CN108110234A - A kind of conducting polymer hydrogel and preparation method and application - Google Patents
A kind of conducting polymer hydrogel and preparation method and application Download PDFInfo
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- CN108110234A CN108110234A CN201711325024.4A CN201711325024A CN108110234A CN 108110234 A CN108110234 A CN 108110234A CN 201711325024 A CN201711325024 A CN 201711325024A CN 108110234 A CN108110234 A CN 108110234A
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- conducting polymer
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- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000000017 hydrogel Substances 0.000 title claims abstract description 35
- 239000002322 conducting polymer Substances 0.000 title claims abstract description 27
- 239000000499 gel Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229920000767 polyaniline Polymers 0.000 claims abstract description 28
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 7
- 230000001376 precipitating effect Effects 0.000 claims abstract description 7
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 6
- 239000012046 mixed solvent Substances 0.000 claims abstract description 6
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 6
- 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 5
- 239000010405 anode material Substances 0.000 claims abstract description 5
- 230000003068 static effect Effects 0.000 claims abstract description 4
- 238000001308 synthesis method Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 25
- WREIMONEIYZPSH-UHFFFAOYSA-N aniline prop-2-enoic acid Chemical compound NC1=CC=CC=C1.C(C=C)(=O)O WREIMONEIYZPSH-UHFFFAOYSA-N 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000005030 aluminium foil Substances 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- -1 polypropylene Polymers 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 230000005611 electricity Effects 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 239000003125 aqueous solvent Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000013543 active substance Substances 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229920000876 geopolymer Polymers 0.000 claims 1
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003999 initiator Substances 0.000 abstract description 4
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 description 11
- 238000012360 testing method Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000012536 packaging technology Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/04—Acids; Metal salts or ammonium salts thereof
- C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/02—Polyamines
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- 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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Abstract
A kind of conducting polymer hydrogel and preparation method and application.It is related to a kind of hydrogel and preparation method and application, acrylic monomers and aniline monomer is dissolved in water or water mixed solvent, it is static and be sufficiently stirred；Then, weigh initiator and configure aqueous solution；The common solution into above-mentioned acrylic acid and aniline monomer is slowly added dropwise in the aqueous solution configured; then controlling reaction temperature and carry out under inert gas shielding environment copolymerization 0.5 5 it is small when, the polyacrylic acid doped polyaniline for obtaining one-step synthesis method stablizes layer/polyaniline conductive polymer gel；Then add in precipitating reagent to be precipitated, filter, wash and be dried to obtain sample.The conductive polymer gel prepares lithium battery as positive electrode application, as anode material for lithium-ion batteries, has good charge-discharge performance, cyclical stability and capacity retention ratio.
Description
Technical field
The present invention relates to a kind of hydrogel and preparation method and application, more particularly to a kind of conducting polymer hydrogel
And preparation method and application.
Background technology
High water absorbency polymer be it is a kind of appropriately crosslinked and with three-dimensional net structure new functional macromolecule material, energy
The moisture of tens times or even thousands of times of own wt is absorbed, even if the moisture absorbed will not overflow under elevated pressure.Before 30 years,
High water absorbency polymer progressively expands to other need with preferably water suction and water-retaining property for the first time for agricultural and health care
The field of energy.In recent years, the researcher in relation to high water absorbency polymer mainly develops its new application, such as：Conduction material
Material, biomaterial, sensor, drug release material and absorbing material etc..At present, prepared by the methods of modification, grafting, copolymerization
Multi-functional high water absorbency polymer has become a research hotspot to meet reality needs.
However, the report that conducting polymer and hydrogel are prepared based on high water absorbency polymer is less.Due to conduction
Hydrogel has many advantages, such as that high conductivity, colloidal stability, cheap and preparation process are simple, can be used for preparing fuel electricity
Pond, capacitor, fuel sensitivity solar cell and rechargeable type lithium battery etc..Polyaniline is a kind of high conductivity polymer, is led to
It crosses and is combined with polyacrylate high water absorbency polymer, novel conductive hydrogel can be prepared.However, electrically conductive polyaniline hydrogel
Preparation be typically using two-step method, i.e., first prepare water-soluble polymer gel, then carry out the polymerization process system of polyaniline again
Standby electrically conductive polyaniline hydrogel.Since inorganic molecules acid in polymerization process after polyaniline, need to be introduced as dopant acid, Wu Fabao
It demonstrate,proves dopant acid and continues loss and the influence to polyaniline gel electrical property during use after use.Herein by a step aqueous solution
Polymerization has synthesized poly propenoic acid aniline conductive hydrogel.Due in initial reaction stage by aniline monomer and acrylic monomers
Mixing, the rear layer/polyaniline conductive polymer gel using the generation polyacrylic acid doping of one step of copolymerization process, the doping rate of material and
Electrical property is improved.It is a kind of new method for having promising preparation stable type conducting polymer hydrogel.Stable polyphenyl
Amine electric conductivity and exclusive hydrogel caking property are expected to be applied in terms of organic electrode material of lithium battery.
The content of the invention
It is an object of the invention to provide a kind of conducting polymer hydrogel and preparation method and application, a step of the invention
Method prepares polyaniline/polyacrylic acid conductive polymer gel and applied to anode material of lithium battery；Polyaniline prepared by one-step method
The organic acid doped degree of conductive polymer gel is high, and electric performance stablity, the hydrogel of preparation can be used as a kind of potential anode material
Material is applied to organic lithium ion battery.
The purpose of the present invention is what is be achieved through the following technical solutions：
A kind of conducting polymer hydrogel, the conducting polymer hydrogel are a kind of poly- with structure and electrochemical stability
Acrylic acid/layer/polyaniline conductive polymer gel, which is characterized in that its chemical constitution is such as（1）It is shown：
（1）
A kind of conducting polymer hydrogel preparation method, preparation process trigger polymerization to prepare conducting polymer to coagulate altogether using one-step method
Glue；The described method includes following preparation process：
Acrylic monomers and aniline monomer are dissolved in water or water mixed solvent, it is static and be sufficiently stirred；Then, initiation is weighed
Agent simultaneously configures aqueous solution；The common solution into above-mentioned acrylic acid and aniline monomer is slowly added dropwise in the aqueous solution configured, then
Controlling reaction temperature and carry out under inert gas shielding environment copolymerization 0.5-5 it is small when, obtain one-step synthesis method
Polyacrylic acid doped polyaniline stablizes layer/polyaniline conductive polymer gel；Then add in precipitating reagent precipitated, filter, washing and
It is dried to obtain sample.
A kind of conducting polymer hydrogel preparation method, the poly propenoic acid aniline conductive polymer gel
Using inert gas shielding, such as nitrogen or argon gas inert gas in material synthesis processes.
A kind of conducting polymer hydrogel preparation method, the poly propenoic acid aniline gel rubber material synthesized
Included in journey using aqueous solvent：Water, acetone/water mixed solution, ethyl alcohol and water mixed solution.
A kind of conducting polymer hydrogel preparation method uses oxygen in the conductive polymer gel material synthesis processes
Agent is ammonium persulfate, potassium peroxydisulfate, FeCl3、H2O2。
A kind of conducting polymer hydrogel preparation method, oxygen in the conductive polymer gel material synthesis processes
Agent:The mol/mol of monomer=0.1 ~ 1；Reaction time is 0.5 ~ 5 h；- 20 ~ 60 DEG C of reaction temperature use；Precipitating reagent uses third
Ketone, methanol, ethyl alcohol.
A kind of application of conducting polymer hydrogel, the poly propenoic acid aniline gel rubber material of the preparation is as lithium electricity
Pond positive electrode application；Lithium battery anode piece preparation process is：Positive electricity is prepared using aqueous solvent coating method in aluminium foil surface
Pole piece；By poly propenoic acid aniline gel active substance：Conductive acetylene is black=mass ratio 2 ~ 8：2 ~ 5, it is dispersed in water+alcohol mixing
It mills in solvent and is uniformly overlayed on into sticky on clean aluminium foil, then dry and be made in vacuum drying chamber.
Advantages of the present invention is with effect：
（1）Compared with the method for fractional steps of report prepares poly propenoic acid aniline conductive polymer gel, the polyaniline of one-step method preparation
The features such as organic acid doped degree of conductive polymer gel is high, electric performance stablity, and preparation method is easy.
（2）Compared with the inorganic acid doped polyaniline positive electrode of report, poly- the third of one-step method preparation of the present invention
Olefin(e) acid doped polyaniline gel rubber material has the actual specific capacity of 131.2 mAh/g；Meanwhile electrode prepared by electrode has raising
Cyclical stability, and prepare electrode material self-discharge performance improve the advantages that.Therefore, the polypropylene that prepared by one-step method
Acid/layer/polyaniline conductive polyalcohol hydrogel can be used as a kind of very potential positive electrode to be applied to organic lithium ion battery
In positive electrode.
Description of the drawings
First charge-discharge of Fig. 1 poly propenoic acid aniline conductive polymer gels under 20 mA/g charge-discharge velocities is bent
Line（Voltage range: 2.5~4.2 V vs. Li/Li+）；
Cycling of the Fig. 2 with poly propenoic acid aniline conductive polymer gel positive electrode under 20 mA/g charge-discharge velocities is steady
Determine performance map (voltage range: 2.5~4.2 V vs. Li/Li+) 。
Specific embodiment
The present invention is described in detail for illustrated embodiment below in conjunction with the accompanying drawings.
Fig. 1 poly propenoic acid aniline gelatin polymers (a) and PANI-HCl (b) are in 17 mAg-1Under rate for the first time
Charging and discharging curve.
Fig. 2 poly propenoic acid aniline gels (a) and PANI-HCl (b) are in 17 mAg-1The cycle performance to discharge under rate
Figure.
Poly propenoic acid aniline conducting polymer hydrogel of the present invention, chemical constitution is such as（1）It is shown：
（1）
The present invention also provides an one step preparation method of the poly propenoic acid aniline electrically conductive polyaniline, the method is：By one
Quantitative acrylic monomers and aniline monomer is dissolved in the water or water mixed solvent of certain volume, and static certain time is simultaneously abundant
Stirring.Then, weigh a certain amount of initiator and configure a certain concentration aqueous solution.The aqueous solution configured is slowly added dropwise
The acrylic acid and the common solution of aniline monomer stated, then controlling reaction temperature is in a certain range and under inert gas shielding environment
When progress copolymerization 0.5-5 is small.The polyacrylic acid doped polyaniline for obtaining one-step synthesis method stablizes layer/polyaniline conductive polymerization
Object gel.Then add in precipitating reagent to be precipitated, filter, wash and be dried to obtain sample.
In one one step preparation method, the inert gas of use includes, the gases such as nitrogen, argon gas, preferably argon gas.
In the method, reacting the aqueous solvent of use mainly includes, water, acetone/water mixed solution, the mixing of second alcohol and water
Solution, preferably water.
In the method, oxidant mainly includes, ammonium persulfate, potassium peroxydisulfate, FeCl3、H2O2Deng initiator system of ammonium persulfate.
Further, the middle oxidant that feeds intake is reacted:The mol/mol of monomer=0.1 ~ 1；Reaction time is 0.5 ~ 5 h；Reaction
- 20 ~ 60 DEG C of temperature use；Precipitating reagent is using acetone, methanol, ethyl alcohol etc..
The present invention also provides a kind of application of polyaniline gel prepared as lithium battery anode active material.Specifically,
Anode pole piece preparation process and battery packaging technology are：
The preparation of electrode：Solvent coating method, which is adopted water as, in aluminium foil surface prepares electrode film.By poly propenoic acid aniline gel
Active material：Conductive acetylene is black to be dispersed in water+alcohol in the mixed solvent and mills and uniformly overlayed on into sticky on clean aluminium foil, Ran Hou
It dries and is made in vacuum drying chamber.
Further, electrode substance quality group becomes, active material polymer gel：Conductive agent acetylene black=2 ~ 8：2 ~ 5,
It is preferred that 5 ~ 7：3~4.
The assembling of battery：Using conventional batteries packaging technology.Specifically, electricity is carried out using CR2032 type battery devices system
Chemical property and the charge-discharge performance test in pond.Using lithium as cathode and reference electrode, electrolyte is 1 M LiPF6EC:
DMC =1:1 (v/v) solution, membrane are the microporous polypropylene membranes (Celgard 2300) of industrial use, are prepared before
Electrode for anode, in the glove box of argon gas atmosphere（Water number and oxygen value are below 1 ppm）It is assembled into half electricity of CR2032 simulations
Pond.And it places it in battery test system and carries out constant current charge-discharge test and high rate performance test.
The present invention for the first time should using layer/polyaniline conductive polymer gel prepared by one-step method as anode material for lithium-ion batteries
With on lithium ion battery, and assemble them into simulated battery device and tested and obtain preferable battery performance.
Embodiment 1
The preparation of poly propenoic acid aniline conductive polymer gel
At room temperature, by 15 g acrylic monomers, 0.4656 g aniline monomers, 0.0308 g crosslinking agents are dissolved in 50 ml distilled water
Form aniline acrylates（Such as Fig. 1）Mixed solution.The mixed liquor is stirred evenly and is placed in 50oHeating is stirred in C water-baths
It mixes, the 10 ml solution containing 0.5705 g initiator ammonium persulfates is added dropwise, react and be stirred to react 1 h under inert argon protection.
Reaction polymer gel is precipitated with a large amount of acetone precipitations, and is filtered, washs, dried, and obtains the production of poly propenoic acid aniline hydrogel
Object.
Embodiment 2
The preparation of electrode and battery assembling
（1）The preparation of electrode.Electrode slice is prepared using coating method in aluminium foil surface.By active material polymer powder：Conductive agent
Acetylene black=mass ratio 7：3 ratios formation viscous liquid soluble in water.The liquid is coated in the scraper of 90 nm again clean
Aluminium foil on, then 60oVacuum drying is until film quality is constant under C.
（2）The assembling of battery.Herein mainly using CR2032 type battery devices system carry out battery chemical property and
Charge-discharge performance is tested.Using lithium as cathode and reference electrode, electrolyte is the EC of 1 M LiPF6:DMC =1:1 (v/v) is molten
Liquid, membrane are the microporous polypropylene membranes (Celgard 2300) of industrial use, and the electrode prepared before is anode, in argon
In the glove box of gas atmosphere（Water number and oxygen value are below 1 ppm）It is assembled into CR2032 simulation half-cells.Before test, will first it install
Battery be placed on 12 h in drier.This measure is for electrolyte and pole piece is made preferably to infiltrate, so that test data is more steady
It is fixed.Electrochemical property test is carried out to the battery being prepared, in the case where current density is the charge-discharge velocity of 20 mA/g, 1
mol/L LiPF6 EC/DMC(V/V, 1:1) in electrolyte, charge and discharge and cycling are carried out in 2.5 V-4.2 V voltage ranges
Performance test.
Battery performance test shows that poly propenoic acid aniline conductive polymer gel is shown as cell positive material
Higher specific discharge capacity（131.2 mAh/g）（Fig. 1）, and with improved cyclical stability（Fig. 2）.The simulation button electricity of assembling
The storage performance in pond is improved, and is stored by 2 months, and capacity retention ratio is the 70% of initial capacity（More traditional salt
52 % capacity retention ratios of acid doped polyaniline anode）.
Claims (7)
1. a kind of conducting polymer hydrogel, which is characterized in that the conducting polymer hydrogel has structure and electricity to be a kind of
The poly propenoic acid aniline conductive polymer gel of chemical stability, which is characterized in that its chemical constitution is such as（1）It is shown：
（1）.
2. a kind of conducting polymer hydrogel preparation method, which is characterized in that preparation process triggers polymerization to make altogether using one-step method
Standby conductive polymer gel；The described method includes following preparation process：
Acrylic monomers and aniline monomer are dissolved in water or water mixed solvent, it is static and be sufficiently stirred；Then, initiation is weighed
Agent simultaneously configures aqueous solution；The common solution into above-mentioned acrylic acid and aniline monomer is slowly added dropwise in the aqueous solution configured, then
Controlling reaction temperature and carry out under inert gas shielding environment copolymerization 0.5-5 it is small when, obtain one-step synthesis method
Polyacrylic acid doped polyaniline stablizes layer/polyaniline conductive polymer gel；Then add in precipitating reagent precipitated, filter, washing and
It is dried to obtain sample.
A kind of 3. conducting polymer hydrogel preparation method according to claim 2, which is characterized in that the polypropylene
Using inert gas shielding, such as nitrogen or argon gas inert gas in acid/layer/polyaniline conductive geopolymer gel material building-up process.
A kind of 4. conducting polymer hydrogel preparation method according to claim 2, which is characterized in that the polypropylene
Included in acid/polyaniline gel material synthesis processes using aqueous solvent：Water, acetone/water mixed solution, the mixing of second alcohol and water are molten
Liquid.
A kind of 5. conducting polymer hydrogel preparation method according to claim 2, which is characterized in that the conducting polymer
Oxidant is used in object gel rubber material building-up process as ammonium persulfate, potassium peroxydisulfate, FeCl3、H2O2。
A kind of 6. conducting polymer hydrogel preparation method according to claim 2, which is characterized in that the conducting polymer
Oxidant in object gel rubber material building-up process:The mol/mol of monomer=0.1 ~ 1；Reaction time is 0.5 ~ 5 h；Reaction temperature use-
20~60℃；Precipitating reagent is using acetone, methanol, ethyl alcohol.
A kind of 7. application of conducting polymer hydrogel, which is characterized in that the poly propenoic acid aniline gel rubber material of the preparation
As anode material of lithium battery application；Lithium battery anode piece preparation process is：Aqueous solvent coating method is used in aluminium foil surface
Prepare electrode film；By poly propenoic acid aniline gel active substance：Conductive acetylene is black=mass ratio 2 ~ 8：2 ~ 5, it is dispersed in water
+ alcohol in the mixed solvent is milled and is uniformly overlayed on into sticky on clean aluminium foil, then dries and is made in vacuum drying chamber.
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| CN108794773A (en) * | 2018-06-29 | 2018-11-13 | 四川理工学院 | A kind of preparation method of conductive hydrogel |
| CN112940643A (en) * | 2021-01-20 | 2021-06-11 | 南京师范大学 | Double-polymer gel material and preparation method and application thereof |
| CN113363574A (en) * | 2021-06-21 | 2021-09-07 | 广东工业大学 | Polymer electrolyte and preparation method thereof |
| CN117050689A (en) * | 2023-07-28 | 2023-11-14 | 江苏理工学院 | Preparation method and application of conductive polymer adhesive |
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| CN108794773A (en) * | 2018-06-29 | 2018-11-13 | 四川理工学院 | A kind of preparation method of conductive hydrogel |
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| CN112940643A (en) * | 2021-01-20 | 2021-06-11 | 南京师范大学 | Double-polymer gel material and preparation method and application thereof |
| CN113363574A (en) * | 2021-06-21 | 2021-09-07 | 广东工业大学 | Polymer electrolyte and preparation method thereof |
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| CN117050689B (en) * | 2023-07-28 | 2024-03-19 | 江苏理工学院 | Preparation method and application of conductive polymer adhesive |
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