CN114204210B - Preparation method of sodium ion battery diaphragm - Google Patents
Preparation method of sodium ion battery diaphragm Download PDFInfo
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- CN114204210B CN114204210B CN202111305119.6A CN202111305119A CN114204210B CN 114204210 B CN114204210 B CN 114204210B CN 202111305119 A CN202111305119 A CN 202111305119A CN 114204210 B CN114204210 B CN 114204210B
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 49
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 56
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 26
- 230000015572 biosynthetic process Effects 0.000 claims description 20
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 20
- 238000003786 synthesis reaction Methods 0.000 claims description 20
- ZHDTXTDHBRADLM-UHFFFAOYSA-N hydron;2,3,4,5-tetrahydropyridin-6-amine;chloride Chemical compound Cl.NC1=NCCCC1 ZHDTXTDHBRADLM-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 16
- PHIQPXBZDGYJOG-UHFFFAOYSA-N sodium silicate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Si]([O-])=O PHIQPXBZDGYJOG-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 14
- 230000002194 synthesizing effect Effects 0.000 claims description 13
- 239000012528 membrane Substances 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 11
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229920000768 polyamine Polymers 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- UPDATVKGFTVGQJ-UHFFFAOYSA-N sodium;azane Chemical compound N.[Na+] UPDATVKGFTVGQJ-UHFFFAOYSA-N 0.000 claims description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- -1 amine salt Chemical class 0.000 abstract description 8
- 239000011964 heteropoly acid Substances 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 7
- 229920002635 polyurethane Polymers 0.000 abstract description 6
- 239000004814 polyurethane Substances 0.000 abstract description 6
- 159000000000 sodium salts Chemical class 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 125000003277 amino group Chemical group 0.000 abstract description 3
- 150000008064 anhydrides Chemical group 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 8
- 239000004642 Polyimide Substances 0.000 description 7
- 229920001721 polyimide Polymers 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical class O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- URQWOSCGQKPJCM-UHFFFAOYSA-N [Mn].[Fe].[Ni] Chemical compound [Mn].[Fe].[Ni] URQWOSCGQKPJCM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a preparation method of a sodium ion battery diaphragm, which relates to the technical field of lithium ion batteries, and aims to improve the ion conductivity of the diaphragm by controlling functional groups at the tail end of a polyurethane molecular chain to enable the surface of the diaphragm to have anhydride groups, enabling an amine salt of silicotungstic heteropolyacid to react with polyurethane through amino groups on the surface to reduce the dielectric constant of the diaphragm, enabling the diaphragm to have better insulating property, and enabling sodium ions in the sodium salt of silicotungstic heteropolyacid to be transmitted in porous nano ions of the diaphragm.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of a sodium ion battery diaphragm.
Background
A Sodium-ion battery (rechargeable battery) is a secondary battery that mainly relies on Sodium ions to move between a positive electrode and a negative electrode to operate, similar to the principle of lithium-ion battery operation.
Sodium ion batteries have the advantages over lithium ion batteries: (1) The sodium salt raw material has rich reserves and low price, and compared with the ternary positive electrode material of the lithium ion battery, the iron-manganese-nickel-based positive electrode material has half of the raw material cost; (2) Due to the characteristic of sodium salt, low-concentration electrolyte (the electrolyte with the same concentration, the conductivity of sodium salt is about 20 percent higher than that of lithium electrolyte) is allowed to be used, so that the cost is reduced; (3) The sodium ions do not form alloy with aluminum, and the negative electrode can adopt aluminum foil as a current collector, so that the cost can be further reduced by about 8 percent, and the weight can be reduced by about 10 percent; (4) The sodium-ion battery is allowed to discharge to zero volts due to its non-overdischarge characteristics. The energy density of the sodium ion battery is more than 100Wh/kg, which is comparable with that of the lithium iron phosphate battery, but the sodium ion battery has obvious cost advantage and is expected to replace the traditional lead-acid battery in large-scale energy storage.
The sodium ion battery is a novel rocking chair battery, and in recent years, as the price of raw materials of the lithium ion battery increases more and more, the sodium ion battery is getting attention of the battery community due to the self cost advantage. However, the research on the sodium ion battery is not as hot as that of the lithium ion battery, and the industrial chain is not mature, so that all main materials are in the research and development stage. The membrane of the sodium ion battery is one of the key links, and the power and energy storage battery requires that the used membrane not only has the basic performance of the common membrane, but also has more excellent high temperature resistance, and many battery manufacturers require that the membrane has 150 ℃ high temperature heat shrinkage performance. In the conventional polyolefin membrane, the melting point of the polyethylene membrane is 130 ℃, and when the melting point is exceeded, the membrane is fused; while polypropylene has a melting point of 163 c, when the temperature reaches 150 c, the separator will shrink by more than 30%. Therefore, the traditional polyolefin diaphragm can not meet the requirements of a power lithium battery, and the traditional polyolefin diaphragm is poor in liquid absorption and liquid retention, so that the internal resistance of the battery is increased.
The Polyimide (PI) material has good thermal stability, chemical stability and outstanding mechanical properties, and the long-term use temperature of the Polyimide (PI) material can reach 300 ℃, so that the Polyimide (PI) material is a film insulating material with the best comprehensive properties. PI has a better affinity for lithium ion electrolyte than polyolefin separators due to having polar groups, and is therefore considered as a next-generation lithium ion battery separator material. Similarly, the silicotungstic heteropoly acid salt is an inorganic porous nano ion, and can be used as a building block in the field of synthesizing organic-inorganic nano composite materials to obviously improve the performance of the materials. Therefore, if the two materials can be used in the separator of the sodium ion battery, the excellent effect will be brought.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a sodium ion battery diaphragm, which is characterized in that functional groups at the tail end of a polyurethane molecular chain are controlled to enable the surface of the functional groups to be provided with acid anhydride groups, and silicotungstic heteropolyacid amine salt reacts with polyurethane through the amino groups on the surface to reduce the dielectric constant of the diaphragm, so that the diaphragm has better insulating property, sodium ions in silicotungstic heteropolyacid sodium salt can be transmitted in porous nano ions of the diaphragm, and the ion conducting property of the diaphragm is improved.
The invention provides a preparation method of a sodium ion battery diaphragm, which comprises the following steps:
the method comprises the steps of (1) adding 4, 4-diaminodiphenyl ether into a three-necked flask at room temperature, adding N, N-dimethylformamide into the 4, 4-diaminodiphenyl ether under nitrogen atmosphere, dissolving and mixing to obtain a mixed solution, and then adding pyromellitic anhydride into the mixed solution for three times at fixed intervals;
preferably, in the polyamine acid synthesis step, 450 ml of N, N-dimethylformamide and 100 mmol of pyromellitic anhydride are added per 100 ml of 4, 4-diaminodiphenyl ether.
More specifically, the fixed time interval is at least 4 hours.
Dissolving sodium silicate nonahydrate in deionized water to prepare a solution I, dissolving sodium tungstate dihydrate in water to prepare a solution II, stirring and mixing the solution I and the solution II, dropwise adding ammonium chloride to adjust the pH value to 5-6, adding sodium chloride to generate a large amount of precipitate, collecting the precipitate, and washing with a saturated sodium chloride solution to obtain sodium ammonium silicotungstate;
and a diaphragm synthesis step, wherein sodium silicotungstate obtained in the sodium silicotungstate synthesis step is added into the mixed solution added with pyromellitic anhydride in the polyamine acid synthesis step under the nitrogen atmosphere, the solution reacts for 12 hours at the reaction temperature of 50 ℃ to obtain a solution with viscosity, and the solution with viscosity is advected onto a clean glass plate and dried for 8 hours at the temperature of 80 ℃ under the nitrogen atmosphere to obtain the sodium ion battery diaphragm.
Preferably, in the step of synthesizing the diaphragm, 10% of the total mass of the mixed solution added with pyromellitic anhydride in the step of synthesizing the polyamine acid is added into the sodium ammonium silicotungstate prepared in the step of synthesizing the sodium ammonium silicotungstate.
In the membrane synthesis step, the area of the solution with viscosity on a clean glass plate is required to be equal to the thickness of the sodium ion battery membrane which can be prepared after drying to be 10-20 um.
Still further, for each sodium ion battery separator prepared, 10 ml of 4, 4-diaminodiphenyl ether, 45 ml of N, N-dimethylformamide, 10 mmol of pyromellitic anhydride, 14.2 g of sodium silicate nonahydrate, and 182 g of sodium tungstate dihydrate were required.
Preferably, in the sodium silicotungstate amine synthesis step, 14.2 g of sodium silicate nonahydrate is added to every 100 ml of deionized water in the solution I, and 182 g of sodium tungstate dihydrate is added to every 300 ml of deionized water in the solution II.
More preferably, in each preparation of a sodium ion battery diaphragm, in the step of synthesizing sodium silicotungstate, 180 ml of ammonium chloride is added dropwise to adjust the pH value to 5-6 after stirring and mixing the solution I and the solution II, and then 100 g of sodium chloride is added to perform precipitation.
Compared with the prior art, the preparation method of the sodium ion battery diaphragm has the advantages that the functional groups at the tail ends of the polyurethane molecular chains are controlled to enable the surfaces of the sodium ion battery diaphragm to have anhydride groups, at the moment, the silicotungstic heteropolyacid amine salt reacts with the polyurethane through the amino groups on the surfaces to form an organic-inorganic nanocomposite connected through covalent bonds, and the silicotungstic heteropolyacid amine salt can reduce the dielectric constant of the diaphragm, so that the diaphragm has better insulating property; and sodium ions in the silicotungstic acid sodium salt can be transmitted in the porous nano ions, so that the ion conducting property of the diaphragm can be improved, the positive ion amine radical ions and sodium ions of the silicotungstic acid salt and the silicotungstic acid anions form the silicotungstic acid amine sodium, and the advantages of the two salts are combined to form the sodium ion battery diaphragm.
Detailed Description
The technical solution for achieving the object of the present invention will be further described with reference to several specific examples, but it should be noted that the technical solution claimed in the present invention includes but is not limited to the following examples.
Example 1
The preparation method of the sodium ion battery diaphragm disclosed in the embodiment 1 comprises the following steps:
and a step of synthesizing the polyamino acid, wherein 10 millimoles of 4, 4-diaminodiphenyl ether is added into a three-necked flask at the temperature of 25 ℃ at room temperature, 45 milliliters of N, N-dimethylformamide is added under the nitrogen atmosphere, and after the 4, 4-diaminodiphenyl ether is fully dissolved, 10 millimoles of pyromellitic anhydride is added, and the pyromellitic anhydride is added into the solution three times at intervals of 4 hours.
14.2 g of sodium silicate nonahydrate is dissolved in 100 ml of deionized water, 182 g of sodium tungstate dihydrate is dissolved in 300 ml of water, the sodium silicate nonahydrate and the sodium silicate nonahydrate are mixed and strongly stirred, 180 ml of ammonium chloride is dropwise added, the pH value is regulated to be 5-6, the mixture is slightly stirred, 100 g of sodium chloride is added, a large amount of precipitate is generated, the precipitate is collected and washed by sodium chloride, and the obtained product is sodium ammonium silicotungstate.
And a diaphragm synthesis step, namely adding sodium silicotungstate of which the total mass is 10% of the total mass of the solution into the solution under the nitrogen atmosphere after the solution in the polyamine acid synthesis step is completely reacted, keeping the reaction temperature at 50 ℃ for 12 hours, flatly flowing the obtained solution with viscosity onto a clean glass plate, and drying the solution at 80 ℃ for 8 hours under the nitrogen atmosphere to obtain the sodium ion battery diaphragm with the thickness of 10-20 um.
Example 2
The preparation method of the sodium ion battery diaphragm disclosed in the embodiment 2 comprises the following steps:
and a step of synthesizing the polyamino acid, wherein 10 millimoles of 4, 4-diaminodiphenyl ether is added into a three-necked flask at the temperature of 25 ℃ at room temperature, 45 milliliters of N, N-dimethylformamide is added under the nitrogen atmosphere, and after the 4, 4-diaminodiphenyl ether is fully dissolved, 10 millimoles of pyromellitic anhydride is added, and the pyromellitic anhydride is added into the solution three times at intervals of 4 hours.
14.2 g of sodium silicate nonahydrate is dissolved in 100 ml of deionized water, 182 g of sodium tungstate dihydrate is dissolved in 300 ml of water, the sodium silicate nonahydrate and the sodium silicate nonahydrate are mixed and strongly stirred, 2800 ml of ammonium chloride is dropwise added, the pH value is regulated to be 5-6, the mixture is slightly stirred, 50 g of sodium chloride is added, a large amount of precipitate is generated, the precipitate is collected and washed by sodium chloride, and the obtained product is sodium ammonium silicotungstate.
And a diaphragm synthesis step, namely adding sodium silicotungstate of which the total mass is 10% of the total mass of the solution into the solution under the nitrogen atmosphere after the solution in the polyamine acid synthesis step is completely reacted, keeping the reaction temperature at 50 ℃ for 12 hours, flatly flowing the obtained solution with viscosity onto a clean glass plate, and drying the solution at 80 ℃ for 8 hours under the nitrogen atmosphere to obtain the sodium ion battery diaphragm with the thickness of 10-20 um.
Example 3
Example 3 discloses a method for preparing a sodium ion battery separator, comprising the following steps:
and a step of synthesizing the polyamino acid, wherein 10 millimoles of 4, 4-diaminodiphenyl ether is added into a three-necked flask at the temperature of 25 ℃ at room temperature, 45 milliliters of N, N-dimethylformamide is added under the nitrogen atmosphere, and after the 4, 4-diaminodiphenyl ether is fully dissolved, 10 millimoles of pyromellitic anhydride is added, and the pyromellitic anhydride is added into the solution three times at intervals of 4 hours.
14.2 g of sodium silicate nonahydrate is dissolved in 100 ml of deionized water, 182 g of sodium tungstate dihydrate is dissolved in 300 ml of water, the sodium silicate nonahydrate and the sodium silicate nonahydrate are mixed and strongly stirred, 180 ml of ammonium chloride is dropwise added, the pH value is regulated to be 5-6, the mixture is slightly stirred, 200 g of sodium chloride is added, a large amount of precipitate is generated, the precipitate is collected and washed by sodium chloride, and the obtained product is sodium ammonium silicotungstate.
And a diaphragm synthesis step, namely adding sodium silicotungstate of which the total mass is 10% of the total mass of the solution into the solution under the nitrogen atmosphere after the solution in the polyamine acid synthesis step is completely reacted, keeping the reaction temperature at 50 ℃ for 12 hours, flatly flowing the obtained solution with viscosity onto a clean glass plate, and drying the solution at 80 ℃ for 8 hours under the nitrogen atmosphere to obtain the sodium ion battery diaphragm with the thickness of 10-20 um.
Example 4
Example 4 discloses a method for preparing a sodium ion battery separator, comprising the following steps:
and a step of synthesizing the polyamino acid, wherein 10 millimoles of 4, 4-diaminodiphenyl ether is added into a three-necked flask at the temperature of 25 ℃ at room temperature, 45 milliliters of N, N-dimethylformamide is added under the nitrogen atmosphere, and after the 4, 4-diaminodiphenyl ether is fully dissolved, 10 millimoles of pyromellitic anhydride is added, and the pyromellitic anhydride is added into the solution three times at intervals of 4 hours.
14.2 g of sodium silicate nonahydrate is dissolved in 100 ml of deionized water, 182 g of sodium tungstate dihydrate is dissolved in 300 ml of water, the solution is strongly stirred, the pH value is regulated to 5-6, the solution is slightly stirred, 100 g of sodium chloride is added, a large amount of precipitate is generated, the precipitate is collected and washed by the sodium chloride, and the obtained product is sodium ammonium silicotungstate.
And a diaphragm synthesis step, namely adding sodium silicotungstate of which the total mass is 10% of the total mass of the solution into the solution under the nitrogen atmosphere after the solution in the polyamine acid synthesis step is completely reacted, keeping the reaction temperature at 50 ℃ for 12 hours, flatly flowing the obtained solution with viscosity onto a clean glass plate, and drying the solution at 80 ℃ for 8 hours under the nitrogen atmosphere to obtain the sodium ion battery diaphragm with the thickness of 10-20 um.
Comparative example 1
The preparation method of the sodium ion battery diaphragm disclosed in comparative example 1 comprises the following steps:
and a step of synthesizing the polyamino acid, wherein 10 millimoles of 4, 4-diaminodiphenyl ether is added into a three-necked flask at the temperature of 25 ℃ at room temperature, 45 milliliters of N, N-dimethylformamide is added under the nitrogen atmosphere, and after the 4, 4-diaminodiphenyl ether is fully dissolved, 10 millimoles of pyromellitic anhydride is added, and the pyromellitic anhydride is added into the solution three times at intervals of 4 hours.
And a diaphragm synthesis step, namely after the reaction of the polyamine acid synthesis step is completed, advecting the obtained solution with viscosity onto a clean glass plate, and drying the solution at 80 ℃ for 8 hours in a nitrogen atmosphere to finally obtain the sodium ion battery diaphragm with the thickness of 10-20 um.
The sodium ion battery separators prepared in examples 1 to 4 and comparative example 1 above were tested as follows:
1. subjecting the prepared membrane to a dielectric constant test;
2. assembling the prepared diaphragm, detecting the internal resistance of the prepared battery, and judging the ionic conductance of the diaphragm;
the test results can be referred to in Table 1 below
TABLE 1
That is, as can be seen from table 1, the sodium ion battery separator prepared by the method of the present invention has a dielectric constant superior to that of the sodium ion battery separator prepared by the conventional technical scheme, and the internal resistance of the lithium battery prepared by the sodium ion battery separator prepared by the method of the present invention is also significantly lower than that of the lithium battery prepared by the conventional technical scheme.
Claims (3)
1. The preparation method of the sodium ion battery diaphragm is characterized by comprising the following steps of:
the method comprises the steps of (1) adding 4, 4-diaminodiphenyl ether into a three-necked flask at room temperature, adding N, N-dimethylformamide into the 4, 4-diaminodiphenyl ether under nitrogen atmosphere, dissolving and mixing to obtain a mixed solution, and then adding pyromellitic anhydride into the mixed solution for three times at fixed intervals; specifically, 450 ml of N, N-dimethylformamide and 100 mmol of pyromellitic anhydride are added per 100 ml of 4, 4-diaminodiphenyl ether;
dissolving sodium silicate nonahydrate in deionized water to prepare a solution I, dissolving sodium tungstate dihydrate in water to prepare a solution II, stirring and mixing the solution I and the solution II, dropwise adding ammonium chloride to adjust the pH value to 5-6, adding sodium chloride to precipitate, collecting precipitate, and washing with a saturated sodium chloride solution to obtain sodium ammonium silicotungstate; specifically, 14.2 g of sodium silicate nonahydrate is added to every 100 ml of deionized water in the solution I, and 182 g of sodium tungstate dihydrate is added to every 300 ml of deionized water in the solution II;
a diaphragm synthesis step, namely adding sodium silicotungstate obtained in the sodium silicotungstate synthesis step into the mixed solution added with pyromellitic anhydride in the polyamine acid synthesis step in a nitrogen atmosphere, reacting for 12 hours at a reaction temperature of 50 ℃ to obtain a solution with viscosity, and advecting the solution with viscosity onto a clean glass plate and drying for 8 hours at a temperature of 80 ℃ in the nitrogen atmosphere to obtain a sodium ion battery diaphragm; specifically, 10% of the total mass of the mixed solution added with pyromellitic anhydride in the step of synthesizing the polyamine acid is added with sodium silicotungstate prepared in the step of synthesizing sodium silicotungstate;
the fixed time interval is at least 4 hours;
in the step of synthesizing sodium silicotungstate, 180 ml of ammonium chloride is added dropwise to adjust the pH value to 5-6 after the solution I and the solution II are stirred and mixed, and then 100 g of sodium chloride is added to precipitate.
2. The method for preparing the sodium ion battery diaphragm according to claim 1, wherein the method comprises the following steps: in the membrane synthesis step, the area of the solution with viscosity on a clean glass plate is required to be leveled, and the thickness of the sodium ion battery membrane which can be prepared after drying is required to be 10-20 microns.
3. The method for preparing the sodium ion battery diaphragm according to claim 1, wherein the method comprises the following steps: 10 ml of 4, 4-diaminodiphenyl ether, 45 ml of N, N-dimethylformamide, 10 mmol of pyromellitic anhydride, 14.2 g of sodium silicate nonahydrate and 182 g of sodium tungstate dihydrate were required for each preparation of a sodium ion battery separator.
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| CN102460787A (en) * | 2009-06-17 | 2012-05-16 | 索尼公司 | Nonaqueous electrolyte battery, positive electrode for nonaqueous electrolyte battery, negative electrode for nonaqueous electrolyte battery, separator for nonaqueous electrolyte battery, electrolyte for nonaqueous electrolyte battery, and method for |
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