, filling the dried roll core into a preset shell, and assembling the aramid fiber diaphragm battery 1.
Example 2
step 2, stacking the anode sheet, the cut aramid fiber diaphragm sheet and the cathode sheet in a sequencing mode, performing pressure winding under the pressure of 8kg, and performing winding operation from one end of the stacked material to obtain a target winding core;
step 3, performing microwave baking on the target winding core for 32 hours in a vacuum environment, and controlling the baking temperature to be 70 ℃;
and 4, filling the dried roll core into a preset shell, and assembling the aramid fiber diaphragm battery 2.
Example 3
step 2, stacking the anode plate, the cut aramid fiber diaphragm plate and the cathode plate in a sequencing mode, performing pressure winding under the pressure of 10kg, and performing winding operation from the middle end of the stacked material to obtain a target winding core;
step 3, performing microwave baking on the target winding core for 40 hours in a vacuum environment, and controlling the baking temperature to be 60 ℃;
and 4, filling the dried roll core into a preset shell, and assembling the aramid fiber diaphragm battery 3.
Further, in order to verify the effects of the manufactured batteries of the above-described manufacturing methods, the batteries manufactured according to the prior art and the batteries manufactured according to the present invention were subjected to high-temperature, steel needle puncture, cyclic discharge, and extrusion experiments as follows.
High temperature experiment
The aramid fiber diaphragm batteries 1-3 of the invention are respectively heated intermittently with the existing battery 1 (a battery prepared by adopting lithium manganate as a positive electrode material, graphite as a negative electrode material and polypropylene as a diaphragm) and the existing battery 2 (a battery prepared by adopting lithium cobaltate as a positive electrode material, polyethylene as a diaphragm and graphite as a negative electrode material), and the actual conditions of the battery and the further working conditions of the battery after heating are recorded at the temperature of 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ and 90 ℃, and the details are as follows:
TABLE 1 working conditions of the cell after heating at high temperature
As can be seen from table 1, when the conventional battery 1 and the conventional battery 2 are heated to 60-70 ℃, the battery is ignited, and the battery cannot be used continuously, and meanwhile, the aramid fiber membrane battery 1-3 of the present invention can normally operate when heated to a temperature exceeding 70 ℃ to 90 ℃.
Steel needle puncture experiment
The aramid fiber membrane battery 1-3 of the invention, a battery (the existing battery 1) prepared by ternary materials and common membranes and a battery (the existing battery 2) prepared by lithium cobaltate and common membranes are respectively subjected to steel needle puncture experiments, specifically, a steel needle with the diameter of 5mm vertically penetrates through the surface of the battery in specific experimental equipment, the puncture speed is 20mm/s, and the voltage and temperature conditions of each battery are recorded. The details are as follows:
TABLE 2 State Change of the Battery after Steel needle puncture
As can be seen from table 2, after the steel needle puncture test is performed on the conventional battery 1 and the conventional battery 2, the battery voltage drops, the batteries expand violently, smoke and fire are ignited, and the temperatures of the batteries after ignition are both close to 300 ℃ at most, while the voltages and the battery surface temperatures of the aramid fiber diaphragm batteries 1 to 3 of the present invention slightly fluctuate after the puncture test is performed, no expansion phenomenon occurs, no smoke and no fire are ignited, so that the aramid fiber diaphragm batteries of the present invention have high safety performance.
Cyclic discharge experiment
The aramid fiber diaphragm battery 1, a battery (the existing battery 1) prepared from ternary materials and a common diaphragm, and a battery (the existing battery 2) prepared from lithium cobaltate and the common diaphragm are respectively subjected to 1C charging and discharging cycle times, wherein the cycle time of the existing battery 1 can reach 800 times, the cycle time of the existing battery 2 can reach 1000 times, the cycle time of the aramid fiber diaphragm battery can reach 3000 times, and 80% of stored electricity can be kept. As can be seen, the aramid fiber diaphragm battery 1 of the present invention has a longer life cycle. In addition, the results obtained by carrying out the cyclic discharge experiments on the aramid fiber membrane batteries 2-3 and the conventional battery 1/2 under the same conditions are basically similar to the results of the aramid fiber membrane battery 1.
Extrusion test
The aramid fiber diaphragm battery 2, a battery (the existing battery 1) prepared from a ternary material and a common diaphragm, and a battery (the existing battery 2) prepared from lithium cobaltate and the common diaphragm are respectively applied with an acting force of 13KN (1.72Mpa) between two plane metal plates and are continuously kept for 30 minutes, and finally, the existing battery 1 and the existing battery 2 have smoke, but the aramid fiber diaphragm battery of the invention has no smoke and can normally work. Therefore, the aramid fiber diaphragm battery 2 also has a certain anti-extrusion effect, and the safety performance of the battery is guaranteed. Furthermore, the results obtained by subjecting each of the aramid separator batteries 2 to 3 and the conventional battery 1/2 to a squeezing test under the same conditions were substantially the same as those of the aramid separator battery 1.
In addition, in order to verify the effect of long service life of the battery prepared by the preparation method of the invention, the aramid fiber diaphragm battery 3 is subjected to charge and discharge tests with a traditional high-rate ternary or lithium cobaltate battery at normal temperature, as shown in fig. 2, wherein the battery assembled by the invention still can maintain good battery capacity retention rate when the cycle number of the battery exceeds 600 times, and the battery capacity retention rate of the traditional ternary battery is obviously reduced after the cycle number of the battery exceeds 400 times. Moreover, the curve of the battery capacity change rate of the aramid fiber diaphragm battery 1-2 is basically overlapped with that of the aramid fiber diaphragm battery 1, and further extra drawing is not needed. Further, it is found that the batteries obtained by the production methods of examples 1 to 3 have a larger number of battery cycles and a longer service life.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or system. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a process, method, article, or system that comprises the element.
The above-mentioned serial numbers of the embodiments of the present invention are merely for description and do not represent the merits of the embodiments.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by using the contents of the present specification and the accompanying drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (9)
1. The preparation method of the aramid fiber membrane is characterized by comprising the following steps of:
(1) grinding aramid fibers, aluminum oxide and lithium glycerol to 10-50 microns in a preset mass ratio, and uniformly mixing the ground particles in a water-ethanol mixed solvent with a volume ratio of 1:1 to obtain aramid fiber composite slurry;
(2) and coating the aramid fiber composite slurry on a polypropylene or polyethylene diaphragm to obtain the aramid fiber diaphragm.
2. The method for preparing the aramid separator as claimed in claim 1, wherein the step (2) comprises:
and (3) coating the aramid fiber composite slurry on the surfaces of two sides of a polypropylene or polyethylene diaphragm in a spraying manner, wherein the coating thickness is 0.5-4 microns.
3. The method for preparing the aramid separator as claimed in claim 1, wherein the step (1) comprises: the mass ratio of the aramid fiber to the aluminum oxide to the lithium glycerol is (0.5-1.8): 1.2: (1.1-3.5).
4. An aramid membrane characterized by being produced by the method for producing an aramid membrane according to any one of claims 1 to 3.
5. A preparation method of an aramid diaphragm battery is characterized in that the aramid diaphragm disclosed in claim 4 is adopted, and the method comprises the following steps:
cutting the aramid fiber membrane to a target size according to a preset requirement;
laminating a positive plate, a negative plate and the cut aramid fiber diaphragm and performing winding operation to obtain a target winding core, wherein the positive plate comprises a lithium iron manganese phosphate material;
carrying out microwave treatment on the target winding core under vacuum;
and (5) putting the dried roll core into a preset shell, and assembling into the target battery.
6. The method for preparing the aramid separator battery according to claim 5, wherein the step of laminating the positive electrode sheet, the negative electrode sheet and the slit aramid separator and performing a winding operation comprises:
stacking according to the sequence from the positive plate, the cut aramid fiber diaphragm to the negative plate;
and winding the laminated composite material from one end or the middle part under the pressure of 6-10 kg.
7. The preparation method of the aramid separator battery as claimed in claim 5, wherein the step of baking the target winding core under vacuum comprises:
and carrying out microwave treatment on the target winding core under vacuum for a preset time, wherein the temperature of the microwave treatment is 60-80 ℃, and the preset time is 30-40 hours.
8. The method for preparing the aramid separator battery according to claim 5, wherein the step of baking the target winding core under vacuum further comprises:
the target core was microwaved at 80 ℃ for 32 hours under vacuum.
9. An aramid separator battery, characterized in that the aramid separator battery is manufactured by the method for manufacturing an aramid separator battery according to any one of claims 5 to 8.
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