CN110690387A - Preparation method of in-situ growth nanoparticle modified polymer diaphragm - Google Patents
Preparation method of in-situ growth nanoparticle modified polymer diaphragm Download PDFInfo
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- CN110690387A CN110690387A CN201910836178.2A CN201910836178A CN110690387A CN 110690387 A CN110690387 A CN 110690387A CN 201910836178 A CN201910836178 A CN 201910836178A CN 110690387 A CN110690387 A CN 110690387A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- 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
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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
- H01M50/431—Inorganic material
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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
- H01M50/44—Fibrous material
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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
- 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 provides a preparation method of an in-situ growth nanoparticle modified polymer diaphragm, which comprises the following steps: 1) preparing tetraethyl orthosilicate solution and ethanol solution, and uniformly mixing the tetraethyl orthosilicate solution and the ethanol solution; 2) placing a polyethylene diaphragm, a polypropylene diaphragm or a non-woven fabric diaphragm in the mixed solution for a period of time, and then taking out the diaphragm; 3) soaking the diaphragm in an acetone solution, taking out and placing in an ethanol solution; 4) placing the diaphragm in an oven for drying, and then taking out the diaphragm; wherein, in the step 1), after the tetraethyl orthosilicate solution and the ethanol solution are uniformly mixed, the ethanol solution of ammonia water is prepared and uniformly mixed with the two solutions; or in the step 2), after the diaphragm is taken out, preparing an ethanol solution of ammonia water, and soaking the diaphragm in the solution. The method can efficiently prepare the modified coated lithium battery diaphragm, improves the safety performance of the diaphragm, and does not damage the overall electrical performance of the battery.
Description
Technical Field
The invention relates to the technical field of lithium battery diaphragms, in particular to a method for in-situ modification of a polymer diaphragm, which can be used for efficiently preparing a polymer diaphragm coated with inorganic nano-particles and improving the safety and the discharge performance of a lithium battery.
Background
With the vigorous development of new energy industry, the rapid development of new energy automobiles requires people to pay more and more attention to the charging and discharging speed of lithium batteries and the overall safety of the batteries. In the lithium battery, the diaphragm plays a role in isolating the positive electrode and the negative electrode and simultaneously ensuring the transmission of lithium ions. The current commonly used diaphragm is prepared from a polymer, the melting point of the polymer is usually low, and the polymer has certain heat shrinkage performance, so that the diaphragm shrinks in volume at high temperature, and the anode and the cathode are in contact, so that the battery is overheated, and further a fire disaster is possibly caused. Meanwhile, the affinity performance of the diaphragm and the electrolyte is poor, so that the migration rate of lithium ions in the battery and the internal resistance of the battery are high, and the release of the whole electrochemical performance of the battery is hindered. The existing common solution is to coat inorganic materials on two sides of the diaphragm, and the safety of the diaphragm is improved by utilizing the high-temperature resistance of the inorganic materials. However, since the inorganic particles are adhered to both sides of the separator by coating, the inorganic particles are easily detached during the assembly of the battery, thereby deteriorating the electrochemical performance of the battery. The coating of the inorganic particles may also enter the pores of the separator, resulting in pore blocking of the battery separator, further reducing the lithium ion transport rate inside the separator, and affecting the overall performance of the battery. Therefore, the invention provides a new coating method, which improves the safety performance of the diaphragm without damaging the overall electrical performance of the battery and is a problem to be solved urgently at present.
Disclosure of Invention
The invention aims to overcome the technical defect of inorganic nanoparticle coating, and provides a preparation method of a modified polymer diaphragm of in-situ grown nanoparticles, which can be used for efficiently preparing a modified coated lithium battery diaphragm, improving the safety performance of the diaphragm and simultaneously not damaging the overall electrical property of the battery.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of an in-situ growth nanoparticle modified polymer diaphragm comprises the following steps:
1) preparing tetraethyl orthosilicate solution with the volume percentage of 0.1-10% and ethanol solution with the volume percentage of 30-90%, and uniformly mixing the tetraethyl orthosilicate solution and the ethanol solution;
2) placing a polyethylene diaphragm, a polypropylene diaphragm or a non-woven fabric diaphragm in the mixed solution, placing for 30min-24h, and then taking out the diaphragm;
3) placing the diaphragm in an acetone solution, soaking for 30min-3h, taking out, placing in an ethanol solution, and standing for 30min-3 h;
4) placing the diaphragm in an oven, setting the temperature of the oven at 60-80 ℃, drying for 3-24 h, and taking out the diaphragm;
wherein, in the step 1), after the tetraethyl orthosilicate solution and the ethanol solution are uniformly mixed, the ethanol solution of ammonia water with the volume percentage of 1-50% is prepared and is uniformly mixed with the two solutions; or in the step 2), after the diaphragm is taken out, preparing an ethanol solution of ammonia water with the volume percentage of 1-50%, placing the diaphragm in the solution, and soaking for 30min-24 h.
An in-situ growth nanoparticle modified polymer diaphragm prepared by the preparation method.
Drawings
Fig. 1 is an SEM image of the in-situ grown nanoparticle-modified membrane prepared in example 1.
Figure 2 is an SEM image of the in-situ grown nanoparticle modified membrane prepared in example 2.
Figure 3 is an SEM image of the in-situ grown nanoparticle modified membrane prepared in example 3.
Fig. 4 is an SEM image of the in-situ grown nanoparticle-modified membrane prepared in example 4.
Fig. 5 is an SEM image of the in-situ grown nanoparticle-modified membrane prepared in example 5.
Fig. 6 is an SEM image of the in-situ grown nanoparticle-modified membrane prepared in example 6.
Fig. 7 is an SEM image of the in-situ grown nanoparticle-modified membrane prepared in example 7.
Fig. 8 is an SEM image of the in-situ grown nanoparticle-modified membrane prepared in example 8.
Fig. 9 is an SEM image of the in-situ grown nanoparticle-modified membrane prepared in example 9.
Detailed Description
The present invention is described in further detail below by way of specific examples, which are not intended to limit the invention, and those skilled in the art can make various modifications and improvements based on the basic idea of the invention without departing from the scope of the invention.
Example 1
Preparing an in-situ growth nanoparticle modified polymer diaphragm:
A. preparing tetraethyl orthosilicate solution with the volume percentage of 0.1 percent and ethanol solution with the volume percentage of 30 percent, then uniformly mixing the tetraethyl orthosilicate solution and the ethanol solution with the volume percentage of 1 percent and ammonia water, and uniformly mixing the tetraethyl orthosilicate solution and the ethanol solution.
B. And placing the polyethylene diaphragm in the prepared solution, standing for 30min, and then taking out the diaphragm.
C. The membrane is placed in acetone solution, soaked for 30min, taken out and placed in ethanol solution, and the standing time is 30 min.
D. And (3) placing the diaphragm in an oven, setting the temperature of the oven at 60 ℃, drying for 3h, and taking out the diaphragm.
Example 2
Preparing an in-situ growth nanoparticle modified polymer diaphragm:
A. preparing 1 volume percent tetraethyl orthosilicate solution and 30 volume percent ethanol solution, then uniformly mixing the tetraethyl orthosilicate solution and the ethanol solution, and uniformly mixing the tetraethyl orthosilicate solution and the ethanol solution in which the volume percent is 1 percent ammonia water.
B. And placing the polyethylene diaphragm in the prepared solution, placing for 1h, and taking out the diaphragm.
C. The membrane is placed in acetone solution, soaked for 30min, taken out and placed in ethanol solution, and the standing time is 30 min.
D. And (3) placing the diaphragm in an oven, setting the temperature of the oven at 60 ℃, drying for 3h, and taking out the diaphragm.
Example 3
Preparing an in-situ growth nanoparticle modified polymer diaphragm:
A. preparing 1 volume percent tetraethyl orthosilicate solution and 50 volume percent ethanol solution, then uniformly mixing the tetraethyl orthosilicate solution and the ethanol solution, and preparing 10 volume percent ammonia water ethanol solution, and uniformly mixing the ethanol solution and the ethanol solution.
B. And placing the polyethylene diaphragm in the prepared solution, placing for 6h, and taking out the diaphragm.
C. The diaphragm is placed in an acetone solution, soaked for 1h, taken out and placed in an ethanol solution for 1 h.
D. And (3) placing the diaphragm in an oven, setting the temperature of the oven at 60 ℃, drying for 10h, and taking out the diaphragm.
Example 4
Preparing an in-situ growth nanoparticle modified polymer diaphragm:
A. preparing tetraethyl orthosilicate solution with the volume percentage of 5 percent and ethanol solution with the volume percentage of 80 percent, then uniformly mixing the tetraethyl orthosilicate solution and the ethanol solution with the volume percentage of 30 percent and uniformly mixing the tetraethyl orthosilicate solution and the ethanol solution.
B. And placing the polyethylene diaphragm in the prepared solution, placing for 24h, and taking out the diaphragm.
C. The diaphragm is placed in an acetone solution, soaked for 2 hours, taken out and placed in an ethanol solution, and the standing time is 2 hours.
D. And (3) placing the diaphragm in an oven, setting the temperature of the oven at 70 ℃, drying for 15h, and taking out the diaphragm.
Example 5
Preparing an in-situ growth nanoparticle modified polymer diaphragm:
A. preparing 7 volume percent tetraethyl orthosilicate solution and 50 volume percent ethanol solution, then uniformly mixing the tetraethyl orthosilicate solution and the ethanol solution, and preparing 5 volume percent ammonia water ethanol solution, and uniformly mixing the ethanol solution and the ethanol solution.
B. And placing the polyethylene diaphragm in the prepared solution, placing for 24h, and taking out the diaphragm.
C. The diaphragm is placed in an acetone solution, soaked for 3 hours, taken out and placed in an ethanol solution, and the standing time is 3 hours.
D. And (3) placing the diaphragm in an oven, setting the temperature of the oven at 80 ℃, drying for 18h, and taking out the diaphragm.
Example 6
Preparing an in-situ growth nanoparticle modified polymer diaphragm:
A. preparing a tetraethyl orthosilicate solution with the volume percentage of 10 percent and an ethanol solution with the volume percentage of 80 percent, then uniformly mixing the tetraethyl orthosilicate solution and the ethanol solution with the volume percentage of 50 percent and ammonia water, and uniformly mixing the tetraethyl orthosilicate solution and the ethanol solution.
B. And placing the polyethylene diaphragm in the prepared solution, placing for 24h, and taking out the diaphragm.
C. The diaphragm is placed in an acetone solution, soaked for 3 hours, taken out and placed in an ethanol solution, and the standing time is 3 hours.
D. And (3) placing the diaphragm in an oven, setting the temperature of the oven at 80 ℃, drying for 24h, and taking out the diaphragm.
Example 7
Preparing an in-situ growth nanoparticle modified polymer diaphragm:
A. preparing tetraethyl orthosilicate solution with the volume percentage of 0.1 percent and ethanol solution with the volume percentage of 30 percent, and then soaking the polyethylene diaphragm for 30 min.
B. Preparing 1% ammonia water solution, soaking the diaphragm in the ammonia water for 30min, and taking out the diaphragm.
C. The membrane is placed in acetone solution, soaked for 30min, and then taken out and soaked in ethanol solution for 30 min.
D. And (3) placing the diaphragm in an oven, setting the temperature of the oven at 60 ℃, drying for 3h, and taking out the diaphragm.
Example 8
Preparing an in-situ growth nanoparticle modified polymer diaphragm:
A. preparing tetraethyl orthosilicate solution with the volume percentage of 5 percent and ethanol solution with the volume percentage of 50 percent, and then soaking the polyethylene diaphragm for 12 hours.
B. Preparing a 20% ammonia water solution, soaking the diaphragm in the ammonia water, gathering for 12 hours, and then taking out the diaphragm.
C. The diaphragm is placed in an acetone solution and soaked for 1h, and then taken out and soaked in an ethanol solution for 1 h.
D. And (3) placing the diaphragm in an oven, setting the temperature of the oven at 70 ℃, drying for 12h, and taking out the diaphragm.
Example 9
Preparing an in-situ growth nanoparticle modified polymer diaphragm:
A. preparing a tetraethyl orthosilicate solution with the volume percentage of 10 percent and an ethanol solution with the volume percentage of 90 percent, and then soaking the polyethylene diaphragm for 24 hours.
B. Preparing 50% ammonia water solution, soaking the diaphragm in the ammonia water for 24h, and then taking out the diaphragm.
C. The diaphragm is placed in an acetone solution and soaked for 3 hours, and then taken out and soaked in an ethanol solution for 3 hours.
D. And (3) placing the diaphragm in an oven, setting the temperature of the oven at 80 ℃, drying for 24h, and taking out the diaphragm.
Table 1 table of performance characterization data
From the results in table 1, it can be found that when the ammonia water concentration is 5% and the diaphragm is soaked for 24 hours, the internal resistance of the diaphragm is the minimum, which indicates that the inorganic particles are adsorbed on the surface of the diaphragm the most, the wettability of the electrolyte is better, and the resistance of the diaphragm is lower.
From the SEM image, it can be seen that in example 5, the nanoparticles are distributed most on the surface of the separator, and the surface of the separator is coated with the nanoparticles, which is also a cause of the decrease in internal resistance of the separator, and the increase of the nanoparticles also improves the heat-resistant stability of the separator and increases the safety performance of the battery.
Meanwhile, in example 5, the first discharge capacity (0.1C, lithium iron phosphate positive electrode material) of the battery is 157mAh g-1And after 100 cycles of 1C, the battery capacity is attenuated to 140.1mAh g-1And the calculated capacity retention rate is 96.28%, so that the battery assembled by the novel lithium ion battery in-situ coating diaphragm has stable performance.
Claims (10)
1. The preparation method of the in-situ grown nanoparticle modified polymer diaphragm is characterized by comprising the following steps of:
1) preparing tetraethyl orthosilicate solution and ethanol solution, and uniformly mixing the tetraethyl orthosilicate solution and the ethanol solution;
2) placing a polyethylene diaphragm, a polypropylene diaphragm or a non-woven fabric diaphragm in the mixed solution for a period of time, and then taking out the diaphragm;
3) soaking the diaphragm in an acetone solution, taking out and placing in an ethanol solution;
4) placing the diaphragm in an oven for drying, and then taking out the diaphragm;
wherein, in the step 1), after the tetraethyl orthosilicate solution and the ethanol solution are uniformly mixed, the ethanol solution of ammonia water is prepared and uniformly mixed with the two solutions; or in the step 2), after the diaphragm is taken out, preparing an ethanol solution of ammonia water, and soaking the diaphragm in the solution.
2. The method of claim 1, wherein the tetraethyl orthosilicate solution in step 1) is configured to have a volume percent of 0.1% to 10%.
3. The method of claim 1, wherein in step 1), the volume percent of the ethanol solution is configured to be 30% -90%.
4. The method of claim 1, wherein in step 2), the polyethylene membrane, the polypropylene membrane or the non-woven fabric membrane is placed in the mixed solution for 30min to 24 h.
5. The method of claim 1, wherein in step 3), the membrane is soaked in the acetone solution for 30min to 3 h.
6. The method of claim 1, wherein in step 3), the mixture is placed in an ethanol solution for 30min to 3 h.
7. The method as claimed in claim 1, wherein in the step 4), the oven temperature is set to 60-80 ℃ and the drying time is 3-24 h.
8. The method of claim 1, wherein the volume percent of the ethanol solution of ammonia is 1% to 50%.
9. The method of claim 1, wherein the membrane is soaked in an ethanol solution of ammonia for 30min to 24 h.
10. An in-situ grown nanoparticle modified polymer separator prepared by the method of any one of claims 1-9.
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| CN201910836178.2A CN110690387A (en) | 2019-09-05 | 2019-09-05 | Preparation method of in-situ growth nanoparticle modified polymer diaphragm |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111430670A (en) * | 2020-04-13 | 2020-07-17 | 阮弟根 | Positive electrode plate, processing method thereof, application of positive electrode plate in preparation of lithium battery, and lithium battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106221480A (en) * | 2016-07-26 | 2016-12-14 | 广东工业大学 | A kind of lithium ion battery separator coating and its preparation method and application |
| CN108807800A (en) * | 2018-08-08 | 2018-11-13 | 哈尔滨理工大学 | A kind of organo-mineral complexing lithium ion battery separator and preparation method thereof |
| CN109449355A (en) * | 2018-10-29 | 2019-03-08 | 郑州大学 | A kind of battery modified polyacrylonitrile non-woven fabrics/aerosil composite diaphragm and preparation method thereof |
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- 2019-09-05 CN CN201910836178.2A patent/CN110690387A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106221480A (en) * | 2016-07-26 | 2016-12-14 | 广东工业大学 | A kind of lithium ion battery separator coating and its preparation method and application |
| CN108807800A (en) * | 2018-08-08 | 2018-11-13 | 哈尔滨理工大学 | A kind of organo-mineral complexing lithium ion battery separator and preparation method thereof |
| CN109449355A (en) * | 2018-10-29 | 2019-03-08 | 郑州大学 | A kind of battery modified polyacrylonitrile non-woven fabrics/aerosil composite diaphragm and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111430670A (en) * | 2020-04-13 | 2020-07-17 | 阮弟根 | Positive electrode plate, processing method thereof, application of positive electrode plate in preparation of lithium battery, and lithium battery |
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Application publication date: 20200114 |