CN115490804A - Corrosion inhibitor, preparation method thereof and application of corrosion inhibitor in zinc-manganese battery coated paper - Google Patents
Corrosion inhibitor, preparation method thereof and application of corrosion inhibitor in zinc-manganese battery coated paper Download PDFInfo
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- CN115490804A CN115490804A CN202211024016.7A CN202211024016A CN115490804A CN 115490804 A CN115490804 A CN 115490804A CN 202211024016 A CN202211024016 A CN 202211024016A CN 115490804 A CN115490804 A CN 115490804A
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- 238000005260 corrosion Methods 0.000 title claims abstract description 97
- 230000007797 corrosion Effects 0.000 title claims abstract description 95
- 239000003112 inhibitor Substances 0.000 title claims abstract description 78
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 32
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 32
- 239000002002 slurry Substances 0.000 claims abstract description 29
- 229920000881 Modified starch Polymers 0.000 claims abstract description 27
- 239000004368 Modified starch Substances 0.000 claims abstract description 27
- 235000019426 modified starch Nutrition 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 17
- 229920002472 Starch Polymers 0.000 claims description 39
- 239000008107 starch Substances 0.000 claims description 39
- 235000019698 starch Nutrition 0.000 claims description 39
- 229920006322 acrylamide copolymer Polymers 0.000 claims description 31
- 239000002608 ionic liquid Substances 0.000 claims description 13
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 12
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 12
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 12
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 239000007888 film coating Substances 0.000 claims description 2
- 238000009501 film coating Methods 0.000 claims description 2
- 238000010409 ironing Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052725 zinc Inorganic materials 0.000 abstract description 22
- 239000011701 zinc Substances 0.000 abstract description 22
- 230000005764 inhibitory process Effects 0.000 abstract description 10
- 229920000642 polymer Polymers 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 238000002955 isolation Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 229920000831 ionic polymer Polymers 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- -1 vinyl bis-imidazole Chemical compound 0.000 description 2
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012490 blank solution Substances 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000013055 pulp slurry Substances 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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Classifications
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- 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
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/38—Corrosion-inhibiting agents or anti-oxidants
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
- D21H25/04—Physical treatment, e.g. heating, irradiating
- D21H25/06—Physical treatment, e.g. heating, irradiating of impregnated or coated paper
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of metal corrosion and protection, and discloses a corrosion inhibitor, a preparation method thereof and application of the corrosion inhibitor in zinc-manganese battery coated paper. The corrosion inhibitor is used for preparing the zinc-manganese battery coated paper, accounts for 0.001-3% of the total mass of the slurry, and comprises 1-10% of polyvinyl alcohol (PVA), 10-50% of Polyacrylamide (PAM), 2-5% of carboxymethyl cellulose (CMC), 1-15% of modified starch and the balance of deionized water. Compared with the organic micromolecular corrosion inhibitor, the polymer corrosion inhibitor for the coated paper has higher coverage rate on the metal surface. The inhibitor is used as an environment-friendly inhibitor, can effectively inhibit corrosion inhibition of zinc sheets in the zinc-manganese battery, and prolongs the service life of the battery. The prepared pulp paper is used as an electrode isolation layer in a zinc-manganese dry battery, so that the discharge storage performance of the battery is improved, and a good corrosion inhibition effect is achieved on a zinc electrode.
Description
Technical Field
The invention relates to the technical field of metal corrosion and protection, in particular to a corrosion inhibitor, a preparation method thereof and application of the corrosion inhibitor in zinc-manganese battery coated paper.
Background
The zinc-manganese battery is widely used due to simple production process, low cost and large capacity, television and air conditioner remote controller batteries even national defense and agricultural production lighting become an indispensable part in national economy, the pulp paper is used as a diaphragm for separating positive and negative electrodes in the battery, the addition of the pulp paper ensures that two electrode materials can not directly contact and inhibit a zinc cylinder, and the electrolyte can smoothly pass through the battery to absorb a certain electrolyte when the battery normally works, so that the current during the maintenance period is smooth, the acidic electrolyte in the battery is easy to expose out of corrosion equipment, in order to reduce the corrosion of zinc skin during the storage period of a dry battery and prevent the zinc cylinder from corroding and perforating, the mercury chloride is added in the electrolyte used as the corrosion inhibitor, but the mercury is extremely toxic, and the research on environment-friendly and nontoxic corrosion inhibitor has great significance for environmental protection, and the addition of the corrosion inhibitor into the preparation of the existing pulp paper has great research significance, so that the corrosion inhibitor and the preparation method thereof and the application of the pulp paper for the zinc-manganese battery are provided.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides the corrosion inhibitor, the preparation method thereof and the application of the corrosion inhibitor in the zinc-manganese battery coated paper, the corrosion inhibitor has the advantages of effectively reducing the self-corrosion efficiency of a zinc electrode and prolonging the discharge and storage time of the zinc-manganese battery, and the problems of over-fast self-corrosion of the electrode and over-short storage time of the zinc-manganese battery in the current battery preparation process are solved.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a bis-imidazolyl ionic liquid-acrylamide copolymer corrosion inhibitor is prepared by copolymerization of Acrylamide (AM) and vinyl bis-imidazole ionic liquid under the action of an initiator, and is called PAM-IL for short, wherein the structural formulas of the Acrylamide (AM) and the Ionic Liquid (IL) are respectively as follows:
in the structural formula, R is (CH 2) n, n =4,5,6, the anion is selected from one of Br, BF4 and HSO4, and P is the abbreviation of polymerization.
The polymer corrosion inhibitor is used in the zinc-manganese battery slurry paper, after the vinyl diimidazole ionic liquid and acrylamide are subjected to graft copolymerization, a complex formed by the formed polymer corrosion inhibitor and metal zinc can cover the surface of the polymer corrosion inhibitor to protect metal from corrosion, so that the corrosion of a zinc electrode in a zinc-manganese battery is effectively inhibited, the stability is high, and the corrosion inhibitor is an environment-friendly corrosion inhibitor.
Preferably, the bis-imidazolyl ionic liquid-acrylamide copolymer corrosion inhibitor can be prepared by the following simple method: 1-vinyl imidazole and (CH 2) nBr2 (wherein N is one of 4,5 and 6) react for 12 hours at 75 ℃ in an acetonitrile solvent under the nitrogen atmosphere, then the solvent is removed by rotary evaporation, the remainder is dissolved in water and separated to obtain an intermediate 1, then the intermediate 1 reacts with N-methyl imidazole at 80 ℃ for 12 hours to obtain an intermediate 2, the intermediate 2 reacts with acid HX to prepare target ionic liquid, the target ionic liquid reacts with acrylamide and an ammonium persulfate-sodium bisulfite initiator under the nitrogen atmosphere at 70 ℃ for 12 hours, and the product is dried at 90 ℃ in vacuum to obtain a copolymer, namely the bisimidazolyl ionic liquid-acrylamide copolymer corrosion inhibitor which is water-soluble; wherein X = Br, BF4 or HSO4.
The structural formulas of the intermediate 1 and the intermediate 2 are as follows:
wherein R = (CH 2) n (wherein n =4,5, 6)
Preferably, in the preparation of the bis-imidazolyl ionic liquid-acrylamide copolymer, the selected initiator is an ammonium persulfate-sodium bisulfite redox system, so that the activation energy required by the reaction can be reduced, the initiation efficiency is high, the cost is low, the reproducibility is high, the environment is protected, and the industrial control is easy.
Preferably, the application of the bis-imidazolyl ionic liquid-acrylamide copolymer corrosion inhibitor is used for preparing sizing agent for zinc-manganese battery pulp layer paper. The slurry consists of a bis-imidazolyl ionic liquid-acrylamide copolymer corrosion inhibitor (PAM-IL), polyacrylamide (PAM), polyvinyl alcohol (PVA), carboxymethyl cellulose, modified starch and deionized water; wherein the bis-imidazolyl ionic liquid-acrylamide copolymer corrosion inhibitor accounts for 0.001-3% of the total mass of the slurry, the polyvinyl alcohol (PVA) accounts for 1-10% of the total mass of the slurry, the Polyacrylamide (PAM) accounts for 10-50% of the total mass of the slurry, the carboxymethyl cellulose (CMC) accounts for 2-5% of the total mass of the slurry, the modified starch accounts for 1-15% of the total mass of the slurry, and the balance is deionized water.
Preferably, the pulp for the coated paper comprises the following components in percentage by weight: 0.01-2% of bis-imidazolyl ionic liquid-acrylamide copolymer corrosion inhibitor, 1-9% of PVA, 15-40% of PAM, 2-4% of CMC, 1-14% of modified starch and the balance of deionized water.
Preferably, the size for the coated paper consists of the following components in percentage by weight: 0.01-1% of bis-imidazolyl ionic liquid-acrylamide copolymer corrosion inhibitor, 1-8% of PVA, 20-40% of PAM, 3-4% of CMC, 2-13% of modified starch and the balance of deionized water.
The preparation process of the sizing agent for the coated paper comprises the following steps:
s101, uniformly stirring a certain proportion of cross-linked starch and etherified starch in deionized water to prepare modified starch for later use;
s102, dissolving a certain amount of PVA in boiled deionized water, adding quantitative PAM and CMC after completely dissolving, continuously stirring until the mixture is uniformly stirred, and dropwise adding 2mol/L HCl to adjust the pH value of the solution to be acidic;
s103, adding modified starch and a composite corrosion inhibitor into the solution, and mixing uniformly to obtain slurry;
s104, coating the filtered pulp on base paper by using a wire bar film coating machine, preheating at low temperature in a drying stage, drying at high temperature (95-100 ℃), ironing at low temperature, and cutting the pulp layer paper for later use.
Preferably, in the preparation method, the modified starch is one or two of cross-linked starch and etherified starch, and when the modified starch is a mixture of the cross-linked starch and the etherified starch, the mass ratio of the cross-linked starch to the etherified starch is: etherified starch =1 (1-5).
In the above preparation method, preferably, when the modified starch is a mixture of a crosslinked starch and an etherified starch, the mass ratio of the crosslinked starch to the etherified starch is 1.5.
Compared with the prior art, the invention provides the corrosion inhibitor and the preparation method thereof and the application of the corrosion inhibitor in the zinc-manganese battery coated paper, and the corrosion inhibitor has the following beneficial effects:
1. the corrosion inhibitor for the coated paper belongs to one of polyion liquid, and compared with other single organic micromolecule corrosion inhibitors, the corrosion inhibitor for the coated paper has a good corrosion inhibition effect under a small using amount. The existence of multiple bonds on the surface of the zinc enables the polymer to be firmly adsorbed on the surface of the zinc, so that the desorption of the polymer is a slow process, thereby effectively inhibiting the contact between the surface of the zinc and a corrosive medium in the electrolyte, and further slowing down the corrosion of the zinc.
2. Compared with the traditional ionic liquid corrosion inhibitor and polymer corrosion inhibitor, the polyionic liquid is green and environment-friendly, has stable property and good film forming property and strength, and can improve the discharge performance of the battery.
3. The bis-imidazolyl ionic liquid-acrylamide copolymer corrosion inhibitor is not easy to generate gas, avoids the occurrence of swelling and leakage of a battery, and reduces the explosion risk of the battery and the requirement on the sealing technology of the battery.
4. The preparation process of the sizing agent for the coated paper is simple, and the bis-imidazolyl ionic liquid-acrylamide copolymer corrosion inhibitor, polyvinyl alcohol, polyacrylamide, carboxymethyl cellulose, modified starch and deionized water are mixed according to different proportions. And coating the prepared pulp on base paper, drying, slitting and rewinding to obtain the coated paper. Compared with the common batteries sold in the market, the battery performance of the battery assembled by the pulp layer paper is improved by more than 10 percent.
Drawings
FIG. 1 is a schematic diagram of the process of making the pulp for coated paper of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
preparation of bis-imidazolyl ionic liquid-acrylamide copolymer corrosion inhibitor
The bis-imidazolyl ionic liquid-acrylamide copolymer corrosion inhibitor is prepared by the following method: the 1-vinylimidazole and (CH 2) nBr2 (where n = 6) reactants were reacted as follows 1:1.2, carrying out reaction reflux for 12h at 75 ℃ in a nitrogen atmosphere, wherein the solvent is acetonitrile, carrying out rotary evaporation at 85 ℃ to remove the acetonitrile after white turbidity appears in the reaction process, dissolving the generated ion product in water, separating the ion product by using a separating funnel, and carrying out rotary evaporation to remove water to obtain an intermediate product 1. Taking 0.07mol of N-methylimidazole to react with the intermediate product 1 at the temperature of 80 ℃ for 12 hours to obtain an intermediate product 2, putting the intermediate product 2 into a three-neck flask, adding a certain amount of anhydrous acetonitrile serving as a solvent, dropwise adding fluoroboric acid with the amount of substances such as a constant-pressure funnel in an ice water bath, after dropwise adding, magnetically stirring at room temperature for 12 hours, after the reaction is finished, filtering to remove insoluble substances, then removing the solvent by rotary evaporation to obtain a target ionic liquid, and then adding 5g of acrylamide, 0.15g of an initiator and part of deionized water to react at the temperature of 70 ℃ for 24 hours in a nitrogen atmosphere to generate a copolymer.
According to the preparation method, the intermediate 1 with different carbon chain lengths is synthesized by changing the size of N (N can be 4, 5) in the reactant (CH 2) nBr2, then the intermediate 2 is prepared by substitution reaction with N-methylimidazole, and imidazole ionic liquids with different anion types are synthesized by using different acid radical ions such as BF4, HSO4 and the like.
Carrying out polarization curve on a corrosion inhibition system through an electrochemical workstation to obtain corrosion inhibition efficiency, wherein the corrosion inhibition efficiency I.E. is calculated by adopting a formula I.E. = (I0corr. -Icor.)/I0corr.X 100%, and the I.E. is the corrosion inhibition efficiency of a corrosion inhibitor on a zinc electrode; i0corr, corrosion current of the zinc electrode in the blank solution, A; icorr. Is the corrosion current of the zinc electrode in the solution with the added corrosion inhibitor, a.
A working electrode adopts a 1cm multiplied by 1cm metal zinc sheet, the thickness is ignored, one surface of the zinc sheet is welded with a copper wire by an electric iron, then the non-working surface is sealed by epoxy resin, and the zinc sheet is dried and placed; the other side of the zinc electrode is polished to be bright by 500# abrasive paper, 800# abrasive paper and 1000# abrasive paper respectively, and then is repeatedly cleaned by deionized water and acetone and dried in vacuum for later use; before testing, the electrode is put into a testing solution for 30min to reach a stable state, a saturated calomel electrode is used as a reference electrode, and a platinum electrode is used as a counter electrode; and (3) placing the three electrodes in 1mol/L HCl solution added with corrosion inhibitors with different contents, and testing a polarization curve after the open-circuit voltage is reached.
In the following examples, bis-imidazolyl ionic liquid-acrylamide copolymer corrosion inhibitors for coated papers were performed as described in example 1.
Example 2:
preparing a bis-imidazolyl ionic liquid-acrylamide copolymer corrosion inhibitor for coated paper, wherein (CH 2) nBr2, n =4 and X is Br in a reactant;
preparing a material for zinc-manganese battery slurry layer paper according to the following method:
accurately weighing 1.7g of PVA, adding the PVA into a beaker filled with 35g of 98 ℃ deionized water, and stirring to dissolve the PVA; when the temperature of the PVA water solution is reduced to 50 ℃, 13g of PAM and 3.2g of CMC are added in sequence and stirred uniformly; adjusting the pH value of the solution to 3.5 by using 1mol/L HCl solution; then 7.5g of modified starch and the prepared bis-imidazolyl ionic liquid-acrylamide copolymer corrosion inhibitor are added, wherein the modified starch is a mixture of cross-linked starch and etherified starch, and the mass ratio of the cross-linked starch is as follows: etherified starch = 1.5, stirring uniformly and adjusting viscosity to obtain slurry, wherein the mass fractions of the corrosion inhibitor, PVA, PAM, CMC, modified starch and deionized water in the slurry are respectively: 4.07%, 2.52%, 19.27%, 4.78%, 11.15%, 58.21%; and coating the prepared pulp on base paper, drying, slitting and rewinding to obtain the pulp layer paper.
The corrosion inhibition efficiency of the coated paper prepared by the corrosion inhibitor on the zinc electrode reaches 90.63%, and the performance of the prepared coated paper meets the GB/T2303-2008 requirement.
Example 3:
preparing a bis-imidazolyl ionic liquid-acrylamide copolymer corrosion inhibitor for coated paper, wherein in a reactant, (CH 2) nBr2, n =5, and X is HSO4;
preparing the sizing agent for the coated paper according to the following method:
accurately weighing 1.5g of PVA, adding the PVA into a beaker filled with 32g of deionized water at 98 ℃, and stirring to dissolve the PVA; when the temperature of the PVA aqueous solution is reduced to 50 ℃, 19.15g of PAM and 3.1g of CMC are added in sequence and stirred uniformly; adjusting the pH value of the solution to 3.5 by using 1mol/L HCl solution; then adding 7.7g of modified starch and the starch graft copolymer corrosion inhibitor prepared above, wherein the modified starch is a mixture of cross-linked starch and etherified starch, and the mass ratio of the cross-linked starch is as follows: etherified starch = 1.5, stirring uniformly and adjusting viscosity to obtain slurry, wherein the mass fractions of the corrosion inhibitor, PVA, PAM, CMC, modified starch and deionized water in the slurry are respectively: 4.59%, 1.8%, 22.99%, 3.73%, 9.24%, 57.65%; and coating the prepared pulp on base paper, drying, slitting and rewinding to obtain the coated paper.
The corrosion inhibition efficiency of the coated paper prepared by the corrosion inhibitor on the zinc electrode reaches 92.39%, and the performance of the prepared coated paper meets the GB/T2303-2008 requirement.
Example 4:
preparing a bis-imidazolyl ionic liquid-acrylamide copolymer corrosion inhibitor for coated paper, wherein in a reactant, (CH 2) nBr2, n =6, and X is BF4;
preparing a pulp slurry of a pulp layer according to the following method:
accurately weighing 1.3g of PVA, adding the PVA into a beaker filled with 30g of 98 ℃ deionized water, and stirring to dissolve the PVA; when the temperature of the PVA aqueous solution is reduced to 50 ℃, 14.4g of PAM and 2.6g of CMC are sequentially added and stirred uniformly; adjusting the pH value of the solution to 3.5 by using 1mol/L HCl solution; then 8.9g of modified starch and the starch graft copolymer corrosion inhibitor prepared above are added, wherein the modified starch is a mixture of cross-linked starch and etherified starch, and the mass ratio of the cross-linked starch: etherified starch = 1.5, stirring uniformly and adjusting viscosity to obtain slurry, wherein the mass fractions of the corrosion inhibitor, PVA, PAM, CMC, modified starch and deionized water in the slurry are respectively: 5.63%, 1.9%, 21.07%, 3.77%, 12.69%, 54.94%; and coating the prepared pulp on base paper, drying, slitting and rewinding to obtain the coated paper.
The corrosion inhibition efficiency of the coated paper prepared by the corrosion inhibitor on the zinc electrode reaches 94.96%, and the performance of the prepared coated paper meets the GB/T2303-2008 requirement.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A bis-imidazolyl ionic liquid-acrylamide copolymer corrosion inhibitor is characterized in that: the acrylamide/ionic liquid copolymer is prepared by copolymerization of Acrylamide (AM) and vinyl diimidazole ionic liquid under the action of an initiator, and the structural formulas of the Acrylamide (AM) and the Ionic Liquid (IL) are respectively as follows:
in the structural formula, R is (CH 2) n, n =4 or 5 or 6, and the anion is selected from one of Br, BF4 and HSO4.
2. The bis-imidazolyl ionic liquid-acrylamide copolymer corrosion inhibitor according to claim 1, which provides an application of the bis-imidazolyl ionic liquid-acrylamide copolymer corrosion inhibitor in zinc-manganese battery coated paper, and is characterized in that: the slurry for preparing the zinc-manganese battery slurry layer paper comprises the following components in percentage by mass:
0.001-3% of bis-imidazolyl ionic liquid-acrylamide copolymer corrosion inhibitor
Polyvinyl alcohol (PVA) 1-10%
10% -50% of Polyacrylamide (PAM)
2% -5% of carboxymethyl cellulose (CMC)
1 to 15 percent of modified starch
The balance of deionized water.
3. The application of the bis-imidazolyl ionic liquid-acrylamide copolymer corrosion inhibitor in zinc-manganese battery coated paper according to claim 2, wherein the corrosion inhibitor comprises the following components in percentage by weight: the prepared slurry for the zinc-manganese battery slurry layer paper comprises the following components in percentage by mass:
0.01 to 2 percent of bis-imidazolyl ionic liquid-acrylamide copolymer corrosion inhibitor
Polyvinyl alcohol (PVA) 1-9%
15-40% of Polyacrylamide (PAM)
2% -4% of carboxymethyl cellulose (CMC)
1 to 14 percent of modified starch
The balance of deionized water.
4. The application of the bis-imidazolyl ionic liquid-acrylamide copolymer corrosion inhibitor in zinc-manganese battery coated paper according to claim 2, wherein the corrosion inhibitor comprises the following components in percentage by weight: the prepared slurry for the zinc-manganese battery slurry layer paper comprises the following components in percentage by mass:
0.01 to 1 percent of bis-imidazolyl ionic liquid-acrylamide copolymer corrosion inhibitor
Polyvinyl alcohol (PVA) 1-8%
Polyacrylamide (PAM) 20-40%
Carboxymethyl cellulose (CMC) 3% -4%
2 to 13 percent of modified starch
The balance of deionized water.
5. The application of the bis-imidazolyl ionic liquid-acrylamide copolymer corrosion inhibitor in zinc-manganese battery coated paper according to claim 2, which provides a preparation method of the bis-imidazolyl ionic liquid-acrylamide copolymer corrosion inhibitor for preparing slurry for the zinc-manganese battery coated paper, and is characterized in that: the preparation of the slurry comprises the following steps:
s101, uniformly stirring a certain proportion of cross-linked starch and etherified starch in deionized water to prepare modified starch for later use;
s102, dissolving a certain amount of PVA in boiled deionized water, adding quantitative PAM and CMC after complete dissolution, continuously stirring until the mixture is uniformly stirred, and dropwise adding 2mol/L HCl to adjust the pH value of the solution to be acidic;
s103, adding the modified starch and the composite corrosion inhibitor into the solution, and mixing uniformly to obtain slurry;
s104, coating the filtered pulp on base paper by using a wire rod film coating machine, preheating at low temperature, drying at high temperature (95-100 ℃) in a drying stage, ironing at low temperature, and cutting the pulp layer paper for later use.
6. The preparation method of the bis-imidazolyl ionic liquid-acrylamide copolymer corrosion inhibitor for preparing the slurry for the coated paper of the zinc-manganese battery, according to claim 5, is characterized in that: and in the step S102, the pH value of the solution is adjusted to 3.5-5.
7. The preparation method of the bis-imidazolyl ionic liquid-acrylamide copolymer corrosion inhibitor for preparing the slurry for the coated paper of the zinc-manganese battery, according to claim 5, is characterized in that: when the modified starch is a mixture of cross-linked starch and etherified starch, the mass ratio of the cross-linked starch to the etherified starch is as follows: etherified starch =1 (1-5).
8. The preparation method of the bis-imidazolyl ionic liquid-acrylamide copolymer corrosion inhibitor for preparing the slurry for the coated paper of the zinc-manganese battery according to claim 5, wherein the preparation method comprises the following steps: when the modified starch is a mixture of cross-linked starch and etherified starch, the mass ratio of the cross-linked starch to the etherified starch is as follows: etherified starch = 1.5.
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