CN115626972A - Water-based high-molecular phosphate and preparation method and application thereof - Google Patents
Water-based high-molecular phosphate and preparation method and application thereof Download PDFInfo
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- CN115626972A CN115626972A CN202211383600.1A CN202211383600A CN115626972A CN 115626972 A CN115626972 A CN 115626972A CN 202211383600 A CN202211383600 A CN 202211383600A CN 115626972 A CN115626972 A CN 115626972A
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 73
- 239000010452 phosphate Substances 0.000 title claims abstract description 73
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229920000098 polyolefin Polymers 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 150000002009 diols Chemical class 0.000 claims abstract description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004945 emulsification Methods 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 239000004970 Chain extender Substances 0.000 claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 239000012948 isocyanate Substances 0.000 claims abstract description 7
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 150000002148 esters Chemical group 0.000 claims abstract description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 10
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims description 8
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 8
- 239000003021 water soluble solvent Substances 0.000 claims description 8
- LAVARTIQQDZFNT-UHFFFAOYSA-N 1-(1-methoxypropan-2-yloxy)propan-2-yl acetate Chemical group COCC(C)OCC(C)OC(C)=O LAVARTIQQDZFNT-UHFFFAOYSA-N 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 125000004427 diamine group Chemical group 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 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 5
- HILAULICMJUOLK-UHFFFAOYSA-N 1,3-diethyl-5-methylbenzene Chemical compound CCC1=CC(C)=CC(CC)=C1 HILAULICMJUOLK-UHFFFAOYSA-N 0.000 claims description 4
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 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 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical group NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000005809 transesterification reaction Methods 0.000 claims description 4
- -1 isophthalic acid glycol ester Chemical class 0.000 claims description 3
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- SAMYCKUDTNLASP-UHFFFAOYSA-N hexane-2,2-diol Chemical compound CCCCC(C)(O)O SAMYCKUDTNLASP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229940100573 methylpropanediol Drugs 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 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 2
- 238000000034 method Methods 0.000 claims 9
- 239000007787 solid Substances 0.000 abstract description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 7
- 230000001804 emulsifying effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000007784 solid electrolyte Substances 0.000 description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000000306 component Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- KCLIFOXATBWLMW-UHFFFAOYSA-M sodium;ethane-1,2-diamine;ethanesulfonate Chemical compound [Na+].NCCN.CCS([O-])(=O)=O KCLIFOXATBWLMW-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002203 sulfidic glass Substances 0.000 description 1
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6523—Compounds of group C08G18/3225 or C08G18/3271 or polyamines of C08G18/38
- C08G18/6529—Compounds of group C08G18/3225 or polyamines of C08G18/38
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
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- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
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Abstract
The invention belongs to the technical field of solid-state batteries, and particularly relates to a water-based high-molecular phosphate and a preparation method and application thereof, wherein the preparation method comprises the following steps: s1, performing ester exchange reaction on dimethyl isophthalate-5-phosphate and dihydric alcohol to prepare glycol isophthalate-5-phosphate; s2, carrying out polymerization reaction on isophthalate diol-5-phosphate, hydroxyl-terminated polyolefin diol and/or hydrogenated hydroxyl-terminated polyolefin diol and isocyanate to obtain an isocyanate-terminated oligomer; s3, carrying out polymerization reaction on the isocyanate-terminated oligomer, AAS salt and acetone to obtain a phosphate-containing isocyanate-terminated hydrophilic oligomer; and S4, adding water for emulsification, then adding a chain extender for chain extension, and continuously emulsifying to obtain the water-based high-molecular phosphate. The aqueous high molecular phosphate has high lithium ion content and high activity, and is suitable for preparing (solid) electrolyte of digital batteries or power batteries.
Description
Technical Field
The invention belongs to the technical field of solid-state batteries, and particularly relates to a water-based high-molecular phosphate and a preparation method and application thereof. The water-based polymer phosphate can be applied to digital or power batteries, and is particularly suitable for processing and manufacturing solid-state batteries.
Background
With the ever-increasing demand for energy and the continuous consumption of fossil fuels, the establishment of a sustainable energy solution has become the key to the sustainable development of society. Under the macroscopic background, the development of electrochemical energy storage devices is accelerated by the construction of new energy automobiles and smart grids, and the most urgent need at present is to obtain an energy storage battery which is safe, high in efficiency, high in specific energy, low in cost, high in stability and high in conductivity.
Currently, the research and application of lithium batteries are the most extensive, and sodium ion batteries and lithium ion batteries are distinguished by the state of electrolyte, and can be divided into liquid lithium ion batteries and solid lithium ion batteries. Compared with a liquid lithium electronic battery, the solid lithium electronic battery has the following advantages: 1. the hidden troubles of liquid electrolyte leakage and corrosion are eliminated, and the thermal stability is higher; 2. the electrochemical window is stable and wide, and can be matched with a high-voltage positive electrode material; 3. the solid electrolyte is generally a single-ion conductor, so that the side reaction is less, and the cycle life is longer; 4. the solid-state lithium ion battery can realize internal series connection through a multilayer stacking technology, and higher output voltage is obtained. Therefore, solid-state batteries have gained a higher degree of attention.
The solid electrolyte, which is a core component of the solid lithium battery, is a key for realizing high energy density, high cycle stability and high safety performance of the solid lithium battery. The solid electrolyte is also called a fast ion conductor and mainly comprises a polymer solid electrolyte and an inorganic solid electrolyte. Wherein the inorganic solid electrolyte further comprises: sulfide solid electrolytes, oxide solid electrolytes, borohydride solid electrolytes, phosphate solid electrolytes, halide solid electrolytes, and the like. Whatever solid electrolyte is used, the resulting interfacial problems are critical to the impact of cell performance. In a solid-state lithium battery, the interface contact between an electrode and an electrolyte is changed from solid-liquid surface contact to solid-point contact, and since the solid phase has no wettability, the solid-solid interface has a higher interface resistance. Meanwhile, a large number of crystal boundaries exist in the solid electrolyte, particularly the ceramic electrolyte, and the crystal boundary resistance is often higher than the bulk resistance of the material, which is not favorable for the transmission of lithium ions between the anode and the cathode.
At present, the sulfide electrolyte is most widely applied, but only part of the sulfide electrolyte has the ionic conductivity close to or exceeding the level of the organic liquid electrolyte, but the electrochemical stability of the sulfide electrolyte is still unsatisfactory due to the problems of interfaces and the like; oxide electrolytes, while having good electrochemical stability, typically require high temperature sintering to ensure good interfacial contact in view of their inherently high mechanical strength; phosphate solid electrolytes are a more mediocre material than other solid electrolytes, and particularly, the stability and thermal stability of phosphate in air are superior to those of sulfide, and phosphate also has the advantage of low cost, but the conductivity of phosphate solid electrolytes is not high, the performance is not particularly outstanding, and the application and development of phosphate solid electrolytes are limited. In view of the fact that no perfect electrolyte can meet the requirements of application and needs to be improved to obtain good comprehensive performance, the invention provides the aqueous high-molecular phosphate and the solid electrolyte prepared from the aqueous high-molecular phosphate, and the conductivity of the phosphate solid electrolyte is improved on the basis of keeping high stability and low cost of the phosphate solid electrolyte.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a water-based high-molecular phosphate, a preparation method and application thereof, which are suitable for electrolytes of digital or power batteries.
The purpose of the invention is realized by the following technical scheme: a preparation method of water-based high polymer phosphate comprises the following steps:
s1, performing ester exchange reaction on dimethyl isophthalate-5-phosphate and dihydric alcohol to prepare glycol isophthalate-5-phosphate;
wherein the dimethyl isophthalate-5-phosphate is one of lithium dimethyl isophthalate-5-phosphate, sodium dimethyl isophthalate-5-phosphate and potassium dimethyl isophthalate-5-phosphate, preferably lithium dimethyl isophthalate-5-phosphate, and the dihydric alcohol is one of ethylene glycol, butanediol, methyl propanediol and methyl pentanediol, preferably ethylene glycol;
s2, carrying out polymerization reaction on the isophthalic acid glycol ester-5-phosphate prepared in the step S1, the hydroxyl-terminated polyolefin diol and/or the hydrogenated hydroxyl-terminated polyolefin diol and isocyanate to prepare an isocyanate-terminated oligomer;
wherein, the hydroxyl-terminated polyolefin dihydric alcohol and/or hydrogenated hydroxyl-terminated polyolefin dihydric alcohol is one or two of hydroxyl acrylic resin, hydroxyl-terminated polybutadiene or hydrogenated hydroxyl-terminated polybutadiene;
s3, carrying out polymerization reaction on the isocyanate-terminated oligomer obtained in the step S2, AAS salt (50% of ethylenediamine ethanesulfonic acid sodium salt aqueous solution) and acetone to obtain a phosphate-containing isocyanate-terminated hydrophilic oligomer;
and S4, adding water into the isocyanate-terminated hydrophilic oligomer containing phosphate prepared in the step S3 for emulsification, then adding a diamine chain extender and a triamine chain extender for chain extension, continuing emulsification, and preparing the aqueous high-molecular phosphate after emulsification is completed.
Further, in step S1, the transesterification is performed under heating conditions in an inert gas atmosphere, the molar ratio of the dimethyl isophthalate-5-phosphate to the ethylene glycol is 1:2-5, preferably 1:4, the temperature of the transesterification is 170-230 ℃, and the reaction time is 8-12h.
Further, in step S2, 100-300ppm of triethylene diamine catalyst is added in the polymerization reaction.
Further, in the step S2, the polymerization reaction is carried out for 3-5h at the temperature of 80-90 ℃. The mol ratio of the isophthalic acid glycol ester diol-5-phosphate to the hydroxyl-terminated polyolefin diol is 5-6:10; the molar ratio of isocyanate to the total of the moles of isophthalate diol-5-phosphate and hydroxyl terminated polyolefin glycol is 1.1-1.25:1.
further, in step S2, the hydroxyl value of the hydrogenated hydroxyl-terminated polyolefin diol is 0.8 to 1.0mmol/g, and the hydroxyl value of the hydroxyl-terminated polyolefin diol is 1.2 to 1.4mmol/g.
Further, in the step S3, the mass amount of the AAS salt is 1/20-1/30 of the total mass of the hydroxyl-terminated polyolefin diol and the hydrogenated hydroxyl-terminated polyolefin diol, and the polymerization reaction is carried out for 0.5-2h at 55-65 ℃.
Further, in step S2, a water-soluble solvent is added to the isophthalic acid glycol ester-5-phosphate, wherein the water-soluble solvent is dipropylene glycol methyl ether acetate;
and/or in step S3, adding a water-soluble solvent into the polymerization reaction, wherein the water-soluble solvent is dipropylene glycol methyl ether acetate.
Further, in step S3, the isocyanate is one of hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate or liquefied diphenylmethane diisocyanate, and is preferably isophorone diisocyanate (IPDI).
Further, in the step S4, the reaction condition of the chain extension crosslinking reaction is 40-50 ℃ for 20-60min;
the diamine chain extender is one of 3, 3-dimethyl-4, 4-diaminodicyclohexylmethane, isophorone diamine and 3, 5-diethyl toluene diamine; the triamine chain extender is diethylenetriamine; the mass ratio of the diamine chain extender to the triamine chain extender is 8-10:1.
the invention also provides application of the aqueous high polymer phosphate in preparing (solid) electrolytes of digital batteries or power batteries.
The invention has the beneficial effects that:
the aqueous high molecular phosphate prepared by the invention has higher lithium ion content and high activity, and is suitable for preparing (solid) electrolyte of digital batteries or power batteries. The aqueous high molecular phosphate prepared by the invention can be coated by a coating machine, the water and the cosolvent are volatilized to form a film, and the performance can be further improved by adding a proper amount of curing agent.
Drawings
FIG. 1 is an IR spectrum of an aqueous high molecular phosphate prepared in example 2 of the present invention;
FIG. 2 is the IR spectrum data of the aqueous polymer phosphate prepared in example 2 of the present invention.
Detailed Description
The technical solutions of the present invention are further described in detail below with reference to the accompanying drawings, but the scope of the present invention is not limited to the following.
EXAMPLE 1 preparation of Isophthalic acid diol 5-phosphate
Putting 429Kg of lithium isophthalate-5-phosphate and 372Kg of ethylene glycol into a polyester reaction kettle, introducing nitrogen for protection, slowly heating to 170 ℃ under the stirring state, preserving heat for 30min at the temperature, then heating at 20 ℃/h, preserving heat for 2h at 210 ℃, then heating to 230 ℃ for 2h, starting vacuumizing when the weight of the fraction is detected to be more than 95% of the theoretical amount, gradually increasing the vacuum degree to 5mmHg, continuously reacting for 3h under the conditions of the temperature and the vacuum degree, releasing pressure, protecting nitrogen, cooling to below 150 ℃, adding 778.5Kg of dipropylene glycol methyl ether acetate, and preparing a solution with the solid content of 40% as a lithium component.
EXAMPLE 2 preparation of aqueous Polymer phosphate
Group 1: hydrogenated hydroxyl-terminated polybutadiene (C:)
HLBH-P2000) 200Kg is put into a reaction kettle to be dehydrated in vacuum at 100 ℃ for 2h, the temperature is reduced to below 80 ℃, 35.75Kg of lithium component is added, 36.8Kg of isophorone diisocyanate (IPDI) is added, the reaction is maintained at 85 ℃ for 1h, 200ppm of catalyst triethylene diamine is added, the reaction is continued for 4h at the temperature, 22.55Kg of dipropylene glycol methyl ether acetate can be used for dilution during the reaction, 20Kg of acetone and 7.6Kg of AAS salt are added when the temperature is reduced to below 60 ℃, the reaction is stopped at 60 ℃ for 1h, the stirring is stopped, 300Kg and 10 ℃ of deionized water are added, a stirring and emulsifying machine is started in sequence, after the emulsification is carried out for 10min, 3.6Kg of isophorone diamine, 0.4Kg of diethylenetriamine and 40Kg of deionized water are added, the emulsification is continued for 5min, the emulsification is stopped, the stirring is maintained at about 45 ℃ for 30min, the removal of the deionized water is removedAnd (5) acetone, discharging and packaging to obtain the aqueous high polymer phosphate with the solid content of 40%.
Group 2: hydrogenated hydroxyl-terminated polybutadiene (C:)
HLBH-P2000) 133Kg and hydroxyl-terminated polybutadiene (HTPB VI, shandong Ji Long) 67Kg are put into a reaction kettle to be dehydrated in vacuum at 100 ℃ for 2h, the temperature is reduced to below 80 ℃, lithium component 43.225Kg and isophorone diisocyanate (IPDI) 44.5Kg are added, the reaction is maintained at 85 ℃ for 1h, 200ppm catalyst triethylene diamine is added, the reaction is continued for 4h at the temperature, 24Kg dipropylene glycol methyl ether acetate can be used for dilution during the reaction, 20Kg of acetone and 7.6Kg of AAS salt are added after the temperature is reduced to below 60 ℃, the reaction is continued for 1h at 60 ℃, the stirring is stopped, 320Kg and 10 ℃ of deionized water are added, a stirring and emulsifying machine is started in sequence, after 10min of emulsification, 3.6Kg of isophorone diamine, 0.4Kg of diethylenetriamine and 40Kg of deionized water are added, the emulsification is continued for 5min, the emulsification is stopped, the emulsification is continued, the stirring is maintained at 45 ℃ for 30min, the acetone is removed, the material is discharged and is packaged, and the aqueous high-molecular phosphate containing 40% of solid phosphate is prepared.
Example 3
The polymers prepared in the above groups 1-2 were mixed with lithium hydroxide at a mass ratio of 100/20, respectively, and solid-state batteries were prepared using a solution coating method, and the conductivity was measured by electrochemical impedance spectroscopy, as follows, for group 1: 8.3X 10 -4 S/cm; group 2: 9.2X 10 -4 S/cm。
The foregoing is illustrative of the preferred embodiments of this invention, and it is to be understood that the invention is not limited to the precise form disclosed herein and that various other combinations, modifications, and environments may be resorted to, falling within the scope of the concept as disclosed herein, either as described above or as apparent to those skilled in the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The preparation method of the water-based high-molecular phosphate is characterized by comprising the following steps:
s1, performing ester exchange reaction on dimethyl isophthalate-5-phosphate and dihydric alcohol to prepare glycol isophthalate-5-phosphate;
wherein the dimethyl isophthalate-5-phosphate is one of lithium dimethyl isophthalate-5-phosphate, sodium dimethyl isophthalate-5-phosphate and potassium dimethyl isophthalate-5-phosphate, and the dihydric alcohol is one of ethylene glycol, butanediol, methyl propanediol and methyl pentanediol;
s2, carrying out polymerization reaction on the isophthalic acid glycol ester-5-phosphate prepared in the step S1, the hydroxyl-terminated polyolefin diol and/or the hydrogenated hydroxyl-terminated polyolefin diol and isocyanate to prepare an isocyanate-terminated oligomer;
wherein, the hydroxyl-terminated polyolefin dihydric alcohol and/or hydrogenated hydroxyl-terminated polyolefin dihydric alcohol is one or two of hydroxyl acrylic resin, hydroxyl-terminated polybutadiene or hydrogenated hydroxyl-terminated polybutadiene;
s3, carrying out polymerization reaction on the isocyanate-terminated oligomer obtained in the step S2, AAS salt and acetone to obtain a phosphate-containing isocyanate-terminated hydrophilic oligomer;
and S4, adding water into the isocyanate-terminated hydrophilic oligomer containing phosphate prepared in the step S3 for emulsification, then adding a diamine chain extender and a triamine chain extender for chain extension, continuing emulsification, and obtaining the water-based high polymer phosphate after emulsification is finished.
2. The method for preparing the water-based high molecular phosphate according to claim 1, wherein in step S1, the transesterification reaction is performed under heating in an inert gas atmosphere, the molar ratio of the dimethyl isophthalate-5-phosphate to the ethylene glycol is 1:2-5, the temperature of the transesterification reaction is 170-230 ℃, and the reaction time is 8-12h.
3. The method for preparing an aqueous high molecular phosphate according to claim 1, wherein in step S2, 100-300ppm of triethylenediamine catalyst is added in the polymerization reaction.
4. The method for preparing an aqueous high molecular phosphate according to claim 3, wherein in step S2, the polymerization reaction is carried out at 80-90 ℃ for 3-5h; the mol ratio of the isophthalic acid glycol ester diol-5-phosphate to the hydroxyl-terminated polyolefin diol is 5-6:10; the molar ratio of isocyanate to the total of moles of isophthalate diol-5-phosphate and hydroxyl-terminated polyolefin diol is 1.1-1.25:1.
5. the method for preparing an aqueous high molecular phosphate according to claim 1, wherein in step S2, the hydroxyl value of the hydrogenated hydroxyl-terminated polyolefin diol is 0.8 to 1.0mmol/g, and the hydroxyl value of the hydroxyl-terminated polyolefin diol is 1.2 to 1.4mmol/g.
6. The method for preparing the water-based high molecular phosphate according to claim 1, wherein in step S3, the amount of the AAS salt is 1/20 to 1/30 of the total mass of the hydroxyl-terminated polyolefin diol and the hydrogenated hydroxyl-terminated polyolefin diol, and the polymerization reaction is carried out at 55-65 ℃ for 0.5-2h.
7. The method for preparing an aqueous polymer phosphate according to claim 1, wherein in step S2, a water-soluble solvent is added to the isophthalic acid glycol ester-5-phosphate, wherein the water-soluble solvent is dipropylene glycol methyl ether acetate;
and/or in step S3, adding a water-soluble solvent into the polymerization reaction, wherein the water-soluble solvent is dipropylene glycol methyl ether acetate.
8. The method for preparing an aqueous high molecular phosphate according to claim 1, wherein in step S3, the isocyanate is one of hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate or liquefied diphenylmethane diisocyanate.
9. The method for preparing the water-based high molecular phosphate according to claim 1, wherein in step S4, the reaction conditions of the chain extension crosslinking reaction are 40-50 ℃ for 20-60min;
the diamine chain extender is one of 3, 3-dimethyl-4, 4-diaminodicyclohexylmethane, isophorone diamine and 3, 5-diethyl toluene diamine; the triamine chain extender is diethylenetriamine; the mass ratio of the diamine chain extender to the triamine chain extender is 8-10:1.
10. use of the aqueous high molecular phosphate prepared by the method of any one of claims 1 to 9 in the preparation of electrolytes for digital batteries or power batteries.
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Citations (3)
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|---|---|---|---|---|
| LU58243A1 (en) * | 1968-03-27 | 1969-07-11 | ||
| US20190020033A1 (en) * | 2017-07-17 | 2019-01-17 | Lionano Inc. | Ionomer electrode manufacturing slurry |
| CN110746457A (en) * | 2019-11-12 | 2020-02-04 | 四川大学 | Ionic monomer containing phosphonate structure, flame-retardant smoke-suppressing ionomer catalytically synthesized by using ionic monomer, and preparation methods and applications of ionic monomer and ionomer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| LU58243A1 (en) * | 1968-03-27 | 1969-07-11 | ||
| US20190020033A1 (en) * | 2017-07-17 | 2019-01-17 | Lionano Inc. | Ionomer electrode manufacturing slurry |
| CN110746457A (en) * | 2019-11-12 | 2020-02-04 | 四川大学 | Ionic monomer containing phosphonate structure, flame-retardant smoke-suppressing ionomer catalytically synthesized by using ionic monomer, and preparation methods and applications of ionic monomer and ionomer |
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| Title |
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| 秦迪: "聚脲和聚氨酯脲单离子聚合物电解质的制备及导电性研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, no. 201802, pages 014 - 483 * |
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