CN114447522B - Polyurethane diaphragm and preparation method and application thereof - Google Patents
Polyurethane diaphragm and preparation method and application thereof Download PDFInfo
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- CN114447522B CN114447522B CN202111653476.1A CN202111653476A CN114447522B CN 114447522 B CN114447522 B CN 114447522B CN 202111653476 A CN202111653476 A CN 202111653476A CN 114447522 B CN114447522 B CN 114447522B
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 42
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 30
- 239000004970 Chain extender Substances 0.000 claims abstract description 28
- -1 ester polyol Chemical class 0.000 claims abstract description 28
- 239000012948 isocyanate Substances 0.000 claims abstract description 28
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 26
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 26
- 229920005862 polyol Polymers 0.000 claims abstract description 26
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 26
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 24
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 238000009987 spinning Methods 0.000 claims description 47
- 239000007788 liquid Substances 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 29
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 23
- 229910001416 lithium ion Inorganic materials 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 11
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 3
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 claims description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043276 diisopropanolamine Drugs 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims 1
- 238000001523 electrospinning Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052744 lithium Inorganic materials 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 description 31
- 239000003792 electrolyte Substances 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000012528 membrane Substances 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011244 liquid electrolyte Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000013508 migration Methods 0.000 description 6
- 230000005012 migration Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000013638 trimer Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 3
- 238000005303 weighing Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the field of lithium battery materials, and discloses a polyurethane diaphragm and a preparation method and application thereof. The polyurethane diaphragm is prepared from isocyanate, rosin ester polyol, a chain extender, a catalyst, silicon dioxide and an organic solvent in a specific proportion, and is prepared through electrostatic spinning. The raw materials used in the invention are easy to obtain, the synthesis operation is simple, and the method is suitable for industrial production and application.
Description
Technical Field
The invention belongs to the field of lithium battery materials, and relates to a polyurethane diaphragm and a preparation method and application thereof.
Background
The lithium ion battery is the most widely used battery in digital products such as mobile phones, notebook computers and the like at present, and comprises a positive electrode, a diaphragm, a negative electrode and electrolyte. The existing lithium ion battery diaphragm is mainly an imported celgar diaphragm, and has the problems that the imported is monopoly and the like; in addition, the existing separator has the problems of poor electrolyte affinity and wettability and low porosity. Therefore, the absorption and retention capacity of the diaphragm to the liquid electrolyte is poor, and the conventional lithium ion battery diaphragm has the problems of insufficient ion conductivity, low migration number of lithium ions and the like in the ether electrolyte, so that the performance of the lithium ion battery is seriously affected.
Disclosure of Invention
The invention provides a polyurethane diaphragm, a preparation method and application thereof, and solves the problems that the lithium ion diaphragm has lower ionic conductivity in ether electrolyte and the like, so that the ionic conductivity is improved; the second technical problem to be solved is that the liquid absorption rate and the liquid retention rate of the lithium ion diaphragm are poor, and the like, so that the liquid absorption rate and the liquid retention rate of the lithium ion diaphragm are improved; the third technical problem to be solved is to solve the problem of low migration number of lithium ions and the like, and to improve the migration number of lithium ions.
The technical scheme of the invention is as follows:
the polyurethane diaphragm comprises the following raw materials in parts by weight:
200-800 parts of isocyanate and the like,
50-250 Parts of rosin ester polyol,
5-20 Parts of a catalyst,
1-50 Parts of chain extender,
10-35 Parts of silicon dioxide,
3000-8000 Parts of organic solvent.
Preferably, the polyurethane diaphragm comprises the following raw materials in parts by weight:
400-700 parts of isocyanate and the like,
100-200 Parts of rosin ester polyol,
10-20 Parts of a catalyst,
5-20 Parts of chain extender,
15-30 Parts of silicon dioxide,
4000-7000 Parts of organic solvent.
Preferably, the chain extender is a trialkanolamine.
Preferably, the ternary alcohol amine is one or more than two of triethanolamine, ethanol diisopropanolamine, diethanol monoisopropanolamine and triisopropanolamine.
Preferably, the silicon dioxide is nano-scale fumed silica with the particle size of 15-20nm; the catalyst is one or more than two of dibutyl tin dilaurate, dibutyl tin dichloride and stannous octoate; the solvent is one of Dimethylformamide (DMF), toluene, ethyl acetate and tetrahydrofuran; the isocyanate is one or more of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene Diisocyanate (HDI) and Lysine Diisocyanate (LDI).
The preparation method of the polyurethane diaphragm comprises the following steps:
(1) Vacuum dehydrating rosin ester polyol and a chain extender; after the air is exhausted by introducing protective gas, the raw materials are mixed with part of organic solvent, and the mixture is subjected to first rotary dispersion at 80+/-20 ℃; then dropwise adding isocyanate for second rotary dispersion, and finally dropwise adding a catalyst for third rotary dispersion to obtain a solution A;
(2) Adding silicon dioxide into the residual organic solvent, stirring, and performing ultrasonic dispersion to obtain uniformly dispersed silicon dioxide dispersion liquid, namely liquid B;
(3) Mixing the A, B solutions, uniformly stirring to obtain a spinning solution, and carrying out electrostatic spinning to obtain an electrostatic spinning diaphragm;
(4) And carrying out vacuum drying on the electrostatic spinning diaphragm, and annealing to obtain the polyurethane diaphragm.
Preferably, the specific steps of the electrostatic spinning are as follows: the distance from the ejector to the tinfoil is adjusted to 15+/-3 cm, parameters of a spinning machine are set, the injection flow rate of the spinning solution is 0.7+/-0.2 uL/min, the rotating speed of the roller is 500+/-200 r/min, the humidity is 30+/-5% RH, and a spinning origin point is set to be positioned at a position above the roller and far to the left; the uniformity of the diaphragm is ensured at ordinary times between the roller and the edge of the device before starting, and the applied voltage is set to 17+/-3 KV and the spinning is carried out at 60+/-10 ℃.
Preferably, the rotation speed of the first and second rotation dispersion in the step (1) is 800+/-200 rpm for 30+/-10 min; the rotation speed of the third rotation dispersion is 600+/-200 rpm, and the time is 60+/-20 min.
Preferably, the stirring conditions in step (2) are: stirring at 8000.+ -. 2000rpm for 1.+ -. 0.5h.
Preferably, the vacuum drying condition in the step (4) is that the vacuum drying is carried out at 60+/-10 ℃ for 24+/-6 hours; the annealing conditions are as follows: annealing at 70+ -10deg.C for 24+ -6 hours.
The polyurethane diaphragm is prepared from isocyanate, rosin ester polyol, a chain extender, a catalyst, silicon dioxide and a solvent in a specific ratio, and is prepared by an electrostatic spinning method.
Compared with the prior art, the invention has the following beneficial effects:
(1) The lithium ion battery prepared by the polyurethane diaphragm has higher ionic conductivity (more than 10 -3 S/cm) in ether electrolyte and higher lithium ion migration number (more than 0.56).
(2) The polyurethane diaphragm has higher liquid absorption rate (more than 1080 percent) and liquid retention rate.
(3) The raw materials used in the invention are easy to obtain, the synthesis operation is simple, and the method is suitable for industrial production and application.
Drawings
FIGS. 1 (a) and (b) are electron microscope scans at different magnifications of the polyurethane separator prepared in comparative example 2; (c) And (d) electron microscopic scans of different magnifications of the polyurethane diaphragm prepared in example 1.
Fig. 2 is a graph showing the rate performance at 0.1C to 2C of lithium batteries prepared in the present invention using example 1, example 4, comparative example 1 and comparative example 2, respectively.
FIG. 3 is a graph showing the long cycle performance at 0.2mA cm -2 of lithium batteries of the present invention using the polyurethane separators of example 1, example 4, comparative example 1 and comparative example 2, respectively.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but embodiments of the present invention are not limited thereto, and may be performed with reference to conventional techniques for process parameters that are not specifically noted.
Example 1
The embodiment provides a polyurethane diaphragm, which is prepared from the following raw materials in parts by weight: 400 parts of isocyanate, 100 parts of rosin ester polyol, 5 parts of chain extender, 10 parts of catalyst, 15 parts of silicon dioxide and 4613 parts of solvent, wherein the isocyanate is TDI trimer and is purchased from Korschun; rosin ester polyol with a hydroxyl number of 400, available from Jurong Ningwu chemical company, jiangsu province; the silicon dioxide is nano-grade gas phase silicon dioxide, the grain diameter is 15-20nm, and the catalyst is dibutyl tin dilaurate; the chain extender is triethanolamine; the solvent was DMF.
The preparation method of the polyurethane diaphragm comprises the following steps:
(1) Into a three-necked flask, 100 parts of rosin ester polyol, 5 parts of chain extender and vacuum dehydration at 110℃and 800rpm were put.
(2) The temperature of the materials is reduced to 80 ℃, nitrogen is introduced to discharge air, 713 parts of solvent is added, and the materials are dispersed for 30 minutes at 800 rpm; 400 parts of isocyanate is added by a constant pressure dropwise adding method, and after dispersing for 30 minutes at a speed of 800rpm, 10 parts of catalyst is added dropwise, and then dispersing reaction is carried out for 1 hour at a speed of 600rpm to obtain solution A.
(3) 15 Parts of silica are weighed into 3900 parts of solvent and the reagent bottle is placed in a constant temperature magnetic stirrer and stirred for 1h at 8000 rpm. And (3) carrying out ultrasonic treatment for 3 hours under a numerical control ultrasonic cleaner to obtain a silica dispersion liquid B liquid which is uniformly dispersed.
(4) Mixing the AB liquid, stirring at room temperature for 30 minutes at 800 revolutions to obtain a spinning liquid, taking the spinning liquid, injecting the spinning liquid into an electrostatic spinning machine, and adjusting the distance from an ejector to the tinfoil to be 15cm. Setting parameters of a spinning machine, injecting a spinning solution at a flow rate of 0.7uL/min, rotating a roller at a speed of 500r/min and humidity of 30% RH, and setting a spinning origin to be positioned at a position above the roller and far to the left. The uniformity of the diaphragm is ensured at ordinary times between the roller and the edge of the device before starting. The applied voltage was set at 17KV and spinning was performed at 60 ℃.
(5) And (3) placing the prepared electrostatic spinning diaphragm at 60 ℃, drying for 24 hours in a vacuum drying oven, and removing redundant solvent and moisture. The prepared membrane is cut into small discs with the diameter of 19mm by a tool, and the small discs are put into a 70 ℃ baking oven to be annealed for 24 hours, thus obtaining the polyurethane membrane.
(6) The CR2032 type coin cell was assembled in a dry argon filled glove box (mildrona, super 1200/750/900). The lithium ion battery with the liquid electrolyte is assembled by stacking a positive electrode shell, a positive electrode plate, a diaphragm, electrolyte (DOL-DME LP-001), a lithium sheet, a gasket, an elastic sheet, a negative electrode shell and the like in sequence, and then the assembled button cell battery is packaged by an MSK-T10 sealing machine.
Example 2
The embodiment provides a polyurethane diaphragm, which is prepared from the following raw materials in parts by weight: 400 parts of isocyanate, 100 parts of rosin ester polyol, 5 parts of chain extender, 10 parts of catalyst, 30 parts of silicon dioxide and 4613 parts of solvent, wherein the isocyanate is TDI trimer and is purchased from Korschun; rosin ester polyol with a hydroxyl number of 400 is purchased from Jurong Ningwu chemical company of Jiangsu province; the silicon dioxide is nano-grade gas phase silicon dioxide, the grain diameter is 15-20nm, and the catalyst is dibutyl tin dilaurate; the chain extender is triethanolamine; the solvent was DMF.
The preparation method of the polyurethane diaphragm comprises the following steps:
(1) Into a three-necked flask, 100 parts of rosin ester polyol, 5 parts of chain extender and vacuum dehydration at 110℃and 800rpm were carried out for 4 hours.
(2) The temperature of the materials is reduced to 80 ℃, nitrogen is introduced to discharge air, 713 parts of solvent is added, and the materials are dispersed for 30 minutes at the speed of 800 rpm; 400 parts of isocyanate is added by a constant pressure dropwise adding method, and after dispersing for 30 minutes at a speed of 800rpm, 10 parts of catalyst is added dropwise, and then dispersing reaction is carried out for 1 hour at a speed of 600rpm to obtain solution A.
(3) 30 Parts of silica are weighed into 3900 parts of solvent, and the reagent bottle is placed in a constant temperature magnetic stirrer and stirred for 1h at 8000 rpm. And (3) carrying out ultrasonic treatment for 3 hours under a numerical control ultrasonic cleaner to obtain a silica dispersion liquid B liquid which is uniformly dispersed.
(4) Mixing the AB liquid with each other, stirring at room temperature for 30 minutes at 800 r.t. to obtain spinning solution, taking the spinning solution, injecting into an electrostatic spinning machine, and adjusting the distance from an ejector to the tinfoil to be 15cm. Setting parameters of a spinning machine, injecting a spinning solution at a flow rate of 0.7uL/min, rotating a roller at a speed of 500r/min and humidity of 30% RH, and setting a spinning origin to be positioned at a position above the roller and far to the left. The uniformity of the diaphragm is ensured at ordinary times between the roller and the edge of the device before starting. The applied voltage was set at 17KV and spinning was performed at 60 ℃.
(5) And (3) placing the prepared electrostatic spinning diaphragm at 60 ℃, drying for 24 hours in a vacuum drying oven, and removing redundant solvent and moisture. The prepared membrane is cut into small discs with the diameter of 19mm by a tool, and the small discs are put into a 70 ℃ baking oven to be annealed for 24 hours, thus obtaining the polyurethane membrane.
(6) The CR2032 type coin cell was assembled in a dry argon filled glove box (mildrona, super 1200/750/900). The lithium ion battery with the liquid electrolyte is assembled by stacking a positive electrode shell, a positive electrode plate, a diaphragm, electrolyte (DOL-DME LP-001), a lithium sheet, a gasket, an elastic sheet, a negative electrode shell and the like in sequence, and then the assembled button cell battery is packaged by an MSK-T10 sealing machine.
Example 3
The embodiment provides a polyurethane diaphragm, which is prepared from the following raw materials in parts by weight: 470 parts of isocyanate, 100 parts of rosin ester polyol, 10 parts of chain extender, 10 parts of catalyst, 15 parts of silicon dioxide and 5243 parts of solvent, wherein the isocyanate is TDI trimer and is purchased from Korschun; rosin ester polyol with a hydroxyl number of 400 is purchased from Jurong Ningwu chemical company of Jiangsu province; the silicon dioxide is nano-grade gas phase silicon dioxide, the grain diameter is 15-20nm, and the catalyst is dibutyl tin dilaurate; the chain extender is triethanolamine; the solvent was DMF.
The preparation method of the polyurethane diaphragm comprises the following steps:
(1) Into a three-necked flask, 100 parts of rosin ester polyol, 10 parts of chain extender and vacuum dehydration at 110℃and 800rpm were carried out for 4 hours.
(2) The temperature of the materials is reduced to 80 ℃, nitrogen is introduced to discharge air, 743 parts of solvent is added, and the materials are dispersed for 30 minutes at the speed of 800 rpm; 470 parts of isocyanate is added by a constant pressure dropwise adding method, dispersed for 30 minutes at a speed of 800rpm, 10 parts of catalyst is added dropwise, and the dispersion reaction is carried out for 1 hour at a speed of 600rpm to obtain solution A.
(3) 15 Parts of silica are weighed into 4500 parts of solvent, the reagent bottle is placed in a constant temperature magnetic stirrer and stirred for 1h at 8000 rpm. And (3) carrying out ultrasonic treatment for 3 hours under a numerical control ultrasonic cleaner to obtain a silica dispersion liquid B liquid which is uniformly dispersed.
(4) Mixing the AB liquid with each other, stirring at room temperature for 30 minutes at 800 r.t. to obtain spinning solution, taking the spinning solution, injecting into an electrostatic spinning machine, and adjusting the distance from an ejector to the tinfoil to be 15cm. Setting parameters of a spinning machine, injecting a spinning solution at a flow rate of 0.7uL/min, rotating a roller at a speed of 500r/min and humidity of 30% RH, and setting a spinning origin to be positioned at a position above the roller and far to the left. The uniformity of the diaphragm is ensured at ordinary times between the roller and the edge of the device before starting. The applied voltage was set at 17KV and spinning was performed at 60 ℃.
(5) And (3) placing the prepared electrostatic spinning diaphragm at 60 ℃, drying for 24 hours in a vacuum drying oven, and removing redundant solvent and moisture. The prepared membrane is cut into small discs with the diameter of 19mm by a tool, and the small discs are put into a 70 ℃ baking oven to be annealed for 24 hours, thus obtaining the polyurethane membrane.
(6) The CR2032 type coin cell was assembled in a dry argon filled glove box (mildrona, super 1200/750/900). The lithium ion battery with the liquid electrolyte is assembled by stacking a positive electrode shell, a positive electrode plate, a diaphragm, electrolyte (DOL-DME LP-001), a lithium sheet, a gasket, an elastic sheet, a negative electrode shell and the like in sequence, and then the assembled button cell battery is packaged by an MSK-T10 sealing machine.
Example 4
The embodiment provides a polyurethane diaphragm, which is prepared from the following raw materials in parts by weight: 540 parts of isocyanate, 100 parts of rosin ester polyol, 15 parts of chain extender, 10 parts of catalyst, 15 parts of silicon dioxide and 6000 parts of solvent, wherein the isocyanate is TDI trimer and is purchased from Korschun; rosin ester polyol with a hydroxyl number of 400 is purchased from Jurong Ningwu chemical company of Jiangsu province; the silicon dioxide is nano-grade gas phase silicon dioxide, the grain diameter is 15-20nm, and the catalyst is dibutyl tin dilaurate; the chain extender is triethanolamine; the solvent was DMF.
The preparation method of the polyurethane diaphragm comprises the following steps:
(1) Into a three-necked flask, 100 parts of rosin ester polyol, 15 parts of chain extender and vacuum dehydration at 110℃and 800rpm were carried out for 4 hours.
(2) The temperature of the materials is reduced to 80 ℃, nitrogen is introduced to discharge air, 800 parts of solvent is added, and the materials are dispersed for 30 minutes at the speed of 800 rpm; 540 parts of isocyanate are added by a constant pressure dropwise adding method, dispersed for 30 minutes at a speed of 800rpm, 10 parts of catalyst are added dropwise, and the dispersion reaction is carried out for 1 hour at a speed of 600rpm to obtain solution A.
(3) 15 Parts of silica are weighed into 5200 parts of solvent, and the reagent bottle is placed into a constant temperature magnetic stirrer for stirring for 1h at 8000 rpm. And (3) carrying out ultrasonic treatment for 3 hours under a numerical control ultrasonic cleaner to obtain a silica dispersion liquid B liquid which is uniformly dispersed.
(4) Mixing the AB liquid with each other, stirring at room temperature for 30 minutes at 800 r.t. to obtain spinning solution, taking the spinning solution, injecting into an electrostatic spinning machine, and adjusting the distance from an ejector to the tinfoil to be 15cm. Setting parameters of a spinning machine, injecting a spinning solution at a flow rate of 0.7uL/min, rotating a roller at a speed of 500r/min and humidity of 30% RH, and setting a spinning origin to be positioned at a position above the roller and far to the left. The uniformity of the diaphragm is ensured at ordinary times between the roller and the edge of the device before starting. The applied voltage was set at 17KV and spinning was performed at 60 ℃.
(5) And (3) placing the prepared electrostatic spinning diaphragm at 60 ℃, drying for 24 hours in a vacuum drying oven, and removing redundant solvent and moisture. The prepared membrane is cut into small discs with the diameter of 19mm by a tool, and the small discs are put into a 70 ℃ baking oven to be annealed for 24 hours, thus obtaining the polyurethane membrane.
(6) The CR2032 type coin cell was assembled in a dry argon filled glove box (mildrona, super 1200/750/900). The lithium ion battery with the liquid electrolyte is assembled by stacking a positive electrode shell, a positive electrode plate, a diaphragm, electrolyte (DOL-DME LP-001), a lithium sheet, a gasket, an elastic sheet, a negative electrode shell and the like in sequence, and then the assembled button cell battery is packaged by an MSK-T10 sealing machine.
Example 5
The embodiment provides a polyurethane diaphragm, which is prepared from the following raw materials in parts by weight: 610 parts of isocyanate, 100 parts of rosin ester polyol, 20 parts of chain extender, 10 parts of catalyst, 15 parts of silicon dioxide and 6632 parts of solvent, wherein the isocyanate is TDI trimer and is purchased from Korschun; rosin ester polyol with a hydroxyl number of 400 is purchased from Jurong Ningwu chemical company of Jiangsu province; the silicon dioxide is nano-grade gas phase silicon dioxide, the grain diameter is 15-20nm, and the catalyst is dibutyl tin dilaurate; the chain extender is triethanolamine; the solvent was DMF.
The preparation method of the polyurethane diaphragm comprises the following steps:
(1) Into a three-necked flask, 100 parts of rosin ester polyol and 20 parts of chain extender were charged, and the mixture was dehydrated in vacuo at 110℃and a rotational speed of 800rpm for 4 hours.
(2) The temperature of the materials is reduced to 80 ℃, nitrogen is introduced to discharge air, 832 parts of solvent is added, and the materials are dispersed for 30 minutes at the speed of 800 rpm; 610 parts of isocyanate are added by a constant pressure dropwise adding method, dispersed for 30 minutes at a speed of 800rpm, 10 parts of catalyst are added dropwise, and the dispersion reaction is carried out for 1 hour at a speed of 600rpm to obtain solution A.
(3) 15 Parts of silica are weighed into 5800 parts of solvent, and the reagent bottle is placed into a constant temperature magnetic stirrer for stirring for 1h at 8000 rpm. And (3) carrying out ultrasonic treatment for 3 hours under a numerical control ultrasonic cleaner to obtain a silica dispersion liquid B liquid which is uniformly dispersed.
(4) Mixing the AB liquid with each other, stirring at room temperature for 30 minutes at 800 r.t. to obtain spinning solution, taking the spinning solution, injecting into an electrostatic spinning machine, and adjusting the distance from an ejector to the tinfoil to be 15cm. Setting parameters of a spinning machine, injecting a spinning solution at a flow rate of 0.7uL/min, rotating a roller at a speed of 500r/min and humidity of 30% RH, and setting a spinning origin to be positioned at a position above the roller and far to the left. The uniformity of the diaphragm is ensured at ordinary times between the roller and the edge of the device before starting. The applied voltage was set at 17KV and spinning was performed at 60 ℃.
(5) And (3) placing the prepared electrostatic spinning diaphragm at 60 ℃, drying for 24 hours in a vacuum drying oven, and removing redundant solvent and moisture. The prepared membrane is cut into small discs with the diameter of 19mm by a tool, and the small discs are put into a 70 ℃ baking oven to be annealed for 24 hours, thus obtaining the polyurethane membrane.
(6) The CR2032 type coin cell was assembled in a dry argon filled glove box (mildrona, super 1200/750/900). The lithium ion battery with the liquid electrolyte is assembled by stacking a positive electrode shell, a positive electrode plate, a diaphragm, electrolyte (DOL-DME LP-001), a lithium sheet, a gasket, an elastic sheet, a negative electrode shell and the like in sequence, and then the assembled button cell battery is packaged by an MSK-T10 sealing machine.
Comparative example 1
(1) A commercial PP separator was cut into a 19mm diameter small disc with a tool as comparative example 1.
Comparative example 2
The embodiment provides a polyurethane diaphragm, which is prepared from the following raw materials in parts by weight: 610 parts of isocyanate, 100 parts of rosin ester polyol, 20 parts of chain extender and 6700 parts of solvent, wherein the isocyanate is TDI trimer purchased from Korschun; rosin ester polyol with a hydroxyl number of 400 is purchased from Jurong Ningwu chemical company of Jiangsu province; the catalyst is dibutyl tin dilaurate; the chain extender is triethanolamine; the solvent was DMF.
The preparation method of the polyurethane diaphragm comprises the following steps:
(1) Into a three-necked flask, 100 parts of rosin ester polyol and 20 parts of chain extender were charged, and the mixture was dehydrated in vacuo at 110℃and a rotational speed of 800rpm for 4 hours.
(2) The temperature of the materials is reduced to 80 ℃, nitrogen is introduced to discharge air, 4600 parts of solvent is added, and the materials are dispersed for 30 minutes at the speed of 800 rpm; 610 parts of isocyanate is added by a constant pressure dripping method, dispersed for 30 minutes at a speed of 800rpm, 10 parts of catalyst is added dropwise, and dispersion reaction is carried out for 1 hour at a speed of 600rpm, so that spinning solution is obtained, the spinning solution is taken out, and the distance from an ejector to tinfoil is adjusted to be 15cm. Setting parameters of a spinning machine, injecting a spinning solution at a flow rate of 0.7uL/min, rotating a roller at a speed of 500r/min and humidity of 30% RH, and setting a spinning origin to be positioned at a position above the roller and far to the left. The uniformity of the diaphragm is ensured at ordinary times between the roller and the edge of the device before starting. The applied voltage was set at 17KV and spinning was performed at 60 ℃.
(3) And (3) placing the prepared electrostatic spinning diaphragm at 60 ℃, drying for 24 hours in a vacuum drying oven, and removing redundant solvent and moisture. The prepared membrane is cut into small discs with the diameter of 19mm by a tool, and the small discs are put into a 70 ℃ baking oven to be annealed for 24 hours, thus obtaining the polyurethane membrane.
(4) The CR2032 type coin cell was assembled in a dry argon filled glove box (mildrona, super 1200/750/900). The lithium ion battery with the liquid electrolyte is assembled by stacking a positive electrode shell, a positive electrode plate, a diaphragm, electrolyte (DOL-DME LP-001), a lithium sheet, a gasket, an elastic sheet, a negative electrode shell and the like in sequence, and then the assembled button cell battery is packaged by an MSK-T10 sealing machine.
For lithium ion battery separators, the liquid absorption capacity of the electrolyte is required to be high. Mainly due to the fact that the high liquid absorption rate can directly influence the ion conduction speed and reduce the impedance problem between interfaces. The test method is generally as follows: firstly, weighing the mass of the diaphragm before the diaphragm is not soaked in electrolyte, and marking the mass as W 0; then soaking the diaphragm in the electrolyte for 24 hours, taking out, removing the electrolyte on the surface of the diaphragm by using a clean filter paper sheet, and weighing the mass of the diaphragm, and recording as W 1; the liquid absorption of the lithium ion battery separator was calculated by the following formula, and the results are shown in table 1.
Liquid absorption (%) = (W) 1-W0)/W0
Table 1 results of liquid absorption test
Meanwhile, the test results of the ionic conductivity and the lithium ion migration number are shown in tables 2 and 3 below.
TABLE 2 ion conductivity test results
TABLE 3 lithium ion migration number test results
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the polyurethane diaphragm is characterized by comprising the following steps of:
(1) Vacuum dehydrating rosin ester polyol and chain extender; after the air is exhausted by introducing protective gas, the raw materials are mixed with part of organic solvent, and the mixture is subjected to first rotary dispersion at 80+/-20 ℃; then dropwise adding isocyanate, and performing second rotation dispersion; finally, adding a catalyst dropwise, and performing third rotation dispersion to obtain a solution A;
(2) Adding silicon dioxide into the residual organic solvent, stirring, and performing ultrasonic dispersion to obtain uniformly dispersed silicon dioxide dispersion liquid, namely liquid B;
(3) Mixing the A, B solutions, uniformly stirring to obtain a spinning solution, and carrying out electrostatic spinning to obtain an electrostatic spinning diaphragm;
(4) Vacuum drying is carried out on the electrostatic spinning diaphragm, and then annealing is carried out, so that the polyurethane diaphragm is obtained;
the raw materials in parts by weight are:
200-800 parts of isocyanate and the like,
50-250 Parts of rosin ester polyol,
5-20 Parts of a catalyst,
1-50 Parts of chain extender,
10-35 Parts of silicon dioxide,
3000-8000 Parts of organic solvent,
The catalyst is one or more than two of dibutyl tin dilaurate, dibutyl tin dichloride and stannous octoate; the organic solvent is one of dimethylformamide, toluene, ethyl acetate and tetrahydrofuran; the isocyanate is one or more than two of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.
2. The method for preparing the polyurethane diaphragm according to claim 1, wherein the raw materials in parts by weight are:
400-700 parts of isocyanate and the like,
100-200 Parts of rosin ester polyol,
10-20 Parts of a catalyst,
5-20 Parts of chain extender,
15-30 Parts of silicon dioxide,
4000-7000 Parts of organic solvent.
3. The method for producing a polyurethane separator according to claim 2, wherein the chain extender is a trialkanolamine.
4. The method for producing a polyurethane separator according to claim 3, wherein the ternary alcohol amine is one or more of triethanolamine, ethanol diisopropanolamine, diethanol monoisopropanolamine and triisopropanolamine.
5. The method for producing a polyurethane separator according to claim 1 or 2 or 3 or 4, wherein the silica is a nanoscale fumed silica having a particle diameter of 15 to 20nm.
6. The preparation method according to claim 5, wherein the specific steps of electrospinning are as follows: the distance from the ejector to the tinfoil is adjusted to 15+/-3 cm, parameters of a spinning machine are set, the injection flow rate of the spinning solution is 0.7+/-0.2 uL/min, the rotating speed of the roller is 500+/-200 r/min, the humidity is 30+/-5% RH, and a spinning origin point is set at a position above the roller to the left; the uniformity of the diaphragm is ensured at ordinary times between the roller and the edge of the device before starting, and the applied voltage is set to 17+/-3 KV and the spinning is carried out at 60+/-10 ℃.
7. The method according to claim 6, wherein the rotational speed of the first and second rotational dispersions in step (1) is 800.+ -. 200rpm for 30.+ -. 10min; the rotation speed of the third rotation dispersion is 600+/-200 rpm, and the time is 60+/-20 min; the stirring conditions in the step (2) are as follows: stirring at 8000.+ -. 2000rpm is carried out at 1.+ -. 0.5 h.
8. The method according to claim 7, wherein the vacuum drying condition in the step (4) is that the drying is performed at 60+ -10deg.C for 24+ -6 h; the annealing conditions are as follows: annealing at 70+ -10deg.C for 24+ -6 hours.
9. The polyurethane separator manufactured by the method according to any one of claims 1 to 8.
10. Use of the polyurethane separator of claim 9 in the preparation of lithium ion batteries.
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| CN109065816A (en) * | 2018-08-14 | 2018-12-21 | 湘潭大学 | A kind of polyurethane-nano material composite diaphragm and Preparation method and use |
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| CN111081954A (en) * | 2019-11-22 | 2020-04-28 | 东莞东阳光科研发有限公司 | Diaphragm coating slurry, diaphragm and preparation method thereof |
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