CN114381016A - Method for in-situ synthesis of polyaniline/manganese dioxide composite hydrogel and application thereof - Google Patents
Method for in-situ synthesis of polyaniline/manganese dioxide composite hydrogel and application thereof Download PDFInfo
- Publication number
- CN114381016A CN114381016A CN202111626391.4A CN202111626391A CN114381016A CN 114381016 A CN114381016 A CN 114381016A CN 202111626391 A CN202111626391 A CN 202111626391A CN 114381016 A CN114381016 A CN 114381016A
- Authority
- CN
- China
- Prior art keywords
- polyaniline
- manganese dioxide
- dioxide composite
- composite hydrogel
- manganese
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 101
- 239000000017 hydrogel Substances 0.000 title claims abstract description 85
- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 23
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 10
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 150000002696 manganese Chemical class 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000004108 freeze drying Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000007774 positive electrode material Substances 0.000 claims description 10
- 229940099596 manganese sulfate Drugs 0.000 claims description 7
- 235000007079 manganese sulphate Nutrition 0.000 claims description 7
- 239000011702 manganese sulphate Substances 0.000 claims description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 239000002121 nanofiber Substances 0.000 abstract description 13
- 239000010405 anode material Substances 0.000 abstract description 5
- 238000004146 energy storage Methods 0.000 abstract description 4
- 230000000717 retained effect Effects 0.000 abstract description 3
- 239000000843 powder Substances 0.000 description 35
- 230000002194 synthesizing effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000007772 electrode material Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0052—Preparation of 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- 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
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
-
- 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
- H01M4/606—Polymers containing aromatic main chain polymers
-
- 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
- C08J2379/00—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 C08J2361/00 - C08J2377/00
- C08J2379/02—Polyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2262—Oxides; Hydroxides of metals of manganese
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a method for in-situ synthesis of polyaniline/manganese dioxide composite hydrogel and application thereof. The method comprises the following steps: 1) dissolving sodium dodecyl benzene sulfonate, aniline hydrochloride and divalent manganese salt in deionized water to obtain a mixed solution system; 2) cooling the mixed solution system obtained in the step 1) to 0-4 ℃, adding an oxidant, uniformly mixing, and standing for reaction to obtain a stable polyaniline hydrogel mixed system; 3) carrying out hydrothermal reaction on the polyaniline hydrogel mixed system obtained in the step 2), washing after the reaction is finished, and carrying out freeze drying to obtain the polyaniline/manganese dioxide composite hydrogel. The method is simple to prepare, the polyaniline/manganese dioxide composite hydrogel is obtained by in-situ synthesis, the nanofiber structure of polyaniline is retained to the maximum extent, and manganese dioxide is uniformly dispersed in the nanofiber structure of polyaniline, so that the energy storage capacity of a composite system is effectively improved, and the application potential of the polyaniline-based zinc-ion battery anode material is increased.
Description
Technical Field
The invention belongs to the technical field of chemical power supplies, and particularly relates to a method for in-situ synthesis of polyaniline/manganese dioxide composite hydrogel and a zinc ion battery anode material prepared by the same.
Background
Chemical power sources are widely used as efficient energy conversion and storage devices in mobile communication equipment, daily necessities, aerospace, machinery and the like. Due to high energy density, long service life and high energy efficiency, lithium ion batteries are one of the most widely used energy storage devices at present. However, flammable and explosive organic electrolytes, limited lithium reserves and high prices have become significant challenges in lithium ion battery applications. In view of this, a zinc ion battery comprising a zinc metal negative electrode, a zinc ion aqueous electrolyte and a positive electrode is in the spotlight of researchers. This is due to its following significant advantages: the zinc metal has abundant resources and high chemical stability, and has suitable oxidation-reduction potential (-0.76V vs. standard hydrogen electrode) and high theoretical specific capacity (the mass and volume specific capacity are 820mAh g respectively)-1And 5855mAh cm-3) (ii) a Neutral zinc salt (ZnSO)4Etc.) the aqueous solution is an electrolyte, and has the advantages of low cost, safety, high ionic conductivity, environmental friendliness and the like. These advantages make it haveHas great competitiveness and application potential. However, due to Zn2+The high polarization characteristic of the zinc-ion battery, and the narrow potential window in which the aqueous electrolyte can stably exist, are important for developing a suitable positive electrode material for the zinc-ion battery.
Polyaniline is a zinc ion organic positive electrode material which is researched more at present, has inherent advantages of organic electrode materials such as resource sustainability, environmental friendliness and structural diversity, has good conductivity and electrochemical activity, and is considered to be one of the most potential zinc ion organic positive electrode materials. Patent CN112736244A proposes polyaniline hydrogel with crosslinked nanofiber structure, which is used as positive material of zinc ion battery to obtain ideal electrochemical performance. However, the specific capacity is limited, which limits the popularization and application of the composite material to a certain extent.
Disclosure of Invention
The invention aims to provide a method for in-situ synthesis of polyaniline/manganese dioxide composite hydrogel and application thereof, which are used for solving the problem of limited energy storage capacity of a polyaniline-based zinc-ion battery anode material. The method is simple to prepare, the polyaniline/manganese dioxide composite hydrogel is obtained by in-situ synthesis, the nanofiber structure of polyaniline is retained to the maximum extent, and manganese dioxide is uniformly dispersed in the nanofiber structure of polyaniline, so that the energy storage capacity of a composite system is effectively improved, and the application potential of the polyaniline-based zinc-ion battery anode material is increased.
In order to solve the technical problems, the invention adopts the following technical scheme:
the method for synthesizing the polyaniline/manganese dioxide composite hydrogel in situ comprises the following steps:
1) dissolving sodium dodecyl benzene sulfonate, aniline hydrochloride and divalent manganese salt in deionized water to obtain a mixed solution system;
2) cooling the mixed solution system obtained in the step 1) to 0-4 ℃, adding an oxidant, uniformly mixing, and standing for reaction to obtain a stable polyaniline hydrogel mixed system;
3) carrying out hydrothermal reaction on the polyaniline hydrogel mixed system obtained in the step 2), washing after the reaction is finished, and carrying out freeze drying to obtain polyaniline/manganese dioxide composite hydrogel powder.
According to the scheme, in the step 1), the mol ratio of the sodium dodecyl benzene sulfonate to the aniline hydrochloride is 1: (1.5-5), wherein the molar ratio of the divalent manganese salt to the aniline hydrochloride is 1: (0.1-10).
According to the scheme, in the step 1), the concentration of the aniline hydrochloride is 0.01-3.0 mol/L.
According to the scheme, in the step 1), the divalent manganese salt is selected from one or a combination of manganese sulfate, manganese nitrate, manganese acetate and manganese chloride.
According to the scheme, in the step 2), the oxidant is selected from one or more of ammonium persulfate, potassium persulfate, sodium persulfate, ferric chloride, ferric sulfate, ferric nitrate and hydrogen peroxide.
According to the scheme, in the step 2), the molar ratio of the oxidant to the sum of the divalent manganese salt and the aniline hydrochloride is 1 (0.8-2).
According to the scheme, in the step 2), the standing reaction conditions are as follows: the time is 1-72 h, and the temperature is 0-40 ℃.
According to the scheme, in the step 3), the hydrothermal reaction conditions are as follows: the temperature is 80-140 ℃ and the time is 1-48 h.
Provides an application of the polyaniline/manganese dioxide composite hydrogel prepared by the method as a positive electrode material in a zinc ion battery.
The invention provides a novel method for in-situ synthesis of polyaniline/manganese dioxide composite hydrogel, which is characterized in that dodecylbenzene sulfonic acid is added into a reaction system as a template agent and is mixed with aniline hydrochloride and divalent manganese salt, the dodecylbenzene sulfonic acid and the aniline hydrochloride are assembled to form a fiber structure under the electrostatic action and the pi-pi stacking action, and the divalent manganese salt is uniformly distributed in the formed fiber structure. After the oxidant is added, polyaniline fiber is generated in situ and is further wound to form stable block-shaped hydrogel, the microstructure of the hydrogel is formed by wound fibers, manganese dioxide is generated in situ by manganous salt and is uniformly attached to the surface of polyaniline nanofiber, and the problem that nanoparticles are easy to agglomerate in the traditional preparation method is solved.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides a novel method for in-situ synthesis of polyaniline/manganese dioxide composite hydrogel, which is characterized in that dodecylbenzenesulfonic acid is added into a reaction system as a template agent and is mixed with aniline hydrochloride and divalent manganese salt, the divalent manganese salt is uniformly distributed in a formed fiber structure, the aniline and the divalent manganese salt are oxidized into polyaniline and manganese dioxide after an oxidant is added, manganese dioxide nanoparticles generated in situ are uniformly attached to the surface of polyaniline nanofibers to obtain the polyaniline/manganese dioxide composite hydrogel which has a complete nanofiber structure, the manganese dioxide is uniformly distributed in the nanofiber structure to provide a continuous conductive path for an electrode, fully exert the action of manganese, improve the electrochemical zinc storage performance of the composite system, and further increase the application potential of a polyaniline-based zinc ion battery anode material.
2. According to the invention, the oxidant is added for one-pot reaction to oxidize the aniline and the divalent manganese salt into the polyaniline and the manganese dioxide, so that the nanofiber structure of the polyaniline is retained to the greatest extent, the defect that the traditional preparation method of nano manganese dioxide is easy to agglomerate is overcome, the process is simpler, the cost is lower, and the method has a wider industrial application prospect.
Drawings
Fig. 1 is a comparison of scanning electron micrographs of a polyaniline/manganese dioxide composite hydrogel (a) prepared in example 4 and a polyaniline hydrogel (b) prepared in comparative example 1.
FIG. 2A positive electrode material of a zinc ion battery with polyaniline/manganese dioxide composite hydrogel prepared in example 4, wherein the current density of the positive electrode material is 0.2Ag-1Charge and discharge curves at current density.
FIG. 3A positive electrode material of a zinc ion battery with polyaniline/manganese dioxide composite hydrogel prepared in example 5, wherein the current density of the positive electrode material is 0.2Ag-1Charge and discharge curves at current density.
FIG. 4 shows that the current density of the positive electrode material of the polyaniline hydrogel zinc-ion battery prepared in comparative example 1 is 0.2Ag-1Charge and discharge curves at current density.
Detailed Description
The invention is further illustrated by the following examples.
Example 1
The method for synthesizing the polyaniline/manganese dioxide composite hydrogel in situ comprises the following steps:
sodium dodecyl benzene sulfonate (1mmol), aniline hydrochloride (2mmol) and manganese sulfate (2mmol) are dissolved in 10mL deionized water to obtain a mixed solution system. And cooling the mixed solution system to 0-4 ℃, adding ferric chloride (4mmol), uniformly mixing, and standing at 4 ℃ for reaction for 12 hours to obtain a stable polyaniline hydrogel mixed system. And then placing the polyaniline/manganese dioxide composite hydrogel powder into a hydrothermal kettle, processing the polyaniline/manganese dioxide composite hydrogel powder for 12 hours at the temperature of 140 ℃, washing the polyaniline/manganese dioxide composite hydrogel powder for 5 times by using deionized water, and freeze-drying the polyaniline/manganese dioxide composite hydrogel powder to obtain the polyaniline/manganese dioxide composite hydrogel powder.
Example 2
The method for synthesizing the polyaniline/manganese dioxide composite hydrogel in situ comprises the following steps:
sodium dodecyl benzene sulfonate (1mmol), aniline hydrochloride (3mmol) and manganese sulfate (2mmol) are dissolved in 10mL deionized water to obtain a mixed solution system. And cooling the mixed solution system to 0-4 ℃, adding ferric chloride (6mmol), uniformly mixing, and standing at 4 ℃ for reaction for 12 hours to obtain a stable polyaniline hydrogel mixed system. And then placing the polyaniline/manganese dioxide composite hydrogel powder into a hydrothermal kettle, processing the polyaniline/manganese dioxide composite hydrogel powder for 12 hours at the temperature of 140 ℃, washing the polyaniline/manganese dioxide composite hydrogel powder for 5 times by using deionized water, and freeze-drying the polyaniline/manganese dioxide composite hydrogel powder to obtain the polyaniline/manganese dioxide composite hydrogel powder.
Example 3
The method for synthesizing the polyaniline/manganese dioxide composite hydrogel in situ comprises the following steps:
sodium dodecyl benzene sulfonate (2mmol), aniline hydrochloride (3mmol) and manganese sulfate (2mmol) are dissolved in 10mL deionized water to obtain a mixed solution system. And cooling the mixed solution system to 0-4 ℃, adding ferric nitrate (5mmol), uniformly mixing, and standing at 4 ℃ for reaction for 12 hours to obtain a stable polyaniline hydrogel mixed system. And then placing the polyaniline/manganese dioxide composite hydrogel powder into a hydrothermal kettle, processing the polyaniline/manganese dioxide composite hydrogel powder for 12 hours at the temperature of 140 ℃, washing the polyaniline/manganese dioxide composite hydrogel powder for 5 times by using deionized water, and freeze-drying the polyaniline/manganese dioxide composite hydrogel powder to obtain the polyaniline/manganese dioxide composite hydrogel powder.
Example 4
The method for synthesizing the polyaniline/manganese dioxide composite hydrogel in situ comprises the following steps:
sodium dodecyl benzene sulfonate (1mmol), aniline hydrochloride (3mmol) and manganese sulfate (3mmol) are dissolved in 10mL deionized water to obtain a mixed solution system. And cooling the mixed solution system to 0-4 ℃, adding ammonium persulfate (6mmol), uniformly mixing, and standing at 4 ℃ for reaction for 12 hours to obtain a stable polyaniline hydrogel mixed system. And then placing the polyaniline/manganese dioxide composite hydrogel powder into a hydrothermal kettle, processing the polyaniline/manganese dioxide composite hydrogel powder for 12 hours at the temperature of 140 ℃, washing the polyaniline/manganese dioxide composite hydrogel powder for 5 times by using deionized water, and freeze-drying the polyaniline/manganese dioxide composite hydrogel powder to obtain the polyaniline/manganese dioxide composite hydrogel powder.
Example 5
The method for synthesizing the polyaniline/manganese dioxide composite hydrogel in situ comprises the following steps:
sodium dodecyl benzene sulfonate (1mmol), aniline hydrochloride (3mmol) and manganese sulfate (5mmol) are dissolved in 10mL deionized water to obtain a mixed solution system. And cooling the mixed solution system to 0-4 ℃, adding ammonium persulfate (5mmol), uniformly mixing, and standing at 4 ℃ for reaction for 12 hours to obtain a stable polyaniline hydrogel mixed system. And then placing the polyaniline/manganese dioxide composite hydrogel powder into a hydrothermal kettle, processing the polyaniline/manganese dioxide composite hydrogel powder for 12 hours at the temperature of 140 ℃, washing the polyaniline/manganese dioxide composite hydrogel powder for 5 times by using deionized water, and freeze-drying the polyaniline/manganese dioxide composite hydrogel powder to obtain the polyaniline/manganese dioxide composite hydrogel powder.
Example 6
The method for synthesizing the polyaniline/manganese dioxide composite hydrogel in situ comprises the following steps:
sodium dodecyl benzene sulfonate (1mmol), aniline hydrochloride (3mmol) and manganese acetate (3mmol) are dissolved in 10mL deionized water to obtain a mixed solution system. And cooling the mixed solution system to 0-4 ℃, adding ammonium persulfate (6mmol), uniformly mixing, and standing at room temperature for 6h to obtain a stable polyaniline hydrogel mixed system. And then placing the polyaniline/manganese dioxide composite hydrogel powder into a hydrothermal kettle, processing the polyaniline/manganese dioxide composite hydrogel powder for 12 hours at the temperature of 140 ℃, washing the polyaniline/manganese dioxide composite hydrogel powder for 5 times by using deionized water, and freeze-drying the polyaniline/manganese dioxide composite hydrogel powder to obtain the polyaniline/manganese dioxide composite hydrogel powder.
Example 7
The method for synthesizing the polyaniline/manganese dioxide composite hydrogel in situ comprises the following steps:
sodium dodecyl benzene sulfonate (1mmol), aniline hydrochloride (3mmol) and manganese chloride (5mmol) are dissolved in 10mL deionized water to obtain a mixed solution system. And cooling the mixed solution system to 0-4 ℃, adding ammonium persulfate (8mmol), uniformly mixing, and standing at 4 ℃ for reaction for 12 hours to obtain a stable polyaniline hydrogel mixed system. And then placing the polyaniline/manganese dioxide composite hydrogel powder into a hydrothermal kettle, processing the polyaniline/manganese dioxide composite hydrogel powder for 24 hours at 120 ℃, washing the polyaniline/manganese dioxide composite hydrogel powder for 5 times by using deionized water, and freeze-drying the polyaniline/manganese dioxide composite hydrogel powder.
Comparative example 1
In order to reflect the superiority of the structure of the polyaniline/manganese dioxide composite hydrogel prepared by the invention, the invention also provides a comparative experiment, and pure polyaniline hydrogel systems are respectively prepared.
Compared with the example 4, the specific preparation process is different only in that: no divalent manganese salt was added during the preparation and the molar amount of oxidant used was the same as the molar amount of aniline hydrochloride used, otherwise the procedure was identical to that of example 4.
Scanning electron microscope characterization was performed on the products prepared in example 4 and comparative example 1, and the results are shown in fig. 1a and 1 b. As can be clearly seen from fig. 1a, the typical nanofiber-like microstructure of the polyaniline/manganese dioxide composite hydrogel, and the manganese dioxide nanoparticles are uniformly distributed on the surface of the polyaniline fiber. These particles are formed in situ on the surface of the polyaniline nanofibers during hydrothermal treatment. In fig. 1b, only polyaniline nanofibers are visible, and no nanoparticles are visible on the surface of the nanofibers. This is caused by the fact that manganese dioxide cannot be formed in situ because no divalent manganese salt is added to the reaction raw materials.
FIGS. 2 to 4 are graphs showing that the electrode materials prepared in example 4, example 5 and comparative example 1 are 0.2Ag-1Under the condition of chargingDischarge curve. The specific discharge capacity of the polyaniline/manganese dioxide composite hydrogel electrode material prepared in example 4 is 172mAhg-1With the increase of the amount of the divalent manganese salt, the amount of manganese dioxide formed in the system will also increase correspondingly, so that the specific discharge capacity of the electrode material prepared in example 5 is higher, reaching 242mAhg-1. The specific capacity of the pure polyaniline hydrogel electrode material (comparative example 1) is only 111mAhg-1. The composite hydrogel electrode material is proved to be capable of playing a role in higher electrochemical energy storage capacity under the synergistic effect of polyaniline and manganese dioxide.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A method for in-situ synthesis of polyaniline/manganese dioxide composite hydrogel is characterized by comprising the following steps:
1) dissolving sodium dodecyl benzene sulfonate, aniline hydrochloride and divalent manganese salt in deionized water to obtain a mixed solution system;
2) cooling the mixed solution system obtained in the step 1) to 0-4 ℃, adding an oxidant, uniformly mixing, and standing for reaction to obtain a stable polyaniline hydrogel mixed system;
3) carrying out hydrothermal reaction on the polyaniline hydrogel mixed system obtained in the step 2), washing after the reaction is finished, and carrying out freeze drying to obtain the polyaniline/manganese dioxide composite hydrogel.
2. The method according to claim 1, wherein in the step 1), the molar ratio of the sodium dodecyl benzene sulfonate to the aniline hydrochloride is 1: (1.5-5), wherein the molar ratio of the divalent manganese salt to the aniline hydrochloride is 1: (0.1-10).
3. The method according to claim 1, wherein the concentration of aniline hydrochloride in step 1) is 0.01-3.0 mol/L.
4. The method as claimed in claim 1), wherein in step 1), the divalent manganese salt is selected from one or more of manganese sulfate, manganese nitrate, manganese acetate and manganese chloride.
5. The method according to claim 1, wherein in the step 2), the oxidizing agent is selected from one or more of ammonium persulfate, potassium persulfate, sodium persulfate, ferric chloride, ferric sulfate, ferric nitrate and hydrogen peroxide.
6. The method according to claim 1, wherein in the step 2), the molar ratio of the oxidant to the sum of the divalent manganese salt and the aniline hydrochloride is 1 (0.8-2).
7. The method according to claim 1, wherein in the step 2), the conditions of the standing reaction are as follows: the time is 1-72 h, and the temperature is 0-40 ℃.
8. The method according to claim 1, wherein in the step 3), the hydrothermal reaction conditions are as follows: the temperature is 80-140 ℃ and the time is 1-48 h.
9. The application of the polyaniline/manganese dioxide composite hydrogel prepared by the method of any one of claims 1 to 8 as a positive electrode material in a zinc ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111626391.4A CN114381016B (en) | 2021-12-28 | 2021-12-28 | Method for in-situ synthesis of polyaniline/manganese dioxide composite hydrogel and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111626391.4A CN114381016B (en) | 2021-12-28 | 2021-12-28 | Method for in-situ synthesis of polyaniline/manganese dioxide composite hydrogel and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114381016A true CN114381016A (en) | 2022-04-22 |
| CN114381016B CN114381016B (en) | 2024-07-23 |
Family
ID=81198049
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111626391.4A Active CN114381016B (en) | 2021-12-28 | 2021-12-28 | Method for in-situ synthesis of polyaniline/manganese dioxide composite hydrogel and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114381016B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696323A (en) * | 2009-10-30 | 2010-04-21 | 华南师范大学 | Method for preparing polyaniline/manganese dioxide composite material for super capacitor |
| CN102408712A (en) * | 2011-09-22 | 2012-04-11 | 扬州大学 | Polyaniline nanofiber/manganese dioxide nanorod composite material and preparation method thereof |
| CN106684331A (en) * | 2016-07-22 | 2017-05-17 | 武汉理工大学 | Rodlike manganese dioxide/polyaniline composite material as well as preparation method and application of rodlike manganese dioxide |
| CN111416096A (en) * | 2020-03-24 | 2020-07-14 | 中南大学 | Graphene oxide/polyaniline/manganese dioxide composite electrode, preparation method thereof and application thereof in seawater battery |
| CN112736244A (en) * | 2020-12-24 | 2021-04-30 | 武汉工程大学 | Preparation method of zinc ion battery positive electrode material and electrode material prepared by preparation method |
-
2021
- 2021-12-28 CN CN202111626391.4A patent/CN114381016B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696323A (en) * | 2009-10-30 | 2010-04-21 | 华南师范大学 | Method for preparing polyaniline/manganese dioxide composite material for super capacitor |
| CN102408712A (en) * | 2011-09-22 | 2012-04-11 | 扬州大学 | Polyaniline nanofiber/manganese dioxide nanorod composite material and preparation method thereof |
| CN106684331A (en) * | 2016-07-22 | 2017-05-17 | 武汉理工大学 | Rodlike manganese dioxide/polyaniline composite material as well as preparation method and application of rodlike manganese dioxide |
| CN111416096A (en) * | 2020-03-24 | 2020-07-14 | 中南大学 | Graphene oxide/polyaniline/manganese dioxide composite electrode, preparation method thereof and application thereof in seawater battery |
| CN112736244A (en) * | 2020-12-24 | 2021-04-30 | 武汉工程大学 | Preparation method of zinc ion battery positive electrode material and electrode material prepared by preparation method |
Non-Patent Citations (1)
| Title |
|---|
| C. ANJU等: "Effect of Mn2+ as a redox additive on ternary doped polyaniline‑metal nanocomposite: an efficient dielectric material", 《JOURNAL OF MATERIALS SCIENCE: MATERIALS IN ELECTRONICS》, vol. 30, 11 November 2019 (2019-11-11), pages 21138 - 21149, XP036951018, DOI: 10.1007/s10854-019-02484-6 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114381016B (en) | 2024-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Selvakumaran et al. | A review on recent developments and challenges of cathode materials for rechargeable aqueous Zn-ion batteries | |
| Zhao et al. | A chemistry and material perspective on lithium redox flow batteries towards high-density electrical energy storage | |
| Nakamoto et al. | Electrolyte dependence of the performance of a Na2FeP2O7//NaTi2 (PO4) 3 rechargeable aqueous sodium-ion battery | |
| CN102185140B (en) | Preparation method of nano-network conductive polymer coated lithium iron phosphate anode material | |
| CN103682274B (en) | A kind of graphene/polyaniline/sulphur composite and preparation method thereof | |
| CN105514378B (en) | A kind of imitative eucaryotic cell structure anode composite material of lithium sulfur battery and preparation method thereof | |
| CN101764254B (en) | Secondary aluminum battery and preparation method of anode thereof | |
| CN105140490B (en) | A kind of flexible anode preparation method of lithium-sulfur cell | |
| CN103259000A (en) | Polypyrrole hollow microsphere/ sulfur composite material as well as preparation method and application thereof | |
| CN107204437A (en) | A kind of preparation method of lithium selenium cell positive electrode | |
| CN113270577B (en) | Aqueous zinc ion battery and positive electrode material | |
| CN108832098A (en) | Lithium-sulphur cell positive electrode S@TiO2/ Pt/Polypyrrole composite material and preparation method | |
| CN114695973A (en) | Preparation method of low-temperature zinc ion battery | |
| CN101901937A (en) | Cerium ion electrolyte using silver ion as anode catalyst and preparation method thereof | |
| CN107871860B (en) | Preparation method of manganese cobalt oxide coated by lithium metatitanate, product and application thereof | |
| CN106058229A (en) | Lithium-sulfur battery positive electrode material and preparation method thereof | |
| CN112736244A (en) | Preparation method of zinc ion battery positive electrode material and electrode material prepared by preparation method | |
| CN117080584A (en) | Maltitol-containing aqueous zinc ion electrolyte additive and application thereof | |
| CN114381016A (en) | Method for in-situ synthesis of polyaniline/manganese dioxide composite hydrogel and application thereof | |
| CN115911377A (en) | Sulfur positive electrode material and preparation method thereof | |
| CN103579597B (en) | Lithium ion secondary battery cathode material lithium titanate composite material and preparation method | |
| CN110299524B (en) | MnO for preparing lithium ion battery negative electrode material2Method for producing Ag | |
| CN111675249B (en) | Preparation method of copper-loaded ternary nanobelt cathode material, product and application thereof | |
| CN111570821B (en) | Nano-silver particle composite sulfur material for lithium-sulfur battery and preparation method thereof | |
| CN110474031B (en) | Method for preparing copper-doped manganous-manganic oxide composite material by using polymeric complexing agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |