CN117335017B - Polymer colloid electrolyte of lead-acid battery and preparation method thereof - Google Patents
Polymer colloid electrolyte of lead-acid battery and preparation method thereof Download PDFInfo
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- CN117335017B CN117335017B CN202311484116.2A CN202311484116A CN117335017B CN 117335017 B CN117335017 B CN 117335017B CN 202311484116 A CN202311484116 A CN 202311484116A CN 117335017 B CN117335017 B CN 117335017B
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 74
- 239000002253 acid Substances 0.000 title claims abstract description 37
- 229920000642 polymer Polymers 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000084 colloidal system Substances 0.000 title claims description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000003365 glass fiber Substances 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000008367 deionised water Substances 0.000 claims abstract description 24
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 24
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000004327 boric acid Substances 0.000 claims abstract description 23
- 229910021485 fumed silica Inorganic materials 0.000 claims abstract description 23
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 20
- 239000011245 gel electrolyte Substances 0.000 claims abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000004913 activation Effects 0.000 claims abstract description 5
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 17
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 17
- 239000004201 L-cysteine Substances 0.000 claims description 15
- 235000013878 L-cysteine Nutrition 0.000 claims description 15
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 14
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 14
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 14
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 11
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 11
- 235000011151 potassium sulphates Nutrition 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 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 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- -1 silicon quaternary ammonium salt Chemical class 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 6
- 235000019743 Choline chloride Nutrition 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 6
- 229960003178 choline chloride Drugs 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 5
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 5
- 229940044175 cobalt sulfate Drugs 0.000 claims description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000413 hydrolysate Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 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 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 claims 1
- 230000036571 hydration Effects 0.000 abstract description 5
- 238000006703 hydration reaction Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 108010009736 Protein Hydrolysates Proteins 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000009974 thixotropic effect Effects 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/08—Selection of materials as electrolytes
- H01M10/10—Immobilising of electrolyte
-
- 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
- H01M10/06—Lead-acid accumulators
- H01M10/12—Construction or manufacture
-
- 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
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a lead-acid battery polymer gel electrolyte and a preparation method thereof, wherein the lead-acid battery polymer gel electrolyte comprises the following raw materials in parts by weight: 100-120 parts of dilute sulfuric acid, 4-8 parts of fumed silica, 10-15 parts of boric acid, 0.1-0.5 part of surfactant, 0.1-0.5 part of sulfate, 0.05-0.2 part of L-cysteine, 1-3 parts of modified glass fiber and 20-30 parts of deionized water, wherein the modified glass fiber is prepared by chemically grafting organosilicon quaternary ammonium salt after glass fiber is subjected to activation treatment. According to the invention, the gel electrolyte is added with the modified glass fiber, so that the three-dimensional network structure of the electrolyte is more stable, the gel strength is improved, the hydration layering phenomenon of the gel electrolyte can be effectively prevented, the poor performance of the battery is caused, and the service life of the battery is reduced.
Description
Technical Field
The invention belongs to the technical field of lead-acid batteries, and particularly relates to a high-molecular colloid electrolyte of a lead-acid battery and a preparation method thereof.
Background
The modern society consumes more and more fossil fuel and has serious environmental pollution. New clean energy sources such as solar energy, tidal energy, wind energy, geothermal energy and the like are attracting more and more attention, but the energy sources need to be stored in batteries for better use. The lead-acid storage battery has the advantages of higher energy density, longer service life, lower self-discharge rate, higher charge-discharge efficiency, lower cost, better environmental adaptability, safety, reliability and the like. These advantages make lead-acid batteries an important energy storage solution for wide application in various fields.
The electrolyte liquid sulfuric acid in the lead-acid battery has the defects of easy leakage of acid liquor, volatilization of acid liquor and the like, so that equipment and human bodies are corroded, and the damage is particularly remarkable when the lead-acid battery is used under the conditions of inclination, vibration and shaking. It is therefore first thought to change the morphology of the electrolyte in the cell without affecting the movement of ions in the electrolyte. The gel electrolyte technology is a new technology for solving the defects of the lead-acid liquid battery. The gel electrolyte is prepared by dispersing a certain proportion of gel agents such as silicon dioxide or silica sol in sulfuric acid solution, and a proper amount of additive is generally added according to the characteristics of a lead-acid battery, so that the gel electrolyte with certain thixotropic property matched with the battery system is obtained. At present, most of gel agents of the colloidal electrolyte are silica sol, the microscopic three-dimensional network structure in an electrolyte system is unstable, and the electrolyte is easy to generate hydration and layering, so that the application of the colloidal electrolyte is limited.
Disclosure of Invention
In order to solve the defects in the background art, the invention aims to provide the high-molecular colloid electrolyte of the lead-acid battery and the preparation method thereof, wherein the colloid electrolyte is added with the modified glass fiber to enable the three-dimensional network structure of the electrolyte to be more stable, the gel strength is improved, the hydration layering phenomenon of the colloid electrolyte can be effectively prevented, the battery performance is poor, and the service life of the battery is reduced.
The aim of the invention can be achieved by the following technical scheme:
the invention provides a lead-acid battery polymer gel electrolyte, which comprises the following raw materials in parts by weight: 100 to 120 parts of dilute sulfuric acid, 4 to 8 parts of fumed silica, 10 to 15 parts of boric acid, 0.1 to 0.5 part of surfactant, 0.1 to 0.5 part of sulfate, 0.05 to 0.2 part of L-cysteine, 1 to 3 parts of modified glass fiber and 20 to 30 parts of deionized water; the concentration of the dilute sulfuric acid is 37-42 wt%; the modified glass fiber is prepared by chemically grafting organic silicon quaternary ammonium salt to glass fiber after activation treatment, and the organic silicon quaternary ammonium salt has the following structural formula:
Further preferably, the surfactant is one or more of polyvinyl alcohol, polyoxyethylene ether and carboxymethyl cellulose.
Further preferably, the sulfate is one or more of stannous sulfate, sodium sulfate, potassium sulfate, cobalt sulfate, nickel sulfate and chromium sulfate.
Further preferably, the organosilicon quaternary ammonium salt is prepared by reacting isophorone diisocyanate, 3-aminopropyl triethoxysilane and choline chloride, and specifically comprises the following steps:
S1, adding isophorone diisocyanate and solvent acetonitrile into a reactor, stirring and dissolving under ice bath conditions, controlling the temperature to be 0-5 ℃,
S2, slowly dropwise adding 3-aminopropyl triethoxysilane under the protection of N 2, and continuing to react for 1h after the dropwise adding is completed for 1-3 h;
s3, adding choline chloride and catalyst dibutyl tin dilaurate, controlling the temperature to be 40-45 ℃ for reaction for 2-4 hours, and distilling under reduced pressure to remove acetonitrile to obtain the organosilicon quaternary ammonium salt.
Further preferably, the preparation method of the modified glass fiber comprises the following steps:
(1) Slowly adding hydrogen peroxide into concentrated sulfuric acid according to a certain proportion to obtain pretreatment liquid, immersing glass fibers to be treated into the pretreatment solution for 10-30 s, washing with deionized water for 3-5 times, and drying with nitrogen to obtain activated glass fibers;
(2) The organosilicon quaternary ammonium salt and tetraethyl silicate are mixed according to the proportion of 1: 3-4, adding the mixed solution into the hydrolysate according to the mass ratio of 1:19-20, and reacting for 3-5 hours under the condition of constant temperature water bath at 30-35 ℃ to obtain the organosilicon quaternary ammonium salt modified treatment solution;
(3) Immersing activated glass fibers in the organic silicon quaternary ammonium salt modification treatment liquid for 3-5 min, taking out, putting the glass fibers into a baking oven at 100-120 ℃ for reaction for 1-3 h, taking out the glass fibers after the reaction is finished, washing the glass fibers with deionized water for 3-5 times, and drying with nitrogen to obtain the modified reinforced glass.
Further preferably, the mass fraction of the hydrogen peroxide in the step (1) is 30%, and the volume ratio of the hydrogen peroxide to the concentrated sulfuric acid is 3:7.
Further preferably, the hydrolysate in the step (2) is prepared from ethanol and deionized water according to a volume ratio of 9-10: 1.
A high molecular colloid electrolyte of lead-acid battery and its preparation method, comprising the following steps:
step one, adding fumed silica into deionized water, and stirring for 8-10 min under the constant temperature water condition of 20-25 ℃ until the fumed silica is completely dispersed to obtain a dispersion liquid;
adding boric acid, a surfactant, sulfate and L-cysteine into dilute sulfuric acid, and fully stirring until the boric acid, the surfactant, the sulfate and the L-cysteine are completely dissolved to obtain dilute sulfuric acid electrolyte;
and thirdly, adding the dilute sulfuric acid electrolyte into the silicon dioxide dispersion liquid, stirring and mixing for 5-10 min, adding the modified glass fiber, continuously stirring for 5-10 min, and cooling to room temperature to obtain the high polymer colloid electrolyte of the lead-acid battery.
The invention has the beneficial effects that:
The lead-acid battery polymer colloid electrolyte is added with boric acid and metal sulfate, so that the corrosion of the electrolyte to the grid is reduced to prolong the service life of the battery, the conductivity of the electrolyte can be improved, and the charge acceptance of the lead-acid battery after deep discharge circulation is enhanced. And the fumed silica and the surfactant are added, the surfactant can be combined with the silica particles, aggregation among the silica particles is prevented, interaction among part of the silica particles, solvent molecules and the silica particles is prevented, the gel time of the colloidal electrolyte is prolonged, and the gel filling into the battery is facilitated. The addition of the modified glass fiber makes the three-dimensional network structure of the electrolyte more stable, improves the gel strength, can effectively prevent the gel electrolyte from hydration layering phenomenon, causes poor battery performance and reduces the service life of the battery. Meanwhile, in order to prevent the aggregation of glass fibers in the colloidal electrolyte, the electrolyte impedance is increased, and quaternary ammonium salt grafting modification is performed after the activation treatment, so that the Zeta potential of the surface of the glass fibers is improved, the aggregation of the glass fibers is reduced, the glass fibers can be more uniformly dispersed in the colloidal electrolyte, and the influence on the impedance of the colloidal electrolyte is reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described, and it will be obvious to those skilled in the art that other drawings can be obtained according to these drawings without inventive effort.
FIG. 1 is an infrared spectrum of a silicone quaternary ammonium salt of example 1 of the present invention;
FIG. 2 is an infrared spectrum of a modified glass fiber according to example 2 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described 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 present invention provides a quaternary organosilicon ammonium salt having the following structural formula:
the organosilicon quaternary ammonium salt is prepared by the reaction of isophorone diisocyanate, 3-aminopropyl triethoxy silane and choline chloride, and the reaction principle is as follows:
the method specifically comprises the following steps:
S1, adding isophorone diisocyanate and solvent acetonitrile into a reactor, stirring and dissolving under ice bath conditions, controlling the temperature to be 5 ℃,
S2, slowly dropwise adding 3-aminopropyl triethoxysilane under the protection of N 2, and continuing to react for 1h after the completion of 2h dropwise adding;
S3, adding choline chloride and a catalyst dibutyl tin dilaurate, controlling the temperature to react at 42 ℃ for 3 hours, and distilling under reduced pressure to remove acetonitrile to obtain the organosilicon quaternary ammonium salt.
The infrared spectrum of the prepared organosilicon quaternary ammonium salt is shown in figure 1 by carrying out Fourier infrared spectrum (FTIR) analysis, and the characteristic peak of-NCO does not appear at 2250cm -1, which indicates that the-NCO in isophorone diisocyanate is basically completely reacted, 3315cm -1 is a single-peak characteristic absorption of-NH, 1719cm -1 is an infrared characteristic absorption peak of-C=O in the functional group structure after the reaction of-NCO and-OH, 1639cm -1 is a strong absorption peak of-C=O in-NH-CO, 1562cm -1 is an infrared characteristic absorption peak of N-CH 3 at 1477cm -1, and the infrared characteristic absorption peaks are basically consistent with the functional groups corresponding to target products.
Example 2 the present invention provides a modified glass fiber, which is activated by glass fiber and then undergoes grafting reaction with organosilicon quaternary ammonium salt and tetraethyl silicate hydrolysate, the reaction principle is as follows:
The preparation method comprises the following steps:
(1) Slowly adding 30wt% of hydrogen peroxide into concentrated sulfuric acid according to a volume ratio of 3:7 to obtain a pretreatment liquid, immersing glass fibers to be treated into the pretreatment solution for 20s, washing with deionized water for 3-5 times, and drying with nitrogen to obtain activated glass fibers;
(2) The organosilicon quaternary ammonium salt and tetraethyl silicate are mixed according to the proportion of 1:3, and then adding the mixed solution into ethanol and deionized water according to the volume ratio of 10, wherein the mass ratio of the mixed solution is 1:20: 1, in the mixed hydrolysate, the hydrolysate reacts for 4 hours under the condition of constant-temperature water bath at 35 ℃ to obtain organosilicon quaternary ammonium salt modified treatment liquid;
(3) Immersing activated glass fibers in the organic silicon quaternary ammonium salt modification treatment liquid for 5min, taking out, putting the glass fibers into a baking oven at 120 ℃ for reaction for 2h, taking out the glass fibers after the reaction is finished, washing the glass fibers with deionized water for 3-5 times, and drying with nitrogen to obtain the modified reinforced glass.
And (3) carrying out Fourier infrared (FTIR) analysis on the prepared modified glass fiber to obtain an infrared spectrogram of the modified glass fiber, wherein the infrared spectrogram is shown in figure 2, and compared with the infrared spectrogram of the organosilicon quaternary ammonium salt, the infrared spectrogram has a strong absorption peak at 1043cm -1, which is a characteristic absorption peak of Si-O-Si, so that the organosilicon quaternary ammonium salt is successfully grafted on the glass fiber.
Example 3 a lead acid battery polymeric colloid electrolyte comprising the following raw materials in parts by weight: 100 parts of 42wt% dilute sulfuric acid, 8 parts of fumed silica, 15 parts of boric acid, 0.2 part of polyvinyl alcohol, 0.05 part of stannous sulfate, 0.1 part of sodium sulfate, 0.1 part of L-cysteine, 2 parts of modified glass fiber and 30 parts of deionized water;
The preparation method comprises the following steps:
adding fumed silica into deionized water, and stirring for 8min under the constant-temperature water condition of 25 ℃ until the fumed silica is completely dispersed to obtain a dispersion liquid;
Adding boric acid, polyvinyl alcohol, stannous sulfate, sodium sulfate and L-cysteine into dilute sulfuric acid, and fully stirring until the boric acid, the polyvinyl alcohol, the stannous sulfate, the sodium sulfate and the L-cysteine are completely dissolved to obtain dilute sulfuric acid electrolyte;
And thirdly, adding the dilute sulfuric acid electrolyte into the silicon dioxide dispersion liquid, stirring and mixing for 5min, adding the modified glass fiber, continuously stirring for 10min, and cooling to room temperature to obtain the high polymer colloid electrolyte of the lead-acid battery.
Example 4a lead acid battery polymeric colloid electrolyte comprising the following raw materials in parts by weight: 120 parts of 37wt% dilute sulfuric acid, 4 parts of fumed silica, 10 parts of boric acid, 0.2 part of carboxymethyl cellulose, 0.1 part of stannous sulfate, 0.05 part of cobalt sulfate, 0.05 part of chromium sulfate, 0.2 part of L-cysteine, 3 parts of modified glass fiber and 20 parts of deionized water;
The preparation method comprises the following steps:
Adding fumed silica into deionized water, and stirring for 10min under the condition of constant temperature water at 20 ℃ until the fumed silica is completely dispersed to obtain a dispersion liquid;
Adding boric acid, carboxymethyl cellulose, stannous sulfate, cobalt sulfate, chromium sulfate and L-cysteine into dilute sulfuric acid, and fully stirring until the boric acid, the carboxymethyl cellulose, the stannous sulfate, the cobalt sulfate, the chromium sulfate and the L-cysteine are completely dissolved to obtain dilute sulfuric acid electrolyte;
and thirdly, adding the dilute sulfuric acid electrolyte into the silicon dioxide dispersion liquid, stirring and mixing for 10min, adding the modified glass fiber, continuously stirring for 5min, and cooling to room temperature to obtain the high polymer colloid electrolyte of the lead-acid battery.
Example 5a lead acid battery polymeric colloid electrolyte comprising the following raw materials in parts by weight: 110 parts of 40wt% dilute sulfuric acid, 6 parts of fumed silica, 12 parts of boric acid, 0.2 part of polyvinyl alcohol, 0.3 part of carboxymethyl cellulose, 0.1 part of stannous sulfate, 0.1 part of potassium sulfate, 0.05 part of L-cysteine, 2 parts of modified glass fiber and 25 parts of deionized water;
The preparation method comprises the following steps:
adding fumed silica into deionized water, and stirring for 8-10 min under the condition of constant temperature water at 22 ℃ until the fumed silica is completely dispersed to obtain a dispersion liquid;
Adding boric acid, polyvinyl alcohol, carboxymethyl cellulose, stannous sulfate, potassium sulfate and L-cysteine into dilute sulfuric acid, and fully stirring until the boric acid, the polyvinyl alcohol, the carboxymethyl cellulose, the stannous sulfate, the potassium sulfate and the L-cysteine are completely dissolved to obtain dilute sulfuric acid electrolyte;
And thirdly, adding the dilute sulfuric acid electrolyte into the silicon dioxide dispersion liquid, stirring and mixing for 8min, adding the modified glass fiber, continuously stirring for 8min, and cooling to room temperature to obtain the high polymer colloid electrolyte of the lead-acid battery.
Comparative example 1a lead acid battery polymeric colloid electrolyte comprising the following raw materials in parts by weight: 110 parts of 40wt% dilute sulfuric acid, 6 parts of fumed silica, 12 parts of boric acid, 0.2 part of polyvinyl alcohol, 0.3 part of carboxymethyl cellulose, 0.1 part of stannous sulfate, 0.1 part of potassium sulfate, 0.05 part of L-cysteine, 2 parts of glass fiber and 25 parts of deionized water;
The preparation method comprises the following steps:
adding fumed silica into deionized water, and stirring for 8-10 min under the condition of constant temperature water at 22 ℃ until the fumed silica is completely dispersed to obtain a dispersion liquid;
Adding boric acid, polyvinyl alcohol, carboxymethyl cellulose, stannous sulfate, potassium sulfate and L-cysteine into dilute sulfuric acid, and fully stirring until the boric acid, the polyvinyl alcohol, the carboxymethyl cellulose, the stannous sulfate, the potassium sulfate and the L-cysteine are completely dissolved to obtain dilute sulfuric acid electrolyte;
and thirdly, adding the dilute sulfuric acid electrolyte into the silicon dioxide dispersion liquid, stirring and mixing for 8min, adding the glass fiber, continuously stirring for 8min, and cooling to room temperature to obtain the polymer colloid electrolyte of the lead-acid battery.
Comparative example 2 a lead acid battery polymeric colloid electrolyte comprising the following raw materials in parts by weight: 110 parts of 40wt% dilute sulfuric acid, 6 parts of fumed silica, 12 parts of boric acid, 0.2 part of polyvinyl alcohol, 0.3 part of carboxymethyl cellulose, 0.1 part of stannous sulfate, 0.1 part of potassium sulfate, 0.05 part of L-cysteine and 25 parts of deionized water;
The preparation method comprises the following steps:
adding fumed silica into deionized water, and stirring for 8-10 min under the condition of constant temperature water at 22 ℃ until the fumed silica is completely dispersed to obtain a dispersion liquid;
Adding boric acid, polyvinyl alcohol, carboxymethyl cellulose, stannous sulfate, potassium sulfate and L-cysteine into dilute sulfuric acid, and fully stirring until the boric acid, the polyvinyl alcohol, the carboxymethyl cellulose, the stannous sulfate, the potassium sulfate and the L-cysteine are completely dissolved to obtain dilute sulfuric acid electrolyte;
And thirdly, adding the dilute sulfuric acid electrolyte into the silicon dioxide dispersion liquid, stirring and mixing for 8min, and cooling to room temperature to obtain the high polymer colloid electrolyte of the lead-acid battery.
Performance detection
(1) Gel strength test: the colloidal electrolytes prepared in examples 3 to 4 and comparative examples 1 to 2 were placed in a test tube having a diameter of 3cm, placed in a water bath at 25℃for 24 hours, and a straight scale having a length of 15cm and an end face of a rectangle (length 16mm and width 1 mm) and a weight of 14g was freely dropped from a height of 10cm from the surface of the colloidal electrolyte using a self-made instrument. Gel strength was shown by the depth of insertion of the ruler into the colloidal electrolyte, and the gel strength was measured H times (required error 3%) and averaged to give the data shown in table 1 below.
TABLE 1 gel strength test results for colloidal electrolytes
As can be seen from the data in table 1, in comparative example 2, the gel strength was significantly lower than that of examples 3 to 5 without adding glass fibers and modified glass fibers, indicating that the addition of modified glass fibers can make the three-dimensional network structure of the electrolyte more stable, can prevent the occurrence of hydration delamination phenomenon of the colloidal electrolyte, resulting in poor battery performance and reduced battery life.
(2) Ion conductivity test: three negative plates and two positive plates are arranged in a staggered manner, the negative plates are wrapped by AGM (advanced glass polymer) diaphragms and are placed into a rectangular organic glass battery shell together, wherein the total amount of active substances on the negative plates is the same as that on the positive plates, the colloidal electrolytes prepared in the embodiment 5 and the comparative examples 1-2 are injected into the battery shell, and after the colloid is solidified, the ionic conductivity of the colloidal electrolyte is tested:
The detection is accomplished by alternating current resistance using an electrochemical workstation. The amplitude of the alternating voltage is set to 5mV and the frequency is between 105 or 106Hz and 0.1 Hz. Film thickness was measured with a thickness gauge after the end of the test. The bulk impedance R b of the electrolyte membrane was obtained from the data measurements. The ionic conductivity σ=l/R b ×s of the electrolyte can be calculated according to the formula, L refers here to the thickness of the electrolyte membrane, S refers here to the contact area of the steel sheet with the electrolyte membrane, and R b refers here to the bulk impedance of the electrolyte. The results are shown in Table 2.
TABLE 2 results of colloidal electrolyte ion conductivity test
As can be seen from the data in table 2, in comparative example 1, unmodified glass fibers were added, and in comparative example 2, glass fibers and modified glass fibers were not added, and the decrease in ion conductivity in comparative example 1 was more pronounced than in comparative example 2, probably due to agglomeration of glass fibers in the colloidal electrolyte, because glass fibers are insulators, migration of ions was blocked after agglomeration of glass fibers in the colloidal electrolyte, and the increase in impedance of the colloidal electrolyte was caused, whereas the decrease in ion conductivity in examples 3 to 4 was less pronounced than in comparative example 2, because the Zeta potential of the surface was increased after the ordinary glass fiber film was subjected to quaternary ammonium salt graft modification by the activation treatment, so that the modified glass fibers could be more uniformly dispersed in the colloidal electrolyte, agglomeration was not likely to occur, and thus the increase in impedance of the electrolyte was not pronounced.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims.
Claims (6)
1. The high polymer colloid electrolyte of the lead-acid battery is characterized by comprising the following raw materials in parts by weight: 100 to 120 parts of dilute sulfuric acid, 4 to 8 parts of fumed silica, 10 to 15 parts of boric acid, 0.1 to 0.5 part of surfactant, 0.1 to 0.5 part of sulfate, 0.05 to 0.2 part of L-cysteine, 1 to 3 parts of modified glass fiber and 20 to 30 parts of deionized water; the concentration of the dilute sulfuric acid is 37-42 wt%; the modified glass fiber is prepared by chemically grafting organic silicon quaternary ammonium salt to glass fiber after activation treatment, and the organic silicon quaternary ammonium salt has the following structural formula:
the organosilicon quaternary ammonium salt is prepared by the reaction of isophorone diisocyanate, 3-aminopropyl triethoxy silane and choline chloride, and specifically comprises the following steps:
S1, adding isophorone diisocyanate and solvent acetonitrile into a reactor, stirring and dissolving under ice bath conditions, controlling the temperature to be 0-5 ℃,
S2, slowly dropwise adding 3-aminopropyl triethoxysilane under the protection of N 2, and continuing to react for 1h after the dropwise adding is completed for 1-3 h;
S3, adding choline chloride and catalyst dibutyl tin dilaurate, controlling the temperature to be 40-45 ℃ for reaction for 2-4 hours, and distilling under reduced pressure to remove acetonitrile to obtain the organosilicon quaternary ammonium salt;
The preparation method of the modified glass fiber comprises the following steps:
(1) Slowly adding hydrogen peroxide into concentrated sulfuric acid according to a certain proportion to obtain pretreatment liquid, immersing glass fibers to be treated into the pretreatment solution for 10-30 s, washing with deionized water for 3-5 times, and drying with nitrogen to obtain activated glass fibers;
(2) The organosilicon quaternary ammonium salt and tetraethyl silicate are mixed according to the proportion of 1: 3-4, adding the mixed solution into the hydrolysate according to the mass ratio of 1:19-20, and reacting for 3-5 hours under the condition of constant temperature water bath at 30-35 ℃ to obtain the organosilicon quaternary ammonium salt modified treatment solution;
(3) Immersing activated glass fibers in the organic silicon quaternary ammonium salt modification treatment liquid for 3-5 min, taking out, putting the glass fibers into a baking oven at 100-120 ℃ for reaction for 1-3 h, taking out the glass fibers after the reaction is finished, washing the glass fibers with deionized water for 3-5 times, and drying with nitrogen to obtain the modified glass fibers.
2. The lead-acid battery polymer colloid electrolyte according to claim 1, wherein the surfactant is one or more of polyvinyl alcohol, polyoxyethylene ether and carboxymethyl cellulose.
3. The polymer colloid electrolyte for lead-acid battery according to claim 1, wherein the sulfate is one or more of stannous sulfate, sodium sulfate, potassium sulfate, cobalt sulfate, nickel sulfate and chromium sulfate.
4. The polymer gel electrolyte of the lead-acid battery according to claim 1, wherein the mass fraction of the hydrogen peroxide in the step (1) is 30%, and the volume ratio of the hydrogen peroxide to the concentrated sulfuric acid is 3:7.
5. The high polymer colloid electrolyte for lead-acid battery according to claim 1, wherein the hydrolysis liquid in the step (2) is prepared from ethanol and deionized water according to a volume ratio of 9-10: 1.
6. The method for preparing a polymer gel electrolyte for a lead-acid battery according to any one of claims 1 to 5, comprising the steps of:
step one, adding fumed silica into deionized water, and stirring for 8-10 min under the constant temperature water condition of 20-25 ℃ until the fumed silica is completely dispersed to obtain a dispersion liquid;
adding boric acid, a surfactant, sulfate and L-cysteine into dilute sulfuric acid, and fully stirring until the boric acid, the surfactant, the sulfate and the L-cysteine are completely dissolved to obtain dilute sulfuric acid electrolyte;
and thirdly, adding the dilute sulfuric acid electrolyte into the silicon dioxide dispersion liquid, stirring and mixing for 5-10 min, adding the modified glass fiber, continuously stirring for 5-10 min, and cooling to room temperature to obtain the high polymer colloid electrolyte of the lead-acid battery.
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