CN114204210A - Preparation method of novel sodium-ion battery diaphragm - Google Patents
Preparation method of novel sodium-ion battery diaphragm Download PDFInfo
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- CN114204210A CN114204210A CN202111305119.6A CN202111305119A CN114204210A CN 114204210 A CN114204210 A CN 114204210A CN 202111305119 A CN202111305119 A CN 202111305119A CN 114204210 A CN114204210 A CN 114204210A
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- sodium
- ion battery
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- diaphragm
- acid
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 58
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 21
- 229920000768 polyamine Polymers 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims description 53
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- 229910052708 sodium Inorganic materials 0.000 claims description 27
- 239000011734 sodium Substances 0.000 claims description 27
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 26
- 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 25
- 230000015572 biosynthetic process Effects 0.000 claims description 24
- 238000003786 synthesis reaction Methods 0.000 claims description 24
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 20
- 230000002194 synthesizing effect Effects 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
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound 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 claims description 18
- 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 17
- 238000000034 method Methods 0.000 claims description 16
- 239000002244 precipitate Substances 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 14
- 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 13
- 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 13
- 239000011780 sodium chloride Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 8
- 229920000805 Polyaspartic acid Polymers 0.000 claims description 7
- 235000019270 ammonium chloride Nutrition 0.000 claims description 7
- 108010064470 polyaspartate Proteins 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 4
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- -1 amine salt Chemical class 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- WNUPENMBHHEARK-UHFFFAOYSA-N silicon tungsten Chemical compound [Si].[W] WNUPENMBHHEARK-UHFFFAOYSA-N 0.000 abstract description 9
- 239000011964 heteropoly acid Substances 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 7
- 159000000000 sodium salts Chemical class 0.000 abstract description 7
- 125000004018 acid anhydride group Chemical group 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 125000003277 amino group Chemical group 0.000 abstract description 2
- 238000009413 insulation Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 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
- 150000003839 salts Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 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
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 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
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 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
- 238000005406 washing Methods 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
Abstract
The invention discloses a preparation method of a novel sodium ion battery diaphragm, which relates to the technical field of lithium ion batteries, wherein an acid anhydride group is arranged on the surface of a polyamine acid molecular chain by controlling a functional group at the tail end of the polyamine acid molecular chain, and the silicon tungsten heteropoly acid amine salt reacts with the polyamine acid through an amino group on the surface to reduce the dielectric constant of the diaphragm, so that the diaphragm has better insulation property, sodium ions in the silicon tungsten heteropoly acid sodium salt can be transmitted in porous nano ions of the diaphragm, and the ion conduction property of the diaphragm is improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of a novel sodium ion battery diaphragm.
Background
A Sodium-ion battery (Sodium-ion battery), which is a secondary battery (rechargeable battery), mainly depends on the movement of Sodium ions between a positive electrode and a negative electrode to work, and is similar to the working principle of a lithium ion battery.
Compared with lithium ion batteries, sodium ion batteries have the following advantages: (1) the sodium salt raw material has abundant reserves and low price, and compared with the ternary cathode material of the lithium ion battery, the adopted ferro-manganese nickel-based cathode material has half of the raw material cost; (2) due to the characteristics of sodium salt, the low-concentration electrolyte (the electrolyte with the same concentration and the sodium salt conductivity higher than that of the lithium electrolyte by about 20%) is allowed to be used, so that the cost is reduced; (3) sodium ions do not form an 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 no over-discharge characteristics. The energy density of the sodium ion battery is more than 100Wh/kg, and the sodium ion battery can be compared with a lithium iron phosphate battery, but the cost advantage is obvious, and the sodium ion battery 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, along with the trend that the price of raw materials of the lithium ion battery rises more and more seriously, the sodium ion battery is more and more concerned by the battery field due to the cost advantage of the sodium ion battery. However, sodium ion batteries are less popular in research than lithium ion batteries, and the industrial chain is not mature, so that all main materials are in the research and development stage. The sodium ion battery diaphragm is one of the key links, the diaphragm used by the power and energy storage battery is required to have more excellent high-temperature resistance besides the basic performance of the common diaphragm, and a plurality of battery manufacturers require the diaphragm to have the high-temperature thermal shrinkage performance of 150 ℃. In the conventional polyolefin diaphragm, the melting point of the polyethylene diaphragm is 130 ℃, and the diaphragm can be fused when the melting point is exceeded; whereas polypropylene has a melting point of 163 ℃ and will shrink by more than 30% when the temperature reaches 150 ℃. Therefore, the traditional polyolefin diaphragm can not meet the requirements of a power lithium battery, and the traditional polyolefin diaphragm has poor liquid absorption and liquid retention properties, so that the internal resistance of the battery is increased.
The Polyimide (PI) material has good thermal stability, chemical stability and outstanding mechanical property, the long-term service temperature can reach 300 ℃, and the PI material is a film type insulating material with the best comprehensive performance at present. Compared with polyolefin separators, PI has a polar group and thus has better lithium ion electrolyte affinity, and is therefore considered as a next-generation lithium ion battery separator material. Similarly, the silicon-tungsten heteropoly acid salt is an inorganic porous nano ion and can obviously improve the performance of the material when being used as a building block in the field of synthesizing organic-inorganic nano composite materials. Therefore, if the two materials can be applied to the separator of the sodium-ion battery, the excellent effect is brought.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a novel sodium ion battery diaphragm, which has better insulating property by controlling a functional group at the tail end of a polyamine acid molecular chain to enable the surface of the polyamine acid molecular chain to have an acid anhydride group and reducing the dielectric constant of the diaphragm through the reaction of amino on the surface of the polyamine silicon tungsten acid with the polyamine acid, and sodium ions in the sodium salt of the heteropoly silicon tungsten acid can be transmitted in porous nano ions of the sodium ion battery diaphragm, so that the ion conducting property of the diaphragm is improved.
The invention provides a preparation method of a novel sodium-ion battery diaphragm, which comprises the following steps:
a step of synthesizing polyaspartic acid, which is to add 4, 4-diaminodiphenyl ether into a three-necked flask at room temperature, add N, N-dimethylformamide into the 4, 4-diaminodiphenyl ether under the nitrogen atmosphere for dissolving and mixing to prepare a mixed solution, and then add pyromellitic dianhydride into the mixed solution for three times at intervals of fixed time;
preferably, in the step of synthesizing the polyamic acid, 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 interval is at least 4 hours.
The method comprises the following steps of (1) synthesizing sodium silicotungstic acid, namely 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, then dropwise adding ammonium chloride to adjust the pH value to be 5-6, then adding sodium chloride to generate a large amount of precipitates, collecting the precipitates, and cleaning the precipitates by using a saturated sodium chloride solution to obtain sodium silicotungstic acid;
and a diaphragm synthesis step, namely adding the ammonium tungstate sodium prepared in the ammonium tungstate sodium synthesis step into the mixed solution added with the pyromellitic anhydride in the polyamine acid synthesis step in the nitrogen atmosphere, reacting at the reaction temperature of 50 ℃ for 12 hours to obtain a solution with viscosity, advecting the solution with viscosity onto a clean glass plate, and drying at the temperature of 80 ℃ for 8 hours in the nitrogen atmosphere to obtain the sodium ion battery diaphragm.
Preferably, in the step of synthesizing the diaphragm, the ammonium tungstate sodium prepared in the step of synthesizing the ammonium tungstate sodium is added according to 10% of the total mass of the mixed solution added with the pyromellitic dianhydride in the step of synthesizing the polyanilic acid.
Furthermore, in the diaphragm synthesis step, the area of the solution with viscosity flowing onto a clean glass plate is required to be 10-20um thick after being dried.
Further, for each one sheet of the 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 step of synthesizing the ammonium silicotungstic acid sodium, 14.2 g of sodium silicate nonahydrate is added into every 100 ml of deionized water in the solution I, and 182 g of sodium tungstate dihydrate is added into every 300 ml of deionized water in the solution II.
More preferably, in each step of preparing a sodium ion battery diaphragm, in the step of synthesizing the ammonium silicotungstic acid, 180 ml of ammonium chloride is required to be dripped after the solution I and the solution II are stirred and mixed to adjust the pH value to be between 5 and 6, and then 100 g of sodium chloride is added for precipitation.
Compared with the prior art, the preparation method of the novel sodium ion battery diaphragm has the advantages that the acid anhydride groups are arranged on the surface of the novel sodium ion battery diaphragm by controlling the functional groups at the tail ends of the polyamine acid molecular chains, at the moment, the silicon tungsten heteropoly acid amine salt reacts with the polyamine acid through the amino groups on the surface to form an organic-inorganic nano composite material connected through covalent bonds, and the silicon tungsten heteropoly acid amine salt can reduce the dielectric constant of the diaphragm, so that the diaphragm has better insulating property; and sodium ions in the silicon-tungsten heteropoly acid sodium salt can be transmitted in the porous nano ions of the silicon-tungsten heteropoly acid sodium salt, so that the ion conducting property of the diaphragm can be improved, the cationic amine radical ions and the sodium ions of the silicon tungstate are simultaneously combined with silicon tungstate anions to form silicon tungstate amine sodium, and the advantages of the two salts are combined to form the novel sodium ion battery diaphragm.
Detailed Description
The technical solutions for achieving the objects of the present invention are further illustrated by the following specific examples, and it should be noted that the technical solutions claimed in the present invention include, but are not limited to, the following examples.
Example 1
The preparation method of the novel sodium-ion battery diaphragm disclosed in the embodiment 1 comprises the following steps:
and a polyaspartic acid synthesis step, namely adding 10 mmol of 4, 4-diaminodiphenyl ether into a three-neck flask at the room temperature of 25 ℃, adding 45 ml of N, N-dimethylformamide under the nitrogen atmosphere, adding 10 mmol of pyromellitic anhydride after the 4, 4-diaminodiphenyl ether is fully dissolved, and adding the pyromellitic anhydride into the solution for three times at intervals of 4 hours.
And (2) a step of synthesizing the ammonium silicotungstic acid sodium, which is to dissolve 14.2 g of sodium silicate nonahydrate into 100 ml of deionized water, dissolve 182 g of sodium tungstate dihydrate into 300 ml of water, mix and intensively stir the sodium silicate nonahydrate and the sodium tungstate dihydrate, dropwise add 180 ml of ammonium chloride, adjust the pH value to be between 5 and 6, slightly stir the mixture, add 100 g of sodium chloride to generate a large amount of precipitates, collect the precipitates, and wash the precipitates with sodium chloride to obtain the product, namely the ammonium silicotungstic acid sodium.
And a diaphragm synthesis step, namely after the solution in the polyamine acid synthesis step is completely reacted, adding ammonium silicotungstic acid sodium with the total mass of 10% of the solution into the solution in a nitrogen atmosphere, keeping the reaction temperature at 50 ℃, reacting for 12 hours, advecting the obtained solution with viscosity onto a clean glass plate, drying the solution at 80 ℃ for 8 hours in the nitrogen atmosphere, and finally obtaining the sodium ion battery diaphragm with the thickness of 10-20 microns.
Example 2
Embodiment 2 discloses a method for preparing a novel sodium ion battery separator, which comprises the following steps:
and a polyaspartic acid synthesis step, namely adding 10 mmol of 4, 4-diaminodiphenyl ether into a three-neck flask at the room temperature of 25 ℃, adding 45 ml of N, N-dimethylformamide under the nitrogen atmosphere, adding 10 mmol of pyromellitic anhydride after the 4, 4-diaminodiphenyl ether is fully dissolved, and adding the pyromellitic anhydride into the solution for three times at intervals of 4 hours.
And (2) a step of synthesizing the ammonium silicotungstic acid sodium, which is to dissolve 14.2 g of sodium silicate nonahydrate into 100 ml of deionized water, dissolve 182 g of sodium tungstate dihydrate into 300 ml of water, mix and intensively stir the sodium silicate nonahydrate and the sodium tungstate dihydrate, dropwise add 2800 ml of ammonium chloride, adjust the pH value to be between 5 and 6, slightly stir the mixture, add 50 g of sodium chloride to generate a large amount of precipitate, collect the precipitate, and wash the precipitate with sodium chloride to obtain the product, namely the ammonium silicotungstic acid sodium.
And a diaphragm synthesis step, namely after the solution in the polyamine acid synthesis step is completely reacted, adding ammonium silicotungstic acid sodium with the total mass of 10% of the solution into the solution in a nitrogen atmosphere, keeping the reaction temperature at 50 ℃, reacting for 12 hours, advecting the obtained solution with viscosity onto a clean glass plate, drying the solution at 80 ℃ for 8 hours in the nitrogen atmosphere, and finally obtaining the sodium ion battery diaphragm with the thickness of 10-20 microns.
Example 3
Embodiment 3 discloses a method for preparing a novel sodium ion battery separator, which comprises the following steps:
and a polyaspartic acid synthesis step, namely adding 10 mmol of 4, 4-diaminodiphenyl ether into a three-neck flask at the room temperature of 25 ℃, adding 45 ml of N, N-dimethylformamide under the nitrogen atmosphere, adding 10 mmol of pyromellitic anhydride after the 4, 4-diaminodiphenyl ether is fully dissolved, and adding the pyromellitic anhydride into the solution for three times at intervals of 4 hours.
And (2) a step of synthesizing the ammonium silicotungstic acid sodium, which is to dissolve 14.2 g of sodium silicate nonahydrate into 100 ml of deionized water, dissolve 182 g of sodium tungstate dihydrate into 300 ml of water, mix and intensively stir the sodium silicate nonahydrate and the sodium tungstate dihydrate, dropwise add 180 ml of ammonium chloride, adjust the pH value to be between 5 and 6, slightly stir the mixture, add 200 g of sodium chloride to generate a large amount of precipitate, collect the precipitate, and wash the precipitate with sodium chloride to obtain the product, namely the ammonium silicotungstic acid sodium.
And a diaphragm synthesis step, namely after the solution in the polyamine acid synthesis step is completely reacted, adding ammonium silicotungstic acid sodium with the total mass of 10% of the solution into the solution in a nitrogen atmosphere, keeping the reaction temperature at 50 ℃, reacting for 12 hours, advecting the obtained solution with viscosity onto a clean glass plate, drying the solution at 80 ℃ for 8 hours in the nitrogen atmosphere, and finally obtaining the sodium ion battery diaphragm with the thickness of 10-20 microns.
Example 4
Embodiment 4 discloses a method for preparing a novel sodium ion battery separator, which comprises the following steps:
and a polyaspartic acid synthesis step, namely adding 10 mmol of 4, 4-diaminodiphenyl ether into a three-neck flask at the room temperature of 25 ℃, adding 45 ml of N, N-dimethylformamide under the nitrogen atmosphere, adding 10 mmol of pyromellitic anhydride after the 4, 4-diaminodiphenyl ether is fully dissolved, and adding the pyromellitic anhydride into the solution for three times at intervals of 4 hours.
And (2) synthesizing sodium silicotungstic acid amine, namely dissolving 14.2 g of sodium silicate nonahydrate in 100 ml of deionized water, dissolving 182 g of sodium tungstate dihydrate in 300 ml of water, strongly stirring, then adjusting the pH value to be between 5 and 6, slightly stirring, adding 100 g of sodium chloride, generating a large amount of precipitates, collecting the precipitates, and washing with the sodium chloride to obtain the product, namely the sodium silicotungstic acid amine.
And a diaphragm synthesis step, namely after the solution in the polyamine acid synthesis step is completely reacted, adding ammonium silicotungstic acid sodium with the total mass of 10% of the solution into the solution in a nitrogen atmosphere, keeping the reaction temperature at 50 ℃, reacting for 12 hours, advecting the obtained solution with viscosity onto a clean glass plate, drying the solution at 80 ℃ for 8 hours in the nitrogen atmosphere, and finally obtaining the sodium ion battery diaphragm with the thickness of 10-20 microns.
Comparative example 1
Comparative example 1 discloses a method for preparing a novel sodium ion battery separator, comprising the following steps:
and a polyaspartic acid synthesis step, namely adding 10 mmol of 4, 4-diaminodiphenyl ether into a three-neck flask at the room temperature of 25 ℃, adding 45 ml of N, N-dimethylformamide under the nitrogen atmosphere, adding 10 mmol of pyromellitic anhydride after the 4, 4-diaminodiphenyl ether is fully dissolved, and adding the pyromellitic anhydride into the solution for three times at intervals of 4 hours.
And a diaphragm synthesis step, after the reaction in the polyamine acid synthesis step is completed, flatly flowing 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 microns.
The sodium ion battery separators prepared in the above examples 1 to 4 and comparative example 1 were tested by the following methods:
1. testing the dielectric constant of the prepared diaphragm;
2. assembling the prepared diaphragm into a battery, and detecting the internal resistance of the prepared battery so as to judge the ionic conductivity of the diaphragm;
the test results can be referred to the following Table 1
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 conventional technical scheme.
Claims (8)
1. A preparation method of a novel sodium-ion battery diaphragm is characterized by comprising the following steps:
a step of synthesizing polyaspartic acid, which is to add 4, 4-diaminodiphenyl ether into a three-necked flask at room temperature, add N, N-dimethylformamide into the 4, 4-diaminodiphenyl ether under the nitrogen atmosphere for dissolving and mixing to prepare a mixed solution, and then add pyromellitic dianhydride into the mixed solution for three times at intervals of fixed time;
the method comprises the following steps of (1) synthesizing sodium silicotungstic acid, namely 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, then dropwise adding ammonium chloride to adjust the pH value to be between 5 and 6, then adding sodium chloride for precipitation, collecting precipitates, and cleaning the precipitates by using a saturated sodium chloride solution to obtain sodium silicotungstic acid;
and a diaphragm synthesis step, namely adding the ammonium tungstate sodium prepared in the ammonium tungstate sodium synthesis step into the mixed solution added with the pyromellitic anhydride in the polyamine acid synthesis step in the nitrogen atmosphere, reacting at the reaction temperature of 50 ℃ for 12 hours to obtain a solution with viscosity, advecting the solution with viscosity onto a clean glass plate, and drying at the temperature of 80 ℃ for 8 hours in the nitrogen atmosphere to obtain the sodium ion battery diaphragm.
2. The method for preparing a novel sodium-ion battery separator as claimed in claim 1, wherein: in the diaphragm synthesis step, the area of a solution with viscosity flowing onto a clean glass plate is horizontally flowed, and the thickness of the sodium ion battery diaphragm prepared after drying is required to be 10-20 um.
3. The method for preparing a novel sodium-ion battery separator as claimed in claim 1, wherein: in the step of synthesizing the diaphragm, the ammonium tungstate sodium prepared in the step of synthesizing the ammonium tungstate sodium is added according to 10% of the total mass of the mixed solution added with the pyromellitic anhydride in the step of synthesizing the polyactic acid.
4. The method for preparing a novel sodium-ion battery separator as claimed in claim 1, wherein: in the synthesis step of the polyamine acid, 450 ml of N, N-dimethylformamide and 100 mmol of pyromellitic anhydride are added to every 100 ml of 4, 4-diaminodiphenyl ether.
5. A method for preparing a novel sodium-ion battery separator as claimed in claim 1 or 3, characterized in that: the interval is fixed for at least 4 hours.
6. The method for preparing a novel sodium-ion battery separator as claimed in claim 3, wherein: further, for each one sheet of the 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.
7. The method for preparing a novel sodium-ion battery separator as claimed in claim 1 or 5, wherein: in the step of synthesizing the ammonium silicotungstic acid sodium, 14.2 g of sodium silicate nonahydrate is added into every 100 ml of deionized water in the solution I, and 182 g of sodium tungstate dihydrate is added into every 300 ml of deionized water in the solution II.
8. The method for preparing a novel sodium-ion battery separator as claimed in claim 6, wherein: in each step of preparing a sodium ion battery diaphragm, in the step of synthesizing the ammonium silicotungstic acid, 180 ml of ammonium chloride is required to be dripped after the solution I and the solution II are stirred and mixed to adjust the pH value to be between 5 and 6, and then 100 g of sodium chloride is added for precipitation.
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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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