CN116376486A - Adhesive for sodium ion battery and preparation method thereof - Google Patents
Adhesive for sodium ion battery and preparation method thereof Download PDFInfo
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- CN116376486A CN116376486A CN202310313877.5A CN202310313877A CN116376486A CN 116376486 A CN116376486 A CN 116376486A CN 202310313877 A CN202310313877 A CN 202310313877A CN 116376486 A CN116376486 A CN 116376486A
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- sodium ion
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- 239000000853 adhesive Substances 0.000 title claims abstract description 44
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 44
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920002678 cellulose Polymers 0.000 claims abstract description 37
- 239000001913 cellulose Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 24
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 12
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims description 39
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 22
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 20
- IXRHKCZOPXFJGP-UHFFFAOYSA-N FC(C(F)(F)F)(O[Si](OC(C(F)(F)F)(F)F)(C(F)(F)F)C(C(F)(F)F)(F)F)C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F Chemical compound FC(C(F)(F)F)(O[Si](OC(C(F)(F)F)(F)F)(C(F)(F)F)C(C(F)(F)F)(F)F)C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F IXRHKCZOPXFJGP-UHFFFAOYSA-N 0.000 claims description 16
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- -1 modified prepolymer Chemical compound 0.000 claims description 13
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 12
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 12
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- 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 11
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 claims description 10
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- DOKHEARVIDLSFF-UHFFFAOYSA-N prop-1-en-1-ol Chemical compound CC=CO DOKHEARVIDLSFF-UHFFFAOYSA-N 0.000 claims description 7
- 229920000875 Dissolving pulp Polymers 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 229940043237 diethanolamine Drugs 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- DNPNFYJXUGCNNC-UHFFFAOYSA-N 4-hydroxy-2-(hydroxymethyl)butanoic acid Chemical compound OCCC(CO)C(O)=O DNPNFYJXUGCNNC-UHFFFAOYSA-N 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/068—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J101/00—Adhesives based on cellulose, modified cellulose, or cellulose derivatives
- C09J101/08—Cellulose derivatives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- 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)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses an adhesive for sodium ion batteries and a preparation method thereof, wherein methyl methacrylate, butyl acrylate, acrylic acid and a modified prepolymer are polymerized and then grafted with reinforced cellulose and dispersed in water to prepare the adhesive, the modified prepolymer is of a resin-like structure, and the single molecular weight of the adhesive contains an organosilicon chain segment, so that the prepared adhesive has good heat-resistant effect, the adhesive can not be decomposed under a high-temperature environment, and meanwhile, the adhesive contains a large number of carboxyl groups in the molecule, so that the adhesive strength is greatly improved, and the adhesive is compounded with the reinforced cellulose, so that the prepared adhesive can not crack after multiple cycles, and further the normal use of an electrode is ensured.
Description
Technical Field
The invention relates to the technical field of preparation of battery adhesives, in particular to an adhesive for a sodium ion battery and a preparation method thereof.
Background
As various facilities of human society are continuously built and perfected, resources are consumed in a large amount, so that environmental pollution is serious. Development of new materials and clean energy is imperative. Lithium ion batteries have played an increasingly important role in new energy sources due to the advantages of high energy output, no environmental pollution and the like. With the wide use of electronic products such as mobile phones and electric automobiles, strong market demands are formed for novel, efficient, energy-saving and environment-friendly batteries, and the market demands are also expanding continuously. The statistics of Internet big data show that the energy consumption of vehicles accounts for the highest proportion of global total resource consumption in the half-century. Therefore, the sodium battery has wide application prospect as one of the future development directions of the battery.
Disclosure of Invention
The invention aims to provide an adhesive for a sodium ion battery and a preparation method thereof, which solve the problems that the adhesive for the sodium ion battery in the present stage has a common bonding effect and an electrode cannot work normally after being used for multiple times.
The aim of the invention can be achieved by the following technical scheme:
the preparation method of the adhesive for the sodium ion battery specifically comprises the following steps:
methyl methacrylate, butyl acrylate, acrylic acid, modified prepolymer, azodiisobutyronitrile and isopropanol are uniformly mixed, nitrogen is introduced for protection, the reaction is carried out for 3-5 hours under the condition that the rotating speed is 150-200 r/min and the temperature is 85-90 ℃, isopropanol is distilled off, a substrate, reinforced cellulose and deionized water are mixed, and the mixture is stirred for 6-8 hours under the condition that the rotating speed is 200-300 r/min and the temperature is 50-60 ℃, so that the adhesive for the sodium ion battery is prepared.
Further, the dosage ratio of methyl methacrylate, butyl acrylate, acrylic acid, modified prepolymer, azodiisobutyronitrile and isopropanol is 5g to 8g to 3g to 15g to 1g to 100mL, and the dosage ratio of substrate, reinforced cellulose and deionized water is 10g to 1g to 22-25mL.
Further, the modified prepolymer is prepared by the following steps:
step A1: adding perfluorohexyl ethyl methyl diethoxy silane and dimethyl dichlorosilane into deionized water, stirring at the rotation speed of 200-300 r/min and the temperature of 25-30 ℃ for 20-30 min, adding tetrahydrofuran and concentrated sulfuric acid, heating to 55-65 ℃, preserving heat for 5-10 min, adding 1, 3-tetramethyl disiloxane, and reacting for 3-5h to obtain an intermediate 1;
step A2: uniformly mixing an intermediate 1, trimethylolpropane triacrylate and dimethylbenzene, stirring and adding chloroplatinic acid at the rotation speed of 200-300 r/min and the temperature of 50-60 ℃, heating to 60-65 ℃, reacting for 6-8 hours, adding propenol to obtain an intermediate 2, uniformly mixing diethanolamine, acrylic acid and methylbenzene, stirring and adding 1-hydroxybenzotriazole at the rotation speed of 150-200 r/min and the temperature of 30-40 ℃, and reacting for 6-8 hours to obtain an intermediate 3;
step A3: uniformly mixing the intermediate 2, the intermediate 3 and the 2, 2-dimethylolpropionic acid, stirring and adding isophorone diisocyanate and dibutyltin dilaurate under the conditions of the rotating speed of 200-300 r/min and the temperature of 80-85 ℃ for reacting for 2-3 hours to obtain the modified prepolymer.
Further, the dosage ratio of perfluorohexyl ethyl methyl diethoxysilane, dimethyl dichlorosilane, deionized water and 1, 3-tetramethyl disiloxane in the step A1 is 2mmo l:3mmo l:5mL:3mmo l, and the dosage of concentrated sulfuric acid is 5-8% of the sum of the weights of perfluorohexyl ethyl methyl diethoxysilane, dimethyl dichlorosilane, deionized water and 1, 3-tetramethyl disiloxane.
Further, the dosage ratio of the intermediate 1, the trimethylolpropane triacrylate and the allyl alcohol in the step A2 is n:2n+1:n+2, n is a natural number greater than 0, and the molar ratio of the diethanolamine, the acrylic acid and the 1-hydroxybenzotriazole is 1:1:1.1.
Further, the mass ratio of the intermediate 2, the intermediate 3, the 2, 2-dimethylolpropionic acid and the isophorone diisocyanate in the step A3 is 10:3:0.7:6, and the dosage of the dibutyl tin dilaurate is 1 per mill.
Further, the reinforced cellulose is prepared by the following steps:
dissolving cellulose in dimethylacetamide, stirring at a rotation speed of 150-200 r/min and a temperature of 115-125 ℃ for 2-3 hours, cooling to 95-105 ℃, adding lithium chloride, stirring to be transparent, cooling to 5-10 ℃, adding triethylamine and p-toluenesulfonyl chloride, stirring for 20-25 hours, adding ice water for precipitation and filtration, drying a filter cake, dissolving in dimethylsulfoxide, adding ethylenediamine, stirring at a rotation speed of 300-500 r/min and a temperature of 100-110 ℃ for 5-7 hours, precipitating the reactant in acetone, and drying to obtain the reinforced cellulose.
Further, the dosage ratio of the cellulose, the lithium chloride, the triethylamine, the p-toluenesulfonyl chloride and the ethylenediamine is 1g:2g:3mL:0.8g:1g.
The invention has the beneficial effects that: the adhesive for sodium ion battery is prepared through polymerizing methyl methacrylate, butyl acrylate, acrylic acid and modified prepolymer, grafting with reinforced cellulose and dispersing in water, the modified prepolymer takes perfluorohexyl ethyl methyl diethoxy silane and dimethyl dichloro silane as raw materials, hydrolyzing and polymerizing with 1, 3-tetramethyl disiloxane to form S i-H end-capped polysiloxane, preparing intermediate 1, reacting intermediate 1 with trimethylolpropane triacrylate, reacting S i-H bond on one side of intermediate 1 with double bond on trimethylolpropane triacrylate by controlling the dosage, adding propenol, reacting double bond on the propenol with S i-H bond on the other side, preparing intermediate 2, reacting diethanolamine with acrylic acid, the carboxyl on acrylic acid is dehydrated and condensed with imine on diethanol amine to prepare an intermediate 3, the intermediate 2, the intermediate 3, 2-dimethylolpropionic acid and isophorone diisocyanate are reacted to prepare a modified prepolymer, the reinforced cellulose takes cellulose as a raw material, the cellulose is firstly swelled and dissolved, then p-toluenesulfonyl chloride is used for processing to obtain p-toluenesulfonyl cellulose, diethylamine is used for replacing p-toluenesulfonyl groups, amino groups are introduced on cellulose molecules to prepare the reinforced cellulose, the modified prepolymer is of a resin-like structure, the single molecular weight contains an organosilicon chain segment, so that the prepared adhesive has good heat-resisting effect, the problem of decomposition of the adhesive can not occur in a high-temperature environment, and meanwhile, a large amount of carboxyl groups are contained in the molecule, so that the adhesive strength is greatly improved and is compounded with the reinforced cellulose, after the prepared adhesive is circulated for a plurality of times, cracks can not appear, and normal use of the electrode is further ensured.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the adhesive for the sodium ion battery specifically comprises the following steps:
methyl methacrylate, butyl acrylate, acrylic acid, modified prepolymer, azodiisobutyronitrile and isopropanol are uniformly mixed, nitrogen is introduced for protection, the reaction is carried out for 3 hours at the temperature of 85 ℃ at the rotation speed of 150 r/min, isopropanol is distilled and removed, a substrate, reinforced cellulose and deionized water are mixed, and the mixture is stirred for 6 hours at the temperature of 50 ℃ at the rotation speed of 200 r/min, so that the adhesive for the sodium ion battery is prepared.
The dosage ratio of methyl methacrylate, butyl acrylate, acrylic acid, modified prepolymer, azodiisobutyronitrile and isopropanol is 5g to 8g to 3g to 15g to 1g to 100mL, and the dosage ratio of substrate, reinforced cellulose and deionized water is 10g to 1g to 22mL.
The modified prepolymer is prepared by the following steps:
step A1: adding perfluorohexyl ethyl methyl diethoxy silane and dimethyl dichlorosilane into deionized water, stirring for 20 min at the rotation speed of 200 r/min and the temperature of 25 ℃, adding tetrahydrofuran and concentrated sulfuric acid, heating to 55 ℃, preserving heat for 5 min, adding 1, 3-tetramethyl disiloxane, and reacting for 3h to obtain an intermediate 1;
step A2: uniformly mixing the intermediate 1, trimethylolpropane triacrylate and dimethylbenzene, stirring and adding chloroplatinic acid under the conditions of the rotating speed of 200 r/min and the temperature of 50 ℃, heating to 60 ℃, reacting for 6 hours, adding propenol to obtain an intermediate 2, uniformly mixing diethanolamine, acrylic acid and methylbenzene, stirring and adding 1-hydroxybenzotriazole under the conditions of the rotating speed of 150 r/min and the temperature of 30 ℃, and reacting for 6 hours to obtain an intermediate 3;
step A3: uniformly mixing the intermediate 2, the intermediate 3 and the 2, 2-dimethylolpropionic acid, stirring and adding isophorone diisocyanate and dibutyltin dilaurate under the conditions of the rotating speed of 200 r/min and the temperature of 80 ℃ for reacting for 2 hours to obtain the modified prepolymer.
The dosage ratio of perfluorohexyl ethyl methyl diethoxysilane, dimethyl dichlorosilane, deionized water and 1, 3-tetramethyl disiloxane in the step A1 is 2mmo l:3mmo l:5mL:3mmo l, and the dosage of concentrated sulfuric acid is 5% of the sum of the mass of perfluorohexyl ethyl methyl diethoxysilane, dimethyl dichlorosilane, deionized water and 1, 3-tetramethyl disiloxane.
The dosage ratio of the intermediate 1 to the trimethylolpropane triacrylate to the allyl alcohol in the step A2 is 1:3:3, and the mol ratio of the diethanolamine to the acrylic acid to the 1-hydroxybenzotriazole is 1:1:1.1.
The mass ratio of the intermediate 2 to the intermediate 3 to the 2, 2-dimethylolpropionic acid to the isophorone diisocyanate in the step A3 is 10:3:0.7:6, and the dosage of the dibutyl tin dilaurate is 1 per mill.
The reinforced cellulose is prepared by the following steps:
dissolving cellulose in dimethylacetamide, stirring at 150 r/min and 115 ℃ for 2 hours, cooling to 95 ℃, adding lithium chloride, stirring to be transparent, cooling to 5 ℃, adding triethylamine and p-toluenesulfonyl chloride, stirring for 20 hours, adding ice water for precipitation and filtration, drying a filter cake, dissolving in dimethylsulfoxide, adding ethylenediamine, stirring at 300 r/min and 100 ℃ for 5 hours, precipitating the reactant in acetone, and drying to obtain the reinforced cellulose.
The dosage ratio of the cellulose, the lithium chloride, the triethylamine, the p-toluenesulfonyl chloride and the ethylenediamine is 1g:2g:3mL:0.8g:1g.
Example 2
The preparation method of the adhesive for the sodium ion battery specifically comprises the following steps:
methyl methacrylate, butyl acrylate, acrylic acid, modified prepolymer, azodiisobutyronitrile and isopropanol are uniformly mixed, nitrogen is introduced for protection, the reaction is carried out for 4 hours at the rotation speed of 180 r/min and the temperature of 90 ℃, isopropanol is distilled and removed, a substrate, reinforced cellulose and deionized water are mixed, and the mixture is stirred for 7 hours at the rotation speed of 200 r/min and the temperature of 55 ℃ to prepare the adhesive for the sodium ion battery.
The dosage ratio of methyl methacrylate, butyl acrylate, acrylic acid, modified prepolymer, azodiisobutyronitrile and isopropanol is 5g to 8g to 3g to 15g to 1g to 100mL, and the dosage ratio of substrate, reinforced cellulose and deionized water is 10g to 1g to 23mL.
The modified prepolymer is prepared by the following steps:
step A1: adding perfluorohexyl ethyl methyl diethoxy silane and dimethyl dichlorosilane into deionized water, stirring for 25 min at the rotation speed of 200 r/min and the temperature of 30 ℃, adding tetrahydrofuran and concentrated sulfuric acid, heating to 60 ℃, preserving heat for 8 min, adding 1, 3-tetramethyl disiloxane, and reacting for 4h to obtain an intermediate 1;
step A2: uniformly mixing the intermediate 1, trimethylolpropane triacrylate and dimethylbenzene, stirring and adding chloroplatinic acid under the conditions of the rotating speed of 200 r/min and the temperature of 55 ℃, heating to 63 ℃, reacting for 7 hours, adding propenol to obtain an intermediate 2, uniformly mixing diethanolamine, acrylic acid and methylbenzene, stirring and adding 1-hydroxybenzotriazole under the conditions of the rotating speed of 180 r/min and the temperature of 35 ℃, and reacting for 7 hours to obtain an intermediate 3;
step A3: uniformly mixing the intermediate 2, the intermediate 3 and the 2, 2-dimethylolpropionic acid, stirring and adding isophorone diisocyanate and dibutyltin dilaurate under the conditions of the rotating speed of 200 r/min and the temperature of 83 ℃ for reaction for 3 hours, and obtaining the modified prepolymer.
The dosage ratio of perfluorohexyl ethyl methyl diethoxysilane, dimethyl dichlorosilane, deionized water and 1, 3-tetramethyl disiloxane in the step A1 is 2mmo l:3mmo l:5mL:3mmo l, and the dosage of concentrated sulfuric acid is 6% of the sum of the mass of perfluorohexyl ethyl methyl diethoxysilane, dimethyl dichlorosilane, deionized water and 1, 3-tetramethyl disiloxane.
The dosage ratio of the intermediate 1 to the trimethylolpropane triacrylate to the allyl alcohol in the step A2 is 2:5:4, n is a natural number greater than 0, and the molar ratio of the diethanolamine to the acrylic acid to the 1-hydroxybenzotriazole is 1:1:1.1.
The mass ratio of the intermediate 2 to the intermediate 3 to the 2, 2-dimethylolpropionic acid to the isophorone diisocyanate in the step A3 is 10:3:0.7:6, and the dosage of the dibutyl tin dilaurate is 1 per mill.
The reinforced cellulose is prepared by the following steps:
dissolving cellulose in dimethylacetamide, stirring at 150 r/min and 120 ℃ for 3 hours, cooling to 100 ℃, adding lithium chloride, stirring to be transparent, cooling to 8 ℃, adding triethylamine and p-toluenesulfonyl chloride, stirring for 23 hours, adding ice water for precipitation and filtration, drying a filter cake, dissolving in dimethylsulfoxide, adding ethylenediamine, stirring at 300 r/min and 105 ℃ for 6 hours, precipitating the reactant in acetone, and drying to obtain the reinforced cellulose.
The dosage ratio of the cellulose, the lithium chloride, the triethylamine, the p-toluenesulfonyl chloride and the ethylenediamine is 1g:2g:3mL:0.8g:1g.
Example 3
The preparation method of the adhesive for the sodium ion battery specifically comprises the following steps:
methyl methacrylate, butyl acrylate, acrylic acid, modified prepolymer, azodiisobutyronitrile and isopropanol are uniformly mixed, nitrogen is introduced for protection, the reaction is carried out for 5 hours at the rotation speed of 200 r/min and the temperature of 90 ℃, isopropanol is distilled and removed, a substrate, reinforced cellulose and deionized water are mixed, and the mixture is stirred for 8 hours at the rotation speed of 300 r/min and the temperature of 60 ℃ to prepare the adhesive for the sodium ion battery.
The dosage ratio of methyl methacrylate, butyl acrylate, acrylic acid, modified prepolymer, azodiisobutyronitrile and isopropanol is 5g to 8g to 3g to 15g to 1g to 100mL, and the dosage ratio of substrate, reinforced cellulose and deionized water is 10g to 1g to 25mL.
The modified prepolymer is prepared by the following steps:
step A1: adding perfluorohexyl ethyl methyl diethoxy silane and dimethyl dichlorosilane into deionized water, stirring for 30 min at the rotation speed of 300 r/min and the temperature of 30 ℃, adding tetrahydrofuran and concentrated sulfuric acid, heating to 65 ℃, preserving heat for 10 min, adding 1, 3-tetramethyl disiloxane, and reacting for 5h to obtain an intermediate 1;
step A2: uniformly mixing the intermediate 1, trimethylolpropane triacrylate and dimethylbenzene, stirring and adding chloroplatinic acid at the rotation speed of 300 r/min and the temperature of 60 ℃, heating to 65 ℃, reacting for 8 hours, adding propenol to obtain an intermediate 2, uniformly mixing diethanolamine, acrylic acid and methylbenzene, stirring and adding 1-hydroxybenzotriazole at the rotation speed of 200 r/min and the temperature of 40 ℃, and reacting for 8 hours to obtain an intermediate 3;
step A3: uniformly mixing the intermediate 2, the intermediate 3 and the 2, 2-dimethylolpropionic acid, stirring and adding isophorone diisocyanate and dibutyltin dilaurate under the conditions of the rotating speed of 300 r/min and the temperature of 85 ℃ for reaction for 3 hours, and obtaining the modified prepolymer.
The dosage ratio of perfluorohexyl ethyl methyl diethoxysilane, dimethyl dichlorosilane, deionized water and 1, 3-tetramethyl disiloxane in the step A1 is 2mmo l:3mmo l:5mL:3mmo l, and the dosage of concentrated sulfuric acid is 8% of the sum of the mass of perfluorohexyl ethyl methyl diethoxysilane, dimethyl dichlorosilane, deionized water and 1, 3-tetramethyl disiloxane.
The dosage ratio of the intermediate 1, the trimethylolpropane triacrylate and the allyl alcohol in the step A2 is 3:7:5, and the mol ratio of the diethanolamine, the acrylic acid and the 1-hydroxybenzotriazole is 1:1:1.1.
The mass ratio of the intermediate 2 to the intermediate 3 to the 2, 2-dimethylolpropionic acid to the isophorone diisocyanate in the step A3 is 10:3:0.7:6, and the dosage of the dibutyl tin dilaurate is 1 per mill.
The reinforced cellulose is prepared by the following steps:
dissolving cellulose in dimethylacetamide, stirring at a rotation speed of 200 r/min and a temperature of 125 ℃ for 3 hours, cooling to 105 ℃, adding lithium chloride, stirring to be transparent, cooling to 10 ℃, adding triethylamine and p-toluenesulfonyl chloride, stirring for 25 hours, adding ice water for precipitation and filtration, drying a filter cake, dissolving in dimethylsulfoxide, adding ethylenediamine, stirring at a rotation speed of 500 r/min and a temperature of 110 ℃ for 7 hours, precipitating the reactant in acetone, and drying to obtain the reinforced cellulose.
The dosage ratio of the cellulose, the lithium chloride, the triethylamine, the p-toluenesulfonyl chloride and the ethylenediamine is 1g:2g:3mL:0.8g:1g.
Comparative example 1
In this comparative example, no reinforcing cellulose was added as compared with example 1, and the rest of the procedure was the same.
Comparative example 2
In this comparative example, the modified prepolymer, the reinforcing cellulose and deionized water were directly mixed to prepare an adhesive in comparison with example 1, and the other steps were the same.
The adhesive prepared in examples 1-3 and comparative examples 1-2 was bonded with aluminum foil and PET respectively, the layers were bonded by pressure bonding with an adhesive, the peel strength was tested under the condition of a peel speed of 30 cm/min, 10mL of the adhesive prepared in examples 1-3 and comparative examples 1-2 was added with 0.2g of conductive agent Super-P and 9.5g of artificial graphite having a specific capacity of 360mAh/g, and after mixing, the mixture was coated on copper foil to obtain electrode sheets, which were transferred into a glove box to assemble a button cell, and the electrolyte was 1MNAPF 6 The EC/DMC mixed solution (volume ratio 1:1) adopts a battery test system with model CT2001A manufactured by Wuhan blue electric company to test the electrochemical performance of the obtained button battery, the discharge cut-off voltage of the test condition is 0.005V, the charge cut-off voltage is 1V, and the charge and discharge times are carried outThe rate was 0.5C, and the results are shown in the following table.
The table shows that the adhesive has good adhesive strength and can ensure the service life of the enhanced battery.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (9)
1. A preparation method of an adhesive for sodium ion batteries is characterized by comprising the following steps: the method specifically comprises the following steps:
methyl methacrylate, butyl acrylate, acrylic acid, modified prepolymer, azodiisobutyronitrile and isopropanol are uniformly mixed, nitrogen is introduced for protection, after the reaction, isopropanol is distilled off, and a substrate, reinforced cellulose and deionized water are mixed and stirred to prepare the adhesive for the sodium ion battery.
2. The method for preparing the adhesive for the sodium ion battery according to claim 1, wherein the method comprises the following steps: the dosage ratio of methyl methacrylate, butyl acrylate, acrylic acid, modified prepolymer, azodiisobutyronitrile and isopropanol is 5g to 8g to 3g to 15g to 1g to 100mL, and the dosage ratio of substrate, reinforced cellulose and deionized water is 10g to 1g to 22-25mL.
3. The method for preparing the adhesive for the sodium ion battery according to claim 1, wherein the method comprises the following steps: the modified prepolymer is prepared by the following steps:
step A1: adding perfluorohexyl ethyl methyl diethoxy silane and dimethyl dichlorosilane into deionized water, stirring, adding tetrahydrofuran and concentrated sulfuric acid, heating and preserving heat, adding 1, 3-tetramethyl disiloxane, and reacting to obtain an intermediate 1;
step A2: mixing and stirring the intermediate 1, trimethylolpropane triacrylate and xylene, adding chloroplatinic acid, heating for reaction, adding propenol to obtain an intermediate 2, mixing and stirring diethanolamine, acrylic acid and toluene, adding 1-hydroxybenzotriazole, and reacting to obtain an intermediate 3;
step A3: the intermediate 2, the intermediate 3 and the 2, 2-dimethylolpropionic acid are mixed and stirred, and isophorone diisocyanate and dibutyltin dilaurate are added for reaction, so that the modified prepolymer is prepared.
4. The method for preparing the adhesive for sodium ion batteries according to claim 3, wherein the method comprises the following steps: the dosage ratio of perfluorohexyl ethyl methyl diethoxysilane, dimethyl dichlorosilane, deionized water and 1, 3-tetramethyl disiloxane in the step A1 is 2mmol:3mmol:5mL:3mmol, and the dosage of concentrated sulfuric acid is 5% of the sum of the weights of perfluorohexyl ethyl methyl diethoxysilane, dimethyl dichlorosilane, deionized water and 1, 3-tetramethyl disiloxane.
5. The method for preparing the adhesive for sodium ion batteries according to claim 3, wherein the method comprises the following steps: the dosage ratio of the intermediate 1, the trimethylolpropane triacrylate and the allyl alcohol in the step A2 is n:2n+1:n+2, n is a natural number greater than 0, and the molar ratio of the diethanolamine, the acrylic acid and the 1-hydroxybenzotriazole is 1:1:1.1.
6. The method for preparing the adhesive for sodium ion batteries according to claim 3, wherein the method comprises the following steps: the mass ratio of the intermediate 2 to the intermediate 3 to the 2, 2-dimethylolpropionic acid to the isophorone diisocyanate in the step A3 is 10:3:0.7:6, and the dosage of the dibutyl tin dilaurate is 1 per mill.
7. The method for preparing the adhesive for the sodium ion battery according to claim 1, wherein the method comprises the following steps: the reinforced cellulose is prepared by the following steps:
dissolving cellulose in dimethylacetamide, stirring, cooling, adding lithium chloride, stirring to be transparent, cooling again, adding triethylamine and p-toluenesulfonyl chloride, stirring, adding ice water for precipitation and filtration, drying a filter cake, dissolving in dimethyl sulfoxide, adding ethylenediamine, stirring, precipitating a reactant in acetone, and drying to obtain the reinforced cellulose.
8. The method for preparing the adhesive for the sodium ion battery according to claim 7, wherein the method comprises the following steps: the dosage ratio of the cellulose, the lithium chloride, the triethylamine, the p-toluenesulfonyl chloride and the ethylenediamine is 1g:2g:3mL:0.8g:1g.
9. An adhesive for sodium ion batteries is characterized in that: the preparation method according to any one of claims 1 to 8.
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