CN110649210A - Nonwoven paper ion battery diaphragm and preparation method thereof - Google Patents
Nonwoven paper ion battery diaphragm and preparation method thereof Download PDFInfo
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- CN110649210A CN110649210A CN201910974459.4A CN201910974459A CN110649210A CN 110649210 A CN110649210 A CN 110649210A CN 201910974459 A CN201910974459 A CN 201910974459A CN 110649210 A CN110649210 A CN 110649210A
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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
- 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
- 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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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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 belongs to the technical field of ion batteries, and particularly relates to a nonwoven paper ion battery diaphragm and a preparation method thereof. The invention provides a preparation method of a non-woven paper ion battery diaphragm, which comprises the following steps: step 1, mixing modified barium titanate powder with an organic solution to obtain a coating slurry; and 2, coating the coating slurry on the surface of non-woven paper, carrying out hot pressing to obtain a non-woven paper ion battery diaphragm, modifying barium titanate to improve the flame retardant effect of barium titanate, improving the compatibility of modified barium titanate powder under the action of an organic solution, embedding the coating slurry into micropores of the non-woven paper through hot pressing treatment, so that the pore diameter of the micropores of the non-woven paper is reduced, the pore diameter and the thickness of the non-woven paper are controlled, the problem of lithium dendrite is solved, and the technical defect that the existing non-woven paper is too large in pore diameter and thickness and cannot be applied to an ion battery is overcome.
Description
Technical Field
The invention belongs to the technical field of ion batteries, and particularly relates to a nonwoven paper ion battery diaphragm and a preparation method thereof.
Background
The ion battery is composed of four parts: positive electrode, electrolyte, diaphragm and negative electrode. The diaphragm basically serves to isolate the positive electrode from the negative electrode and provides a channel for the transmission of lithium ions. Common diaphragms in the market are PP, PE or PP/PE/PP three-layer membranes and the like, but PP and PE are high polymer materials, the melting point of the former is 167 ℃, the melting point of the latter is 135 ℃, and the membranes of the former and the latter are easy to rupture under the high-temperature condition. Moreover, the lithium dendrite growing at the negative electrode can also pierce the polyolefin diaphragm, so that the contact of the positive electrode and the negative electrode of the battery can cause explosion; moreover, PP and PE are nonpolar materials, so that the wettability of the electrolyte is poor, and the liquid absorption and retention performances are poor.
Nonwoven paper diaphragms are widely used in the fields of lead-acid batteries, alkaline batteries, nickel-hydrogen batteries, supercapacitors and the like, and due to the fact that nonwoven paper has excellent heat resistance, high film breaking temperature and other properties, the nonwoven paper has attracted more and more attention in the lithium battery industry in recent years. However, due to the limitation of the preparation process of the non-woven paper, the pore size and thickness of the existing non-woven paper are large, and when the non-woven paper is applied to an ion battery, the pore size is too large, so that the battery is short-circuited, and the non-woven paper is difficult to apply to the field of the ion battery.
Disclosure of Invention
In view of this, the application provides a nonwoven paper ion battery diaphragm and a preparation method thereof, which can effectively solve the technical defects that the existing nonwoven paper has too large aperture and thickness and cannot be applied to an ion battery.
The invention provides a preparation method of a non-woven paper ion battery diaphragm, which comprises the following steps:
step 1, mixing modified barium titanate powder with an organic solution to obtain a coating slurry;
and 2, coating the coating slurry on the surface of non-woven paper, and performing hot pressing to obtain the non-woven paper ion battery diaphragm, wherein the pore diameter of the non-woven paper ion battery diaphragm is 80-500 nm.
Preferably, the solute of the organic solution is selected from one or more of polyvinylidene fluoride, polyethylene oxide and cyclodextrin; more preferably, the solute of the organic solution is selected from PVDF (polyvinylidene fluoride), PVDF has the function of a binder, and meanwhile, PVDF can be matched with modified barium titanate powder to regulate the pore size of the non-woven paper and improve the liquid absorption and retention capacity of the non-woven paper.
Preferably, the solution of the organic solution is selected from one or more of N-methyl-2-pyrrolidone, N-dimethylformamide, and dimethylsulfoxide.
Preferably, the material of the non-woven paper is selected from one of polycarbonate, polypropylene or nylon; more preferably, the material of the non-woven paper is selected from polycarbonate.
Preferably, the method for preparing the modified barium titanate powder comprises the following steps:
step one, dispersing barium titanate, hexachlorocyclotriphosphazene, a monomer and a catalyst in a reaction solvent, and reacting to obtain modified barium titanate; wherein the monomer is polyol or sodium polyol;
and step two, drying the modified barium titanate to obtain modified barium titanate powder.
Wherein the mixing mass ratio of the barium titanate to the hexachlorocyclotriphosphazene is 1 (1-20); the molar ratio of the hexachlorocyclotriphosphazene to the monomer is 1 (3-6); preferably, the molar ratio of the hexachlorocyclotriphosphazene to the monomer is 1 (2-4).
The modified barium titanate is barium titanate particles with the surfaces coated with ring-crosslinked polyphosphazene coating layers, and the flame retardant property of the barium titanate is effectively improved by using polyphosphazene. The polyphosphazene is adopted to coat the barium titanate, and the compatibility of polyvinylidene fluoride (PVDF) and barium titanate can be improved.
Preferably, the particle size of the barium titanate is 20nm to 5000nm, and preferably, the particle size of the barium titanate is 50nm to 1000 nm.
The application uses barium titanate with the particle size of 20 nm-5000 nm, which can control the pore size of the non-woven paper and control the pore size of the non-woven paper in a proper range, and can inhibit shuttling of other tetravalent manganese ions and polysulfide compounds through polarization effect while ensuring shuttling of lithium ions.
Preferably, the reaction temperature is 25-110 ℃, and the reaction time is 0.5-4 h; preferably, the temperature of the reaction is 60 ℃ and the time of the reaction is 4 h.
Preferably, the polyhydric alcohol is one or more of 1, 4-butanediol, ethylene glycol, glycerol, 1, 3-propanediol and 2, 3-butanediol;
the catalyst is one or more of triethylamine, pyridine, calcium hydride and sodium hydride;
the reaction solvent is one or more of acetone, ethanol and acetonitrile.
The application provides a specific preparation method, which comprises the following steps:
a) performing ultrasonic dispersion on barium titanate and hexachlorocyclotriphosphazene in a reaction solvent for 0.2-2 h to obtain a first mixed solution;
b) then adding a monomer and a catalyst, stirring and reacting for 0.5-4 h at 25-110 ℃, filtering, washing, and drying at 75-85 ℃ to obtain modified barium titanate powder.
Preferably, step 1 further comprises a dispersant, and step 1 specifically is to mix modified barium titanate powder, the dispersant and an organic solvent to obtain a coating slurry.
Wherein the dispersant is the conventional dispersant, and is selected from sodium tripolyphosphate or/and sodium dodecyl sulfate.
Preferably, the hot pressing temperature is 30-200 ℃, the hot pressing pressure is 3-70 Mpa, and the hot pressing time is 5-180 s.
More preferably, the hot pressing temperature is 60-150 ℃, the pressure is 5-50 Mpa, and the hot pressing time is 10-120 s.
Preferably, the surface density of the non-woven paper is 5-20 g/cm3Preferably 8 to 18g/cm3。
The application also discloses a non-woven paper ion battery diaphragm which comprises the non-woven paper ion battery diaphragm prepared by the preparation method.
The invention aims to solve the technical problem that the pore diameter and the thickness of the non-woven paper in the prior art are too large, so that the non-woven paper cannot be applied to an ion battery. Therefore, the invention provides a non-woven paper ion battery diaphragm, which is prepared by coating modified barium titanate powder on the surface of non-woven paper and carrying out hot pressing. The barium titanate is modified, the flame retardant effect of the barium titanate is improved, the compatibility of the modified barium titanate powder is improved under the action of an organic solution, the particle size of the modified barium titanate powder can be single particle size or different particle sizes, the coating slurry is embedded into micropores of the non-woven paper through hot pressing, the pore diameter of the micropores of the non-woven paper is reduced, the pore size and the thickness of the non-woven paper are controlled, the problem of lithium dendrite is solved, the pore size and the thickness of the non-woven paper are controlled in a proper range (the pore size of a non-woven paper ion battery diaphragm is 80-500 nm), shuttle of specific ions (such as lithium ions) on the non-woven paper ion battery diaphragm can be guaranteed, shuttle of other ions on the non-woven paper ion battery diaphragm is restrained, and the service life and the safety of the battery are effectively improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a macro topography of a product 1 prepared in example 1 of the present application;
FIG. 2 is a microscopic topography of product 1;
fig. 3 is a micro-topography of the product 10 provided herein.
Detailed Description
The application provides a non-woven paper ion battery diaphragm and a preparation method thereof, which can effectively overcome the technical defects that the existing non-woven paper has too large aperture and thickness and cannot be applied to an ion battery.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The materials used in the following examples are commercially available or self-made, and the nonwoven paper used in the following examples is polycarbonate PC having an areal density of 12g/cm3。
Example 1
The application provides a preparation method of a non-woven paper ion battery diaphragm, which comprises the following specific steps:
firstly, adding 1g of barium titanate with the particle size of 50nm into acetone (100ml) for uniform dispersion, then respectively adding 1, 4-butanediol and hexachlorocyclotriphosphazene (the molar ratio of 1, 4-butanediol to hexachlorocyclotriphosphazene is 3: 2) into acetone containing barium titanate for reaction, stirring and reacting for 4 hours at the temperature of 60 ℃, centrifuging to remove the solvent, and carrying out forced air drying for 2 hours at the temperature of 80 ℃ to obtain modified barium titanate powder; modified barium titanate powder, sodium tripolyphosphate (0.1g) and sodium dodecyl sulfate (0.1g) are added into a DMSO solution of polyvinylidene fluoride (PVDF is 1g, and DMSO is 50ml) to prepare slurry, and the slurry is uniformly mixed to obtain coating slurry.
And coating the obtained coating slurry on the surface of the non-woven paper, airing and hot-pressing. Hot pressing temperature is 60 ℃, pressure is 5Mpa, hot pressing time is 120s, and product 1 is obtained.
The macro-topography and the micro-topography of the product 1 were examined and the results are shown in fig. 1 and 2.
Example 2
The application provides a second preparation method of a nonwoven paper ion battery diaphragm, which comprises the following specific steps:
firstly, adding 1g of barium titanate with the particle size of 50nm into acetone (100ml) for uniform dispersion, then respectively adding 1, 4-butanediol and hexachlorocyclotriphosphazene (the molar ratio of 1, 4-butanediol to hexachlorocyclotriphosphazene is 3: 2) into acetone containing barium titanate for reaction, stirring and reacting for 4 hours at the temperature of 60 ℃, centrifuging to remove the solvent, and carrying out forced air drying for 2 hours at the temperature of 80 ℃ to obtain modified barium titanate powder; modified barium titanate powder, sodium tripolyphosphate (0.1g) and sodium dodecyl sulfate (0.1g) are added into a DMSO solution of polyvinylidene fluoride (PVDF is 1g, and DMSO is 50ml) to prepare slurry, and the slurry is uniformly mixed to obtain coating slurry.
And coating the obtained coating slurry on the surface of the non-woven paper, airing and hot-pressing. Hot pressing temperature is 150 ℃, pressure is 5Mpa, hot pressing time is 10s, and product 2 is obtained.
Example 3
The application provides a preparation method of a third nonwoven paper ion battery diaphragm, which comprises the following specific steps:
firstly, adding 1g of barium titanate with the particle size of 50nm into acetone (100ml) for uniform dispersion, then respectively adding 1, 4-butanediol and hexachlorocyclotriphosphazene (the molar ratio of 1, 4-butanediol to hexachlorocyclotriphosphazene is 3: 2) into acetone containing barium titanate for reaction, stirring and reacting for 4 hours at the temperature of 60 ℃, centrifuging to remove the solvent, and carrying out forced air drying for 2 hours at the temperature of 80 ℃ to obtain modified barium titanate powder; modified barium titanate powder, sodium tripolyphosphate (0.1g) and sodium dodecyl sulfate (0.1g) are added into a DMSO solution of polyvinylidene fluoride (PVDF is 1g, and DMSO is 50ml) to prepare slurry, and the slurry is uniformly mixed to obtain coating slurry.
And coating the obtained coating slurry on the surface of the non-woven paper, airing and hot-pressing. Hot pressing temperature is 60 ℃, pressure is 50Mpa, hot pressing time is 10s, and product 3 is obtained.
Example 4
The application provides a fourth preparation method of a nonwoven paper ion battery diaphragm, which comprises the following specific steps:
firstly, adding 1g of barium titanate with the particle size of 50nm into acetone (100ml) for uniform dispersion, then respectively adding 1, 4-butanediol and hexachlorocyclotriphosphazene (the molar ratio of 1, 4-butanediol to hexachlorocyclotriphosphazene is 3: 2) into acetone containing barium titanate for reaction, stirring and reacting for 4 hours at the temperature of 60 ℃, centrifuging to remove the solvent, and carrying out forced air drying for 2 hours at the temperature of 80 ℃ to obtain modified barium titanate powder; modified barium titanate powder, sodium tripolyphosphate (0.1g) and sodium dodecyl sulfate (0.1g) are added into a DMSO solution of polyvinylidene fluoride (PVDF is 1g, and DMSO is 50ml) to prepare slurry, and the slurry is uniformly mixed to obtain coating slurry.
And coating the obtained coating slurry on the surface of the non-woven paper, airing and hot-pressing. Hot pressing temperature is 150 ℃, pressure is 50Mpa, hot pressing time is 10s, and product 4 is obtained.
Example 5
The application provides a fifth preparation method of a nonwoven paper ion battery diaphragm, which comprises the following specific steps:
firstly, adding 1g of barium titanate with the particle size of 1 mu m into acetone (100ml) for uniform dispersion, then respectively adding 1, 4-butanediol and hexachlorocyclotriphosphazene (the molar ratio of 1, 4-butanediol to hexachlorocyclotriphosphazene is 3: 2) into acetone containing barium titanate for reaction, stirring and reacting for 4 hours at the temperature of 60 ℃, centrifuging to remove the solvent, and carrying out forced air drying for 2 hours at the temperature of 80 ℃ to obtain modified barium titanate powder; modified barium titanate powder, sodium tripolyphosphate (0.1g) and sodium dodecyl sulfate (0.1g) are added into a DMSO solution of polyvinylidene fluoride (PVDF is 1g, and DMSO is 50ml) to prepare slurry, and the slurry is uniformly mixed to obtain coating slurry.
And coating the obtained coating slurry on the surface of the non-woven paper, airing and hot-pressing. Hot pressing temperature is 60 ℃, pressure is 50Mpa, hot pressing time is 10s, and product 5 is obtained.
Example 6
The application provides a sixth preparation method of a nonwoven paper ion battery diaphragm, which comprises the following specific steps:
firstly, adding 1g of barium titanate with the particle size of 1 mu m into acetone (100ml) for uniform dispersion, then respectively adding 1, 4-butanediol and hexachlorocyclotriphosphazene (the molar ratio of 1, 4-butanediol to hexachlorocyclotriphosphazene is 3: 2) into acetone containing barium titanate for reaction, stirring and reacting for 4 hours at the temperature of 60 ℃, centrifuging to remove the solvent, and carrying out forced air drying for 2 hours at the temperature of 80 ℃ to obtain modified barium titanate powder; modified barium titanate powder, sodium tripolyphosphate (0.1g) and sodium dodecyl sulfate (0.1g) are added into a DMSO solution of polyvinylidene fluoride (PVDF is 1g, and DMSO is 50ml) to prepare slurry, and the slurry is uniformly mixed to obtain coating slurry.
And coating the obtained coating slurry on the surface of the non-woven paper, airing and hot-pressing. Hot pressing temperature is 150 ℃, pressure is 50Mpa, hot pressing time is 10s, and product 6 is obtained.
Example 7
The application provides a seventh preparation method of a nonwoven paper ion battery diaphragm, which comprises the following specific steps:
firstly, 0.5g of barium titanate with the particle size of 50nm and 0.5g of barium titanate with the particle size of 1 mu m are added into acetone (200ml) together to be uniformly dispersed, then 1, 4-butanediol and hexachlorocyclotriphosphazene (the molar ratio of the 1, 4-butanediol to the hexachlorocyclotriphosphazene is 3: 2) are respectively added into the acetone containing barium titanate to carry out reaction, the reaction conditions are that after stirring reaction is carried out for 4h at 60 ℃, the solvent is washed away by centrifugation, and forced air drying is carried out for 2h at 80 ℃ to obtain modified barium titanate powder; modified barium titanate powder, sodium tripolyphosphate (0.1g) and sodium dodecyl sulfate (0.1g) are added into a DMSO solution of polyvinylidene fluoride (PVDF is 1g, and DMSO is 50ml) to prepare slurry, and the slurry is uniformly mixed to obtain coating slurry.
And coating the obtained coating slurry on the surface of the non-woven paper, airing and hot-pressing. Hot pressing temperature is 60 ℃, pressure is 5Mpa, hot pressing time is 120s, and product 7 is obtained.
Example 8
The application provides a preparation method of an eighth nonwoven paper ion battery diaphragm, which comprises the following specific steps:
firstly, 0.5g of barium titanate with the particle size of 50nm and 0.5g of barium titanate with the particle size of 1 mu m are added into acetone (200ml) together to be uniformly dispersed, then 1, 4-butanediol and hexachlorocyclotriphosphazene (the molar ratio of the 1, 4-butanediol to the hexachlorocyclotriphosphazene is 3: 2) are respectively added into the acetone containing barium titanate to carry out reaction, the reaction conditions are that after stirring reaction is carried out for 4h at 60 ℃, the solvent is washed away by centrifugation, and forced air drying is carried out for 2h at 80 ℃ to obtain modified barium titanate powder; modified barium titanate powder, sodium tripolyphosphate (0.1g) and sodium dodecyl sulfate (0.1g) are added into a DMSO solution of polyvinylidene fluoride (PVDF is 1g, DMSO is 50ml) to prepare slurry, and the slurry is uniformly mixed to obtain coating slurry.
Coating the obtained slurry on the surface of the non-woven paper, airing and hot-pressing. Hot pressing temperature is 150 ℃, pressure is 50Mpa, hot pressing time is 10s, and the product 8 is prepared.
Comparative example 1
A first comparative example is provided, and the specific manufacturing method is similar to that of example 1, except that the coating slurry is coated on the surface of the nonwoven paper, and dried to obtain a product 11 without hot pressing.
Comparative example 2
A second comparative example is provided, the specific preparation method being similar to that of example 1, except that DMSO instead of PVDF is used to obtain product 12.
Comparative example 3
A third comparative example is provided, and the specific preparation method is similar to that of example 1 except that the particle size of barium titanate is 100 μm, resulting in product 13.
Comparative example 4
A fourth comparative example is provided, the specific preparation method being similar to that of example 1, except that the particle size of barium titanate is 10nm, yielding product 14.
Comparative example 5
A fifth comparative example is provided, the specific preparation method being similar to that of example 1, except that DMSO was replaced with deionized water to give product 15.
The properties of the thickness, pore diameter, air permeability, heat shrinkage, rupture temperature, liquid absorption rate and liquid retention rate of the products obtained in examples 1 to 8 and comparative examples 1 to 5 were measured, and the results are shown in table 1. From the results in table 1, it is known that the higher the hot pressing temperature, the higher the hot pressing pressure, the thinner the thickness of the prepared nonwoven paper ion battery separator, the smaller the pore size, and the greater the air permeability; the hot pressing time is reduced at high hot pressing temperature, so that the efficiency can be improved; the polycarbonate material of the non-woven paper can be degraded under the condition of long-time high heat pressure temperature; the pore size of the obtained non-woven paper ion battery diaphragm product is relatively small, and the air permeability is larger, but the pore size of the non-woven paper ion battery diaphragm is too small (product 14), so that the shuttle of tetravalent manganese ions and polysulfide compounds in the battery is inhibited, meanwhile, the shuttle of lithium ions is also hindered, and the electrochemical performance of the non-woven paper ion battery is greatly reduced.
TABLE 1
Wherein, product 9 in Table 1 is a PE diaphragm purchased in the market, product 10 is a pure polycarbonate PC non-woven paper, and the surface density is 12g/cm3Without coating and hot pressing.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The preparation method of the nonwoven paper ion battery diaphragm is characterized by comprising the following steps:
step 1, mixing modified barium titanate powder with an organic solution to obtain a coating slurry;
and 2, coating the coating slurry on the surface of non-woven paper, and performing hot pressing to obtain the non-woven paper ion battery diaphragm, wherein the pore diameter of the non-woven paper ion battery diaphragm is 80-500 nm.
2. The production method according to claim 1, wherein the solute of the organic solution is selected from one or more of polyvinylidene fluoride, polyethylene oxide, and cyclodextrin; the solution of the organic solution is selected from one or more of N-methyl-2-pyrrolidone, N-dimethylformamide and dimethyl sulfoxide.
3. The method for preparing the non-woven paper according to the claim 1, wherein the non-woven paper is made of one or more materials selected from polycarbonate, polypropylene and nylon.
4. The method according to claim 1, wherein the method for preparing the modified barium titanate powder comprises the steps of:
step one, dispersing barium titanate, hexachlorocyclotriphosphazene, a monomer and a catalyst in a reaction solvent, and reacting to obtain modified barium titanate; wherein the monomer is polyol or sodium polyol;
and step two, drying the modified barium titanate to obtain modified barium titanate powder.
5. The method according to claim 4, wherein the particle size of the barium titanate is 20nm to 5000 nm.
6. The preparation method according to claim 4, wherein the reaction temperature is 25-110 ℃ and the reaction time is 0.5-4 h.
7. The method according to claim 4, wherein the polyhydric alcohol is one or more of 1, 4-butanediol, ethylene glycol, glycerol, 1, 3-propanediol and 2, 3-butanediol;
the catalyst is one or more of triethylamine, pyridine, calcium hydride and sodium hydride;
the reaction solvent is one or more of acetone, ethanol and acetonitrile.
8. The method according to claim 1, wherein the hot-pressing temperature is 30 to 200 ℃, the hot-pressing pressure is 3 to 70MPa, and the hot-pressing time is 5 to 180 s.
9. The preparation method according to claim 1, wherein step 1 further comprises a dispersant, and step 1 is to mix modified barium titanate powder, the dispersant and an organic solvent to obtain the coating slurry.
10. A nonwoven paper ion battery separator comprising the nonwoven paper ion battery separator produced by the production method according to any one of claims 1 to 9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112909324A (en) * | 2021-01-21 | 2021-06-04 | 北京理工大学 | Inorganic/organic composite solid electrolyte and preparation method and application thereof |
| CN114806220A (en) * | 2022-04-11 | 2022-07-29 | 江苏厚生新能源科技有限公司 | Modified barium sulfate powder, preparation method thereof and modified barium sulfate coated diaphragm |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1860626A (en) * | 2003-11-05 | 2006-11-08 | 海霸系统有限公司 | Separator for cylindrical cells |
| CN103199209A (en) * | 2013-04-01 | 2013-07-10 | 中国海诚工程科技股份有限公司 | Non-woven ceramic membrane with excellent closed-pore performance for lithium ion battery and technology |
| CN108475825A (en) * | 2016-01-22 | 2018-08-31 | 旭化成株式会社 | Lithium rechargeable battery |
| CN108822586A (en) * | 2018-05-23 | 2018-11-16 | 广东工业大学 | A kind of preparation method, battery diaphragm and the lithium ion battery of modified barium carbonate material |
| CN208706748U (en) * | 2018-07-26 | 2019-04-05 | 江西省通瑞新能源科技发展有限公司 | A kind of coating composite lithium battery membrane |
| CN110130115A (en) * | 2019-05-21 | 2019-08-16 | 吉林建筑大学 | A kind of preparation method of expanded perlite coating nonwoven cloth diaphragm |
| CN110165126A (en) * | 2019-06-10 | 2019-08-23 | 桑顿新能源科技(长沙)有限公司 | A kind of diaphragm for lithium ion battery and preparation method thereof and its lithium ion battery |
-
2019
- 2019-10-14 CN CN201910974459.4A patent/CN110649210A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1860626A (en) * | 2003-11-05 | 2006-11-08 | 海霸系统有限公司 | Separator for cylindrical cells |
| CN103199209A (en) * | 2013-04-01 | 2013-07-10 | 中国海诚工程科技股份有限公司 | Non-woven ceramic membrane with excellent closed-pore performance for lithium ion battery and technology |
| CN108475825A (en) * | 2016-01-22 | 2018-08-31 | 旭化成株式会社 | Lithium rechargeable battery |
| CN108822586A (en) * | 2018-05-23 | 2018-11-16 | 广东工业大学 | A kind of preparation method, battery diaphragm and the lithium ion battery of modified barium carbonate material |
| CN208706748U (en) * | 2018-07-26 | 2019-04-05 | 江西省通瑞新能源科技发展有限公司 | A kind of coating composite lithium battery membrane |
| CN110130115A (en) * | 2019-05-21 | 2019-08-16 | 吉林建筑大学 | A kind of preparation method of expanded perlite coating nonwoven cloth diaphragm |
| CN110165126A (en) * | 2019-06-10 | 2019-08-23 | 桑顿新能源科技(长沙)有限公司 | A kind of diaphragm for lithium ion battery and preparation method thereof and its lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| 徐志康，万灵书等编著: "《中国战略性新兴产业 新材料 高性能分离膜材料》", 31 December 2017 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112909324A (en) * | 2021-01-21 | 2021-06-04 | 北京理工大学 | Inorganic/organic composite solid electrolyte and preparation method and application thereof |
| CN112909324B (en) * | 2021-01-21 | 2023-04-21 | 北京理工大学 | Inorganic/organic composite solid electrolyte and preparation method and application thereof |
| CN114806220A (en) * | 2022-04-11 | 2022-07-29 | 江苏厚生新能源科技有限公司 | Modified barium sulfate powder, preparation method thereof and modified barium sulfate coated diaphragm |
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