CN109449355B - Modified polyacrylonitrile non-woven fabric/silicon dioxide aerogel composite diaphragm for battery and preparation method thereof - Google Patents
Modified polyacrylonitrile non-woven fabric/silicon dioxide aerogel composite diaphragm for battery and preparation method thereof Download PDFInfo
- Publication number
- CN109449355B CN109449355B CN201811265901.8A CN201811265901A CN109449355B CN 109449355 B CN109449355 B CN 109449355B CN 201811265901 A CN201811265901 A CN 201811265901A CN 109449355 B CN109449355 B CN 109449355B
- Authority
- CN
- China
- Prior art keywords
- woven fabric
- preparation
- silicon dioxide
- battery
- polyacrylonitrile non
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
-
- 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
-
- 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
-
- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
- D06M2101/28—Acrylonitrile; Methacrylonitrile
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a modified polyacrylonitrile non-woven fabric/silicon dioxide aerogel composite diaphragm for a battery and a preparation method thereof. The diaphragm is formed by in-situ growth of silicon dioxide aerogel on the surface of a modified polyacrylonitrile non-woven fabric fiber, and the preparation method comprises the following steps: firstly, preparing polyacrylonitrile non-woven fabric, soaking the polyacrylonitrile non-woven fabric in alkaline solution for hydrolysis, treating the polyacrylonitrile non-woven fabric with ethanol solution of ammonia water, then soaking the modified polyacrylonitrile non-woven fabric in silica sol, wherein the silica aerogel can uniformly grow and wrap the surface of the fiber, and drying the fiber to obtain the composite diaphragm. The invention adopts polyacrylonitrile non-woven fabric which is easy to be applied in large scale as a composite diaphragm substrate, adopts silicon dioxide aerogel with good heat resistance and light weight as a coating material, and the heat-resistant temperature of the composite diaphragm can reach 240 DEGoAnd C, the heat resistance of the diaphragm is greatly improved. The composite diaphragm is suitable for lithium ion batteries and sodium ion batteries, and has excellent safety performance and electrochemical performance.
Description
Technical Field
The invention belongs to the technical field of lithium/sodium ion batteries, and particularly relates to a modified polyacrylonitrile non-woven fabric/silicon dioxide aerogel composite diaphragm for a battery and a preparation method thereof.
Technical Field
With the wide application of energy storage devices such as batteries, battery safety becomes the primary consideration in the development process. The lithium and sodium ion battery mainly comprises a positive electrode, a negative electrode, electrolyte, a diaphragm, a shell and the like. The diaphragm is used as an important component of the battery, plays an important role in isolating the positive electrode and the negative electrode and allowing ions to freely shuttle, and the capacity, the cycle life and the safety performance of the battery are influenced by the performance of the diaphragm. The polypropylene diaphragm and the polyethylene diaphragm of the lithium ion battery which are commercialized at present have poor thermal stability and melting points of only 164 and 92 respectively although the polypropylene diaphragm and the polyethylene diaphragm have strong mechanical propertiesoC, the direct contact of the anode and the cathode of the battery caused by thermal contraction is very easy to occur, and great potential safety hazard is caused to the safety performance of the lithium ion battery; for sodium ion batteries, no commercial separator is available, which prevents the large-scale application of sodium ion batteries. Therefore, the preparation of the diaphragm with excellent chemical stability, high porosity and good heat resistance has great practical significance. The polyacrylonitrile non-woven fabric has the advantages of high porosity, good wettability to electrolyte and easy large-scale preparation, and meanwhile, the silicon dioxide aerogel has very low density and excellent heat resistance and has very high practical significance for improving the heat resistance of the diaphragm.
The modified polyacrylonitrile non-woven fabric/silicon dioxide aerogel composite diaphragm prepared by the invention has excellent heat resistance, and the temperature is 240 DEGoAnd no thermal shrinkage occurs after the temperature is kept for half an hour at the temperature C, so that the safety performance of the battery is greatly improved, and the development of a high-temperature lithium/sodium ion battery is greatly promoted.
Disclosure of Invention
The invention aims to provide a modified polyacrylonitrile non-woven fabric/silicon dioxide aerogel composite diaphragm for a battery and a preparation method thereof, which are characterized in that the polyacrylonitrile non-woven fabric has high porosity, low price and easy mass production, and the silicon dioxide aerogel has the advantages of high temperature resistance, light weight and the like, and the polyacrylonitrile non-woven fabric and the silicon dioxide aerogel are effectively compounded to form a novel high temperature resistant composite diaphragm, and the novel high temperature resistant composite diaphragm is applied to a lithium/sodium ion battery system, so that the safety performance of the battery is greatly improved.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a modified polyacrylonitrile non-woven fabric/silicon dioxide aerogel composite diaphragm for a battery is characterized in that silicon dioxide aerogel grows on the surface of a modified polyacrylonitrile non-woven fabric in situ.
The molecular weight of polyacrylonitrile is 1000-1000000.
The silica aerogel is light nano porous amorphous solid silica aerogel obtained by in-situ growth of silica sol on non-woven fabric fibers.
The preparation method of the modified polyacrylonitrile non-woven fabric/silicon dioxide aerogel composite diaphragm for the battery comprises the following steps:
(1) preparing polyacrylonitrile non-woven fabric: preparing polyacrylonitrile non-woven fabric by wet spinning or dry spinning:
(2) preparing a silica sol: tetraethyl orthosilicate, absolute ethyl alcohol and water are mixed according to the volume ratio of 5:29.2:7.2, hydrochloric acid is dripped to adjust the pH value to be =3-4, and the mixture is uniformly stirred to obtain silicon dioxide sol;
(3) treating polyacrylonitrile non-woven fabric with alkaline solution: soaking the polyacrylonitrile non-woven fabric in an alkaline solution, and then taking out the polyacrylonitrile non-woven fabric to be soaked in an ethanol solution of ammonia water to obtain a modified polyacrylonitrile non-woven fabric;
(4) and (2) dipping the modified polyacrylonitrile non-woven fabric into the silicon dioxide sol, taking out the silicon dioxide sol, putting the silicon dioxide sol into absolute ethyl alcohol, uniformly growing the silicon dioxide aerogel on the surface of the non-woven fabric fiber in situ, and drying to obtain the modified polyacrylonitrile non-woven fabric/silicon dioxide aerogel composite diaphragm for the battery.
The alkaline solution in the step (3) is potassium hydroxide/water solution, potassium hydroxide/ethanol solution, sodium hydroxide/water solution, sodium hydroxide/ethanol solution, oxyhydrogenAny one of lithium hydroxide/water solution or lithium hydroxide/ethanol solution; the mass fraction of the alkali solution is 0.1-20%, the dipping time is 0.1-12 h, and the temperature is 30-70oC。
The concentration of the ethanol solution of the ammonia water in the step (3) is 0.01-0.5 mol/L.
In the step (4), the time for soaking the modified polyacrylonitrile non-woven fabric in the silica sol is set to be 5 s-1 h, the drying is normal pressure drying, and the drying temperature is 30-100 ℃.
The modified polyacrylonitrile non-woven fabric/silicon dioxide aerogel composite diaphragm for the battery can be used for preparing a lithium ion battery, and the electrolyte of the lithium ion battery is obtained by dissolving lithium salt in a solvent, wherein the lithium salt includes but is not limited to LiClO4、LiPF6、LiAsF6、LiBF4LiBOB or LiCF3SO3The solvent comprises one or more of ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, diglyme and fluoroethylene carbonate; the positive electrode material includes but is not limited to lithium iron phosphate, lithium cobaltate or ternary material; negative electrode materials include, but are not limited to, graphite, lithium titanate, alloys, or silicon carbon.
The modified polyacrylonitrile non-woven fabric/silicon dioxide aerogel composite diaphragm for the battery can be used for preparing a sodium ion battery, and the electrolyte of the sodium ion battery is obtained by dissolving sodium salt in a solvent, wherein the sodium salt includes but is not limited to NaBF4、NaSO3CF3、NaClO4、NaPF6、NaN(CF3SO2)2The solvent comprises one or more of ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, diglyme and fluoroethylene carbonate; battery positive electrode materials include, but are not limited to, sodium vanadium phosphate, sodium manganate, iron phosphate, sodium ferrite, sodium iron phosphate, or prussian blue; battery negative electrode materials include, but are not limited to, carbon materials, metal oxides, metal sulfides or alloys.
The invention has the beneficial effects that: the invention has the advantages of light weight, high temperature resistance of the silica aerogel and high porosity and is easy for large-scale productionThe polyacrylonitrile non-woven fabric is compounded to obtain the composite diaphragm which can be simultaneously used in a lithium/sodium battery system and has excellent performance, and a new method is provided for preparing the composite diaphragm. The modified polyacrylonitrile non-woven fabric/silicon dioxide aerogel composite diaphragm prepared by the invention has excellent heat resistance, and the temperature is 240 DEGoNo thermal shrinkage occurred after half an hour at temperature C. Through performance test and structural representation, compared with the traditional commercialized lithium ion battery diaphragm, the diaphragm has good heat resistance and excellent electrochemical performance; meanwhile, a novel diaphragm is provided for the sodium ion battery, and the commercialization of the sodium ion battery is effectively promoted.
Drawings
FIG. 1 microstructure of a polyacrylonitrile nonwoven fabric prepared in example 1;
FIG. 2A modified polyacrylonitrile nonwoven fabric/silica aerogel composite membrane prepared in example 1;
FIG. 3A modified polyacrylonitrile nonwoven fabric/silica aerogel composite membrane prepared in example 3;
FIG. 4A modified polyacrylonitrile nonwoven fabric/silica aerogel composite membrane prepared in example 4;
FIG. 5 composite separator and electrolyte NaClO prepared in example 14Ethylene carbonate + propylene carbonate contact angle;
FIG. 6 composite separator and electrolyte LiPF prepared in example 16A contact angle of ethylene carbonate, dimethyl carbonate and diethyl carbonate;
FIG. 7 the composite membrane prepared in example 1 was maintained in morphology for 0.5 hours at different temperatures;
fig. 8 electrochemical performance of a lithium ion battery assembled from such a separator;
figure 9 electrochemical performance of a sodium ion battery assembled from such a separator.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The preparation method of the modified polyacrylonitrile non-woven fabric/silicon dioxide aerogel composite diaphragm for the battery in the embodiment is as follows:
(1) dissolving polyacrylonitrile powder with a molecular weight of 150000 in a mixed solvent of N, N dimethylformamide and acetone (mass ratio of 7: 3) with a mass fraction of 7%, and magnetically stirring for 6 hours to obtain a uniform spinning solution; and (3) preparing the polyacrylonitrile spinning solution into the non-woven fabric by using electrostatic spinning equipment. The electrostatic spinning needle head is a flat needle head, the needle head is connected with the positive pole of a high-voltage power supply, the spinning solution is pushed out by a micro-injection pump, and the process parameters of electrostatic spinning are as follows: the inner diameter of the needle is 0.8 mm, the voltage of a high-voltage power supply is 18 kV, the extrusion speed of the spinning solution is 0.8 mL/h, the distance from the needle to the receiving roller is 18 cm, the receiving plate is aluminum foil, and the environmental temperature is 25oAnd C, the relative humidity is 30-40%. The polyacrylonitrile nonwoven fabric is shown in figure 1.
(2) 5mL of tetraethyl orthosilicate, 29.2 mL of absolute ethanol and 7.2 mL of deionized water were weighed, mixed, and then 0.1mol/L hydrochloric acid was added dropwise to adjust the pH =3-4, and the mixture was magnetically stirred for more than 6 hours to form a uniform silica sol.
(3) Soaking the modified polyacrylonitrile non-woven fabric in 8% NaOH/H 260 in O solutionoAnd C, modifying for 2 hours, respectively washing for 3 times by using deionized water and ethanol, treating for 10 minutes by using an ethanol solution of ammonia water (3 mL of ammonia water and 80mL of ethanol), then putting the non-woven fabric into the silica sol for 15 seconds, taking out, putting the non-woven fabric into absolute ethanol for 2 hours, taking out, and drying at normal temperature to obtain the modified polyacrylonitrile non-woven fabric/silica aerogel composite membrane (as shown in figure 2).
I modified polyacrylonitrile non-woven fabric/silicon dioxide aerogel composite membrane for carrying out wettability test, and the membrane and NaClO4Ethylene carbonate + propylene carbonate, LiPF6The contact angle of the/ethylene carbonate + dimethyl carbonate + diethyl carbonate is almost 0o(see fig. 5 and 6).
II Heat resistance tests were performed on the separators at 150 and 200oAfter 0.5 h at C, the membrane did not shrink and deform (see fig. 7).
III the modified polyacrylonitrile non-woven fabric/silicon dioxide aerogel composite diaphragm is applied to a lithium ion battery system (button battery 2025), lithium iron phosphate is used as a positive electrode, a lithium sheet is used as a negative electrode, and LiPF6The method comprises the steps of taking ethylene carbonate, dimethyl carbonate and diethyl carbonate as electrolyte, assembling the battery in a glove box filled with argon, and adopting a Newwei battery test system (BTS7) to perform constant-current charge and discharge test at room temperature, wherein the voltage range is 2.5-4.0V, the current density is 0.5C, and the charge and discharge curve is shown in figure 8.
The modified polyacrylonitrile non-woven fabric/silicon dioxide aerogel composite diaphragm is applied to a sodium ion battery system (a button battery 2025), vanadium sodium phosphate is used as a positive electrode, a sodium sheet is used as a negative electrode, and NaClO is added4The ethylene carbonate and propylene carbonate are taken as electrolyte, the battery is assembled in a glove box filled with argon, a Newwei battery test system (BTS7) is adopted for constant current charge and discharge test at room temperature, the voltage range is 2.5-4.0V, the current density is 0.5C, and the charge and discharge curve is shown in figure 9.
Example 2
The preparation method of the modified polyacrylonitrile non-woven fabric/silicon dioxide aerogel composite diaphragm for the battery in the embodiment is as follows:
(1) dissolving polyacrylonitrile powder with molecular weight of 200000 in a mixed solvent of N, N-dimethylformamide and acetone (mass ratio of 7: 3) with mass fraction of 5%, and magnetically stirring for 6 hours to obtain a uniform spinning solution; and (3) preparing the polyacrylonitrile spinning solution into the non-woven fabric by using electrostatic spinning equipment. The electrostatic spinning needle head is a flat needle head, the needle head is connected with the positive pole of a high-voltage power supply, the spinning solution is pushed out by a micro-injection pump, and the process parameters of electrostatic spinning are as follows: the inner diameter of the needle is 0.8 mm, the voltage of a high-voltage power supply is 18 kV, the extrusion speed of the spinning solution is 0.8 mL/h, the distance from the needle to the receiving roller is 18 cm, the receiving plate is aluminum foil, and the environmental temperature is 25oAnd C, the relative humidity is 30-40%. Obtaining polyacrylonitrile non-woven fabric;
(2) 5mL of tetraethyl orthosilicate, 29.2 mL of absolute ethanol and 7.2 mL of deionized water were weighed, mixed, and then 0.1mol/L hydrochloric acid was added dropwise to adjust the pH =3-4, and the mixture was magnetically stirred for more than 6 hours to form a uniform silica sol.
(3) The polyacrylonitrile non-woven fabric is soaked in 8 percent NaOH/H 260 in O solutionoAnd C, modifying for 1 hour, respectively washing for 3 times by using deionized water and ethanol, treating for 10 minutes by using an ethanol solution of ammonia water (3 mL of ammonia water and 80mL of ethanol), then putting the non-woven fabric into the silica sol for 15 seconds, taking out, putting the non-woven fabric into absolute ethanol for 2 hours, taking out, and drying at normal temperature to obtain the modified polyacrylonitrile non-woven fabric/silica aerogel composite membrane.
Example 3
The preparation method of the modified polyacrylonitrile non-woven fabric/silicon dioxide aerogel composite diaphragm for the battery in the embodiment is as follows:
(1) dissolving polyacrylonitrile powder with a molecular weight of 150000 in a mixed solvent of N, N dimethylformamide and acetone (mass ratio of 7: 3) with a mass fraction of 7%, and magnetically stirring for 6 hours to obtain a uniform spinning solution; and (3) preparing the polyacrylonitrile spinning solution into the non-woven fabric by using electrostatic spinning equipment. The electrostatic spinning needle head is a flat needle head, the needle head is connected with the positive pole of a high-voltage power supply, the spinning solution is pushed out by a micro-injection pump, and the process parameters of electrostatic spinning are as follows: the inner diameter of the needle is 0.8 mm, the voltage of a high-voltage power supply is 18 kV, the extrusion speed of the spinning solution is 0.8 mL/h, the distance from the needle to the receiving roller is 18 cm, the receiving plate is aluminum foil, and the environmental temperature is 25oAnd C, the relative humidity is 30-40%. And (5) obtaining the polyacrylonitrile non-woven fabric.
(2) 5mL of tetraethyl orthosilicate, 29.2 mL of absolute ethanol and 7.2 mL of deionized water were weighed, mixed, and then 0.1mol/L hydrochloric acid was added dropwise to adjust the pH =3-4, and the mixture was magnetically stirred for more than 6 hours to form a uniform silica sol.
(3) The polyacrylonitrile non-woven fabric is soaked in 8 percent NaOH/H 260 in O solutionoAnd C, modifying for 2 hours, respectively washing for 3 times by using deionized water and ethanol, treating for 10 minutes by using an ethanol solution of ammonia water (3 mL of ammonia water and 80mL of ethanol), then putting the non-woven fabric into the silica sol for 2 minutes, taking out, putting the non-woven fabric into absolute ethanol for 2 hours, taking out, and drying at normal temperature to obtain the modified polyacrylonitrile non-woven fabric/silica aerogel composite membrane (as shown in figure 3).
Silica aerogel packThe coated modified polyacrylonitrile non-woven fabric composite membrane is subjected to a wettability test and is subjected to a NaClO test4Ethylene carbonate + propylene carbonate, LiPF6The contact angle of the/ethylene carbonate + dimethyl carbonate + diethyl carbonate is almost 0o。
II Heat resistance tests were performed on the separators at 150 and 200oAfter 0.5 h under C, the membrane did not shrink and deform.
Example 4
The preparation method of the modified polyacrylonitrile non-woven fabric/silicon dioxide aerogel composite diaphragm for the battery in the embodiment is as follows:
(1) dissolving polyacrylonitrile powder with a molecular weight of 150000 in a mixed solvent of N, N dimethylformamide and acetone (mass ratio of 7: 3) with a mass fraction of 7%, and magnetically stirring for 6 hours to obtain a uniform spinning solution; and (3) preparing the polyacrylonitrile spinning solution into the non-woven fabric by using electrostatic spinning equipment. The electrostatic spinning needle head is a flat needle head, the needle head is connected with the positive pole of a high-voltage power supply, the spinning solution is pushed out by a micro-injection pump, and the process parameters of electrostatic spinning are as follows: the inner diameter of the needle is 0.8 mm, the voltage of a high-voltage power supply is 18 kV, the extrusion speed of the spinning solution is 0.8 mL/h, the distance from the needle to the receiving roller is 18 cm, the receiving plate is aluminum foil, and the environmental temperature is 25oAnd C, the relative humidity is 30-40%. And (5) obtaining the polyacrylonitrile non-woven fabric.
(2) 5mL of tetraethyl orthosilicate, 29.2 mL of absolute ethanol and 7.2 mL of deionized water were weighed, mixed, and then 0.1mol/L hydrochloric acid was added dropwise to adjust the pH =3-4, and the mixture was magnetically stirred for more than 6 hours to form a uniform silica sol.
(3) The polyacrylonitrile non-woven fabric is soaked in 8 percent NaOH/H 260 in O solutionoAnd C, modifying for 2 hours, respectively washing for 3 times by using deionized water and ethanol, treating for 10 minutes by using an ethanol solution of ammonia water (6 mL of ammonia water and 80mL of ethanol), then putting the non-woven fabric into the silica sol for 2 minutes, taking out, putting the non-woven fabric into absolute ethanol for 2 hours, taking out, drying at normal temperature, and thus obtaining the double-modified polyacrylonitrile non-woven fabric/silica aerogel composite membrane (as shown in figure 4).
I modified polyacrylonitrile non-woven fabric/silicon dioxide aerogel composite membrane for carrying out wettability test, and the membrane and NaClO4Carbon/carbonEthylene acid ester + propylene carbonate, LiPF6The contact angle of the/ethylene carbonate + dimethyl carbonate + diethyl carbonate is almost 0o。
II Heat resistance tests were performed on the separators at 150 and 200oAfter 0.5 h under C, the membrane did not shrink and deform.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
1. A preparation method of a modified polyacrylonitrile non-woven fabric/silicon dioxide aerogel composite diaphragm for a battery is characterized in that silicon dioxide aerogel grows in situ on the surface of modified polyacrylonitrile non-woven fabric fibers, and the preparation method specifically comprises the following steps:
(1) preparing polyacrylonitrile non-woven fabric: preparing polyacrylonitrile non-woven fabric by wet spinning or dry spinning:
(2) preparing a silica sol: mixing tetraethyl orthosilicate, absolute ethyl alcohol and water according to the volume ratio of 5:29.2:7.2, dropwise adding hydrochloric acid, adjusting the pH to be =3-4, and uniformly stirring to obtain silicon dioxide sol;
(3) treating polyacrylonitrile non-woven fabric with alkaline solution: soaking the polyacrylonitrile non-woven fabric in an alkaline solution, and then taking out the polyacrylonitrile non-woven fabric to be soaked in an ethanol solution of ammonia water to obtain a modified polyacrylonitrile non-woven fabric;
(4) and (2) dipping the modified polyacrylonitrile non-woven fabric into the silicon dioxide sol, taking out the silicon dioxide sol, putting the silicon dioxide sol into absolute ethyl alcohol, uniformly growing the silicon dioxide aerogel on the surface of the non-woven fabric fiber in situ, and drying to obtain the modified polyacrylonitrile non-woven fabric/silicon dioxide aerogel composite diaphragm for the battery.
2. The preparation method of the modacrylic nonwoven fabric/silica aerogel composite membrane for the battery according to claim 1, wherein the preparation method comprises the following steps: the molecular weight of polyacrylonitrile is 1000-1000000.
3. The preparation method of the modacrylic nonwoven fabric/silica aerogel composite membrane for the battery according to claim 1, wherein the preparation method comprises the following steps: the silica aerogel is light nano porous amorphous solid silica aerogel obtained by in-situ growth of silica sol on non-woven fabric fibers.
4. The preparation method of the modacrylic nonwoven fabric/silica aerogel composite membrane for the battery according to claim 1, wherein the preparation method comprises the following steps: the alkaline solution in the step (3) is any one of potassium hydroxide/water solution, potassium hydroxide/ethanol solution, sodium hydroxide/water solution, sodium hydroxide/ethanol solution, lithium hydroxide/water solution or lithium hydroxide/ethanol solution; the mass fraction of the alkali solution is 0.1-20%, the dipping time is 0.1-12 h, and the temperature is 30-70oC。
5. The preparation method of the modacrylic nonwoven fabric/silica aerogel composite membrane for the battery according to claim 1, wherein the preparation method comprises the following steps: the concentration of the ethanol solution of the ammonia water in the step (3) is 0.01-0.5 mol/L.
6. The preparation method of the modacrylic nonwoven fabric/silica aerogel composite membrane for the battery according to claim 1, wherein the preparation method comprises the following steps: in the step (4), the time for soaking the modified polyacrylonitrile non-woven fabric in the silica sol is set to be 5 s-1 h, the drying is normal pressure drying, and the drying temperature is 30-100 ℃.
7. The preparation method of the modacrylic nonwoven fabric/silica aerogel composite membrane for the battery according to claim 1, wherein the preparation method comprises the following steps: the composite diaphragm can be used for preparing lithium ion batteries, lithiumThe electrolyte of the ion battery is obtained by dissolving lithium salt in a solvent, wherein the lithium salt comprises but is not limited to LiClO4、LiPF6、LiAsF6、LiBF4LiBOB or LiCF3SO3The solvent comprises one or more of ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, diglyme and fluoroethylene carbonate; the positive electrode material includes but is not limited to lithium iron phosphate, lithium cobaltate or ternary material; negative electrode materials include, but are not limited to, graphite, lithium titanate, alloys, or silicon carbon.
8. The preparation method of the modacrylic nonwoven fabric/silica aerogel composite membrane for the battery according to claim 1, wherein the preparation method comprises the following steps: the composite diaphragm can be used for preparing a sodium ion battery, and the electrolyte of the sodium ion battery is obtained by dissolving sodium salt in a solvent, wherein the sodium salt includes but is not limited to NaBF4、NaSO3CF3、NaClO4、NaPF6、NaN(CF3SO2)2The solvent comprises one or more of ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, diglyme and fluoroethylene carbonate; battery positive electrode materials include, but are not limited to, sodium vanadium phosphate, sodium manganate, iron phosphate, sodium ferrite, sodium iron phosphate, or prussian blue; battery negative electrode materials include, but are not limited to, carbon materials, metal oxides, metal sulfides or alloys.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811265901.8A CN109449355B (en) | 2018-10-29 | 2018-10-29 | Modified polyacrylonitrile non-woven fabric/silicon dioxide aerogel composite diaphragm for battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811265901.8A CN109449355B (en) | 2018-10-29 | 2018-10-29 | Modified polyacrylonitrile non-woven fabric/silicon dioxide aerogel composite diaphragm for battery and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109449355A CN109449355A (en) | 2019-03-08 |
| CN109449355B true CN109449355B (en) | 2021-07-02 |
Family
ID=65549085
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811265901.8A Active CN109449355B (en) | 2018-10-29 | 2018-10-29 | Modified polyacrylonitrile non-woven fabric/silicon dioxide aerogel composite diaphragm for battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109449355B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110690387A (en) * | 2019-09-05 | 2020-01-14 | 青海北捷新材料科技有限公司 | Preparation method of in-situ growth nanoparticle modified polymer diaphragm |
| CN110690388A (en) * | 2019-09-18 | 2020-01-14 | 中国科学院金属研究所 | Heat-shrinkage-resistant organic/inorganic composite lithium battery diaphragm and preparation method thereof |
| CN112786951A (en) * | 2021-01-22 | 2021-05-11 | 中国科学技术大学 | Preparation method of polymer composite solid electrolyte and polymer composite solid electrolyte |
| CN112897581B (en) * | 2021-03-04 | 2023-01-10 | 林源电力(南京)有限公司 | Preparation method of all-vanadium redox battery electrode material |
| CN113113620B (en) * | 2021-04-16 | 2022-11-11 | 峰特(浙江)新材料有限公司 | Preparation method of alkaline zinc-iron flow battery |
| CN114142159B (en) * | 2021-11-18 | 2022-12-27 | 武汉理工大学 | Polyacrylonitrile/cellulose/hydroxyapatite composite diaphragm and preparation method and application thereof |
| CN114583384A (en) * | 2022-02-24 | 2022-06-03 | 上海恩捷新材料科技有限公司 | Porous fiber composite diaphragm and preparation method thereof |
| CN114976472A (en) * | 2022-05-17 | 2022-08-30 | 刘文洁 | Aerogel battery diaphragm and preparation method thereof |
| CN115216785B (en) * | 2022-07-01 | 2024-04-30 | 中国华能集团清洁能源技术研究院有限公司 | Electrode for electrolytic hydrogen production, electrolytic device and method |
| CN115101889A (en) * | 2022-07-07 | 2022-09-23 | 武汉纺织大学 | Preparation method of silicon dioxide compounded polyacrylonitrile lithium battery diaphragm |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103972445A (en) * | 2013-01-28 | 2014-08-06 | 海洋王照明科技股份有限公司 | Electrochemical power supply diaphragm and preparation method thereof, and electrochemical battery or capacitor |
| CN103971950A (en) * | 2013-01-28 | 2014-08-06 | 海洋王照明科技股份有限公司 | Electrochemical power source membrane, preparation method of electrochemical power source membrane and electrochemical battery or capacitor |
| CN106784558A (en) * | 2017-03-13 | 2017-05-31 | 厦门大学 | Ceramic diaphragm with aeroge as powder and its application in lithium ion battery |
-
2018
- 2018-10-29 CN CN201811265901.8A patent/CN109449355B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103972445A (en) * | 2013-01-28 | 2014-08-06 | 海洋王照明科技股份有限公司 | Electrochemical power supply diaphragm and preparation method thereof, and electrochemical battery or capacitor |
| CN103971950A (en) * | 2013-01-28 | 2014-08-06 | 海洋王照明科技股份有限公司 | Electrochemical power source membrane, preparation method of electrochemical power source membrane and electrochemical battery or capacitor |
| CN106784558A (en) * | 2017-03-13 | 2017-05-31 | 厦门大学 | Ceramic diaphragm with aeroge as powder and its application in lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109449355A (en) | 2019-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109449355B (en) | Modified polyacrylonitrile non-woven fabric/silicon dioxide aerogel composite diaphragm for battery and preparation method thereof | |
| CN109004199B (en) | Preparation method of biomass hard carbon material for negative electrode of sodium-ion battery | |
| CN110739427B (en) | Battery diaphragm material and preparation method and application thereof | |
| CN108281705B (en) | Modified nano SiO2Particles, method of preparing the same, and nanofiber membrane, gel electrolyte and lithium metal battery comprising the same | |
| WO2020073915A1 (en) | Lithium ion battery negative electrode material and non-aqueous electrolyte battery | |
| CN112909234A (en) | Preparation method and application of lithium cathode or sodium cathode | |
| CN106505194A (en) | Modified cobalt acid lithium and preparation method thereof, lithium ion battery and its chemical synthesizing method | |
| CN112885985B (en) | Positive pole piece and preparation method thereof, electrochemical energy storage device and pre-metallization method of electrochemical energy storage device | |
| CN110707294B (en) | Lithium-philic heteroatom and metal oxide co-doped three-dimensional fiber framework lithium battery cathode and preparation method thereof | |
| CN108987683A (en) | A kind of preparation method of carbon coating tertiary cathode material | |
| CN109449376B (en) | Composite lithium metal electrode and preparation method thereof | |
| CN112117444A (en) | Carbon-coated cobalt sulfide positive electrode material, preparation method, positive electrode and aluminum ion battery | |
| CN110911741B (en) | Carbon oxide sphere doped solid polymer electrolyte membrane and preparation method and application thereof | |
| CN106654182B (en) | Manganese dioxide sulphur carbon anode and preparation method | |
| CN109193041A (en) | A kind of lithium ion battery that high temperature cyclic performance is excellent | |
| CN111584866A (en) | Preparation method of high-rate artificial graphite negative electrode material | |
| CN114552122A (en) | Diaphragm, preparation method thereof and secondary battery | |
| CN114512723A (en) | Lithium ion secondary battery | |
| CN107978741B (en) | Preparation method of positive electrode composite material for lithium-sulfur battery | |
| CN109037683A (en) | A kind of negative electrode of lithium ion battery plate and its modified technique | |
| CN103682439B (en) | High voltage non-aqueous electrolyte and high voltage nonaqueous electrolyte secondary battery | |
| CN109378444A (en) | A kind of aluminium ion battery and its positive preparation method | |
| CN107946582B (en) | Lithium-sulfur battery positive electrode material, preparation method thereof, lithium battery positive electrode and lithium battery | |
| CN111342117A (en) | Super-hydrophobic solid electrolyte of lithium-air battery and preparation method thereof | |
| CN114843698B (en) | Composite oil-based diaphragm, preparation method thereof and secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |