CN112736244B - Preparation method of zinc ion battery positive electrode material and electrode material prepared by preparation method - Google Patents
Preparation method of zinc ion battery positive electrode material and electrode material prepared by preparation method Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000007774 positive electrode material Substances 0.000 title claims description 9
- 239000007772 electrode material Substances 0.000 title abstract description 16
- 229920000767 polyaniline Polymers 0.000 claims abstract description 52
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 27
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims abstract description 26
- 239000000017 hydrogel Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 239000010405 anode material Substances 0.000 claims abstract description 10
- 238000004108 freeze drying Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 11
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 9
- 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 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 239000012286 potassium permanganate Substances 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
- 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
- 239000010406 cathode material Substances 0.000 claims 1
- 230000001351 cycling effect Effects 0.000 abstract description 12
- 239000002121 nanofiber Substances 0.000 abstract description 9
- 230000000052 comparative effect Effects 0.000 description 27
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 239000005457 ice water Substances 0.000 description 8
- 239000011701 zinc Substances 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- -1 alum series Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004146 energy storage Methods 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
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- 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
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical group N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- MMCPOSDMTGQNKG-UJZMCJRSSA-N aniline;hydrochloride Chemical compound Cl.N[14C]1=[14CH][14CH]=[14CH][14CH]=[14CH]1 MMCPOSDMTGQNKG-UJZMCJRSSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
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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
- H01M4/606—Polymers containing aromatic main chain polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation method of a zinc ion battery anode material and an electrode material prepared by the preparation method, which comprises the following steps: respectively dissolving sodium dodecyl benzene sulfonate and aniline hydrochloride into water to obtain a mixed solution system, wherein the concentration of the sodium dodecyl benzene sulfonate is 0.01-1.0 mol/L, the concentration of the aniline hydrochloride is 0.03-3.0 mol/L, and the molar ratio of the sodium dodecyl benzene sulfonate to the aniline hydrochloride is 1 (3-5); cooling the mixed solution system to 0-4 ℃, adding an oxidant, uniformly mixing, and standing for reaction to obtain stable polyaniline hydrogel, wherein the molar ratio of the oxidant to the aniline hydrochloride is 0.1-3.0; and washing the polyaniline hydrogel with water for a plurality of times, and freeze-drying to obtain the polyaniline material. The preparation method of the zinc ion battery anode material is simple in preparation and low in preparation cost; the prepared polyaniline hydrogel zinc ion battery anode material has a complete nanofiber structure, and the cycling stability of the electrode material is improved.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a preparation method of a zinc ion battery positive electrode material and an electrode material prepared by the preparation method.
Background
Due to the high energy density, long life and high energy efficiency, lithium ion batteries are one of the most widely used energy storage devices today, however, flammable, explosive organic electrolytes, limited lithium reserves and high prices are significant challenges in lithium ion battery applications. For this reason, some aqueous metal ion batteries, which are rich in element reserves and inexpensive, are increasingly attracting attention of researchers, and among them, zinc ion batteries composed of a zinc metal anode, a zinc ion aqueous electrolyte and a cathode are favored by researchers, which is that zinc has the following significant advantages: the zinc metal has rich resources, high chemical stability, proper oxidation-reduction potential (-0.76V vs. standard hydrogen electrode) and high theoretical specific capacity (820 mAh.g) -1 ) The method comprises the steps of carrying out a first treatment on the surface of the The neutral zinc salt aqueous solution is electrolyte, has the advantages of low cost, safety, high ionic conductivity, environmental friendliness and the like, and has great competitiveness in large-scale application as an energy storage device. However, for zinc ion batteries, due to Zn 2+ The high polarization characteristics of (2) and the narrow potential window in which the aqueous electrolyte can stably exist are important in developing a suitable positive electrode material.
Currently, research on positive electrode materials of zinc ion batteries is becoming a research hotspot, and four types of reported material systems mainly exist: manganese series, alum series, prussian blue series compounds and organic materials. The three electrode materials are inorganic matters and mainly derived from mineral matters, so that the natural environment is damaged by over mining, and the problem of resource withholding is likely to be faced in the future; in addition, they all have the difficult problems of poor conductivity and poor cycling stability. At present, the research on organic electrode materials is not more visible, and although the capacity is not particularly outstanding, the organic electrode materials have the characteristics of resource sustainability, structural diversity, designability, flexibility and the like, and are important development directions in the future.
In the organic electronic material, polyaniline has good conductivity and is synthesizedSimple and environment-friendly, is one of the most studied organic anode materials of zinc ion batteries, and although polyaniline has ideal conductivity and electrochemical zinc storage capacity, the cycling stability in the charge and discharge process is not ideal. In order to solve the above problems, sun et al synthesized a polyaniline copolymer positive electrode (Angewandte Chemie International Edition,2018,57,16359-16363) having a self-doping structure, and had a complex synthesis process; chen et al utilized a novel electrolyte (Zn (CF 3 SO 3 ) 2) constructing the polyaniline-based zinc ion battery (Advanced Functional Materials 2018,28, 1804975) with a composite zinc storage mechanism. Although they all achieve ideal cycle stability, there are problems such as expensive electrolyte.
Disclosure of Invention
The technical problems solved by the invention are as follows: the preparation method of the zinc ion battery anode material is simple in preparation and low in preparation cost, and is used for solving the problems of complex process and high price in the prior art; the prepared polyaniline hydrogel zinc ion battery anode material has a complete nanofiber structure, effectively improves the cycling stability of the electrode material, and has great application value.
The specific solution provided by the invention is as follows:
the invention provides a preparation method of a zinc ion battery anode material, which comprises the following steps:
firstly, respectively dissolving sodium dodecyl benzene sulfonate and aniline hydrochloride into water to obtain a mixed solution system, wherein the concentration of the sodium dodecyl benzene sulfonate is 0.01-1.0 mol/L, the concentration of the aniline hydrochloride is 0.03-3.0 mol/L, and the molar ratio of the sodium dodecyl benzene sulfonate to the aniline hydrochloride is 1 (3-5);
step two, cooling the mixed solution system to 0-4 ℃, adding an oxidant, uniformly mixing, and standing for reaction to obtain stable polyaniline hydrogel, wherein the molar ratio of the oxidant to the aniline hydrochloride is 0.1-3.0;
and thirdly, washing the polyaniline hydrogel with water for a plurality of times, and freeze-drying to obtain the polyaniline material.
The method based on the invention has the following beneficial effects:
(1) The zinc ion battery anode material provided by the invention has the advantages of easily available raw materials, simple preparation process and low cost.
(2) The microstructure of the electrode material is a complete nanofiber structure, so that a continuous conductive path can be provided for the electrode, the conductivity of the material is improved, and the cycling stability of the electrode can be effectively improved.
(3) Adding dodecylbenzene sulfonic acid as a template agent, forming a compound under the action of static electricity, forming pi-pi stacking effect after the compound, assembling sodium dodecylbenzene sulfonate and aniline hydrochloride under the action of static electricity and pi-pi stacking effect to form a fiber structure, specifically, the sodium dodecylbenzene sulfonate and aniline hydrochloride are mutually close under the action of static electricity, assembling to form a fiber structure further through pi-pi effect of benzene rings among sodium dodecylbenzene sulfonate molecules and pi-pi effect among aniline hydrochloride molecules, forming polyaniline fiber in situ after adding an oxidant, and further winding to form stable blocky hydrogel, wherein the microstructure of the obtained hydrogel is formed by winding fibers, and the polyaniline material with a nanofiber structure can be obtained after freeze drying.
(4) The existence of impurity ions in the polyaniline material of the product can influence the conductivity of the material, and the aniline hydrochloride is used as a raw material, so that impurity HCl in the product is easy to remove by vacuum drying, the purity of the polyaniline material is improved, and the stability of the electrode material property is ensured.
Based on the scheme, the invention can also be improved as follows:
further, the oxidant is selected from one or more of ammonium persulfate, potassium persulfate, sodium persulfate, potassium permanganate, ferric chloride, ferric sulfate and hydrogen peroxide.
The oxidant can be used as an initiator for synthesizing polyaniline in a large scale, and is easy to be industrially carried out.
Preferably, the oxidizing agent is ammonium sulfate.
Ammonium persulfate does not contain metal ions, has strong oxidizing capacity and is convenient for post-treatment.
Further, the temperature of the standing reaction is 0 to 50 ℃.
Preferably, the temperature of the standing reaction is 0 to 25 ℃.
Under the condition, heating is not needed, and the polyaniline material with the nanofiber structure and the regular morphology and good conductivity can be obtained.
The reaction time is 1-72 h after further standing. Under these conditions, the respective raw materials can be sufficiently reacted.
Further, the number of washing is 5 to 10. Most of impurities can be washed off under the condition, and the cycling stability of the electrode is effectively improved.
A zinc ion battery anode material is prepared according to the preparation method.
The electrode material prepared by the method has a microstructure of a complete nanofiber structure, so that a continuous conductive path can be provided for the electrode, and the cycling stability of the electrode can be effectively improved.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
Fig. 1 is an SEM image of the polyaniline material prepared in example 4 of the present invention: (a) low magnification and (b) high magnification.
Fig. 2 is an SEM image of comparative sample 1 prepared in comparative example 1: (a) low magnification and (b) high magnification.
Fig. 3 is an SEM image of comparative sample 2 prepared in comparative example 2: (a) low magnification and (b) high magnification.
FIG. 4 shows the current density of the polyaniline material prepared in example 4, comparative sample 1 and comparative sample 2 at 0.1 A.g -1 Comparison of the cycling stability below.
FIG. 5 is a diagram showing the polyaniline material prepared in example 4Material, comparative sample 1 and comparative sample 2 were tested at a current density of 0.5 A.g -1 Comparison of the cycling stability below.
Detailed Description
For a better understanding of the present invention, the following examples are further illustrated, but are not limited to the following examples.
Example 1
Firstly, 2mmol of sodium dodecyl benzene sulfonate and 10mmol of aniline hydrochloride are added into 40mL of deionized water in sequence, and the sodium dodecyl benzene sulfonate and the aniline hydrochloride are stirred to be completely dissolved. Then, the mixed solution system is placed in an ice-water bath, cooled to 0-4 ℃, 10mmol of ammonium persulfate is added, and after uniform stirring, the mixture is kept stand for reaction for 12 hours at the temperature of 4 ℃ to form stable polyaniline hydrogel. And finally, washing the polyaniline hydrogel for 5 times by using a large amount of deionized water, and freeze-drying to obtain the polyaniline product which can be used as the positive electrode material of the zinc ion battery.
Example 2
Firstly, 2mmol of sodium dodecyl benzene sulfonate and 12mmol of aniline hydrochloride are added into 40mL of deionized water in sequence, and the sodium dodecyl benzene sulfonate and the aniline hydrochloride are stirred to be completely dissolved. Then, the mixed solution system is placed in an ice-water bath, cooled to 0-4 ℃, 7mmol of potassium permanganate is added, and after uniform stirring, the mixture is kept stand for reaction for 12 hours at the temperature of 4 ℃ to form stable polyaniline hydrogel. Finally, washing the polyaniline hydrogel for 5 times by using a large amount of deionized water, and freeze-drying to obtain the polyaniline material.
Example 3
Firstly, 2mmol of sodium dodecyl benzene sulfonate and 12mmol of aniline hydrochloride are added into 40mL of deionized water in sequence, and the sodium dodecyl benzene sulfonate and the aniline hydrochloride are stirred to be completely dissolved. Then, the mixed solution system is placed in an ice-water bath, cooled to 0-4 ℃, added with 12mmol of ammonium persulfate, stirred uniformly, and then kept stand for reaction for 24 hours at the temperature of 4 ℃ to form stable polyaniline hydrogel. Finally, washing the polyaniline hydrogel for 5 times by using a large amount of deionized water, and freeze-drying to obtain the polyaniline material.
Example 4
First, 4mmol of sodium dodecyl benzene sulfonate and 12mmol of aniline hydrochloride were added to 40mL of deionized water in this order, and stirred to dissolve the sodium dodecyl benzene sulfonate and aniline hydrochloride completely. Then, the mixed solution system is placed in an ice-water bath, cooled to 0-4 ℃, added with 12mmol of ammonium persulfate, stirred uniformly, and then kept stand for reaction for 24 hours at the temperature of 4 ℃ to form stable polyaniline hydrogel. Finally, washing the polyaniline hydrogel for 5 times by using a large amount of deionized water, and freeze-drying to obtain the polyaniline material.
Example 5
First, 4mmol of sodium dodecyl benzene sulfonate and 12mmol of aniline hydrochloride were added to 40mL of deionized water in this order, and stirred to dissolve the sodium dodecyl benzene sulfonate and aniline hydrochloride completely. Then, the mixed solution system is placed in an ice-water bath, cooled to 0-4 ℃, added with 12mmol of ferric chloride, stirred uniformly, and then kept stand for reaction for 24 hours at the temperature of 4 ℃ to form stable polyaniline hydrogel. Finally, washing the polyaniline hydrogel for 5 times by using a large amount of deionized water, and freeze-drying to obtain the polyaniline material.
Example 6
First, 4mmol of sodium dodecyl benzene sulfonate and 12mmol of aniline hydrochloride were added to 40mL of deionized water in this order, and stirred to completely dissolve sodium dodecyl benzene sulfonate and aniline hydrochloride. Then, the mixed solution system is placed in an ice-water bath, cooled to 0-4 ℃, added with 12mmol of ammonium persulfate, stirred uniformly, and then kept stand for reaction for 12 hours at room temperature to form stable polyaniline hydrogel. Finally, the polyaniline hydrogel is washed 3 times by a large amount of deionized water, and the polyaniline material is obtained by freeze drying.
Comparative example 1:
in order to reflect the superiority of the structure of the polyaniline material prepared by the present invention, a comparative experiment was also performed in this example, and the specific preparation process is different from that of example 4 only in that: sodium dodecyl benzene sulfonate was not added during the preparation process, and other operations were consistent with example 4.
The preparation process comprises the following steps:
to 40mL of deionized water was added 12mmol of aniline hydrochloride, and the mixture was stirred, and the aniline hydrochloride was completely dissolved. Then, the mixed solution system is placed in an ice-water bath, cooled to 0-4 ℃, added with 12mmol of ammonium persulfate, stirred uniformly, and then kept stand for reaction for 24 hours at the temperature of 4 ℃ to form a suspension. Finally, the suspension was filtered, and the filtrate was washed 5 times, and freeze-dried to obtain comparative sample 1.
Comparative example 2
The specific preparation process differs from example 4 only in that: the procedure of example 4 was otherwise identical except that the sodium dodecylbenzenesulfonate added in example 4 was replaced with sodium dodecylsulfate.
The preparation process comprises the following steps:
first, 4mmol of sodium dodecyl sulfate and 12mmol of aniline hydrochloride were added to 40mL of deionized water in this order, and stirred to dissolve sodium dodecyl sulfate and aniline hydrochloride completely. Then, the mixed solution system is placed in an ice-water bath, cooled to 0-4 ℃, added with 12mmol of ammonium persulfate, stirred uniformly, and then kept stand for reaction for 24 hours at the temperature of 4 ℃ to form stable polyaniline hydrogel. Finally, the polyaniline hydrogel was washed 5 times with a large amount of deionized water, and freeze-dried to obtain comparative sample 2.
SEM characterization is performed on the polyaniline materials prepared in example 4, comparative example 1 and comparative example 2, and the results are shown in fig. 1-3, and fig. 1a and fig. 1b are SEM images of the polyaniline material prepared in example 4 of the present invention, and it can be clearly seen from fig. 1b that the microscopic morphology of the electrode material is a continuous nanofiber structure, and this structure not only can provide continuous conductive channels for the electrode, but also can effectively improve the stability of the structure of the electrode; FIGS. 2a and 2b are SEM images of comparative sample 1 prepared in comparative example 1, and it can be clearly seen that the polyaniline material exhibits an irregular morphology; fig. 3a and 3b are SEM images of comparative sample 2 prepared in comparative example 2, and the polyaniline material morphology is a three-dimensional porous structure formed by aggregation of nanoparticles.
Electrochemical stability test was performed on the polyaniline materials prepared in example 4, comparative example 1 and comparative example 2 by using a constant current charge-discharge method, and graphs were obtained4 and fig. 5. FIG. 3 shows the current density of the sample prepared in example 4 of the present invention and the comparative samples 1 and 2 at 0.1 A.g -1 As can be seen from the comparison of the cycle stability of the polyaniline material prepared in example 4, the specific capacity was not found to be significantly attenuated in the test interval; at low current density, after the charge and discharge cycles of the comparative sample 1 are performed for 20 times, the specific capacity is rapidly reduced, and the stability of the electrode material can be improved by the three-dimensional structure of the comparative sample 2, but the stability of the nanofiber structure of the sample of example 4 is better; FIG. 4 shows the current density of the polyaniline material prepared in example 4 of the present invention, comparative sample 1 and comparative sample 2 at 0.5 A.g -1 As can be seen from the comparison of the cycling stability, the sample prepared in example 4 shows an excellent cycling stability with a specific capacity retention rate of 81% after 1500 charge and discharge cycles at a higher current density, and the specific capacity drops sharply after no more than 100 charge and discharge cycles of comparative sample 1, and the specific capacity drops significantly as compared with an increase in the number of charge and discharge cycles of sample 2.
The microstructure of the electrode material prepared by the preparation method provided by the invention has a complete nanofiber structure, so that the cycling stability of the electrode can be effectively improved, and the electrode material has a good application prospect.
Although embodiments of the present invention have been described in detail above, one of ordinary skill in the art will appreciate that: many changes, modifications, substitutions and variations may be made to the embodiments without departing from the spirit and principles of the invention, the scope of which is defined by the claims and their equivalents.
Claims (5)
1. The preparation method of the zinc ion battery anode material is characterized by comprising the following steps:
firstly, respectively dissolving sodium dodecyl benzene sulfonate and aniline hydrochloride into water to obtain a mixed solution system, wherein the concentration of the sodium dodecyl benzene sulfonate is 0.01-1.0 mol/L, the concentration of the aniline hydrochloride is 0.03-3.0 mol/L, and the molar ratio of the sodium dodecyl benzene sulfonate to the aniline hydrochloride is 1 (3-5);
step two, cooling the mixed solution system to 0-4 ℃, adding an oxidant, uniformly mixing, and standing for reaction to obtain stable polyaniline hydrogel, wherein the molar ratio of the oxidant to the aniline hydrochloride is 0.1-3.0;
step three, washing the polyaniline hydrogel for a plurality of times by using water, and freeze-drying to obtain a product polyaniline material;
the oxidant is selected from one or more of ammonium persulfate, potassium persulfate, sodium persulfate, potassium permanganate, ferric chloride, ferric sulfate and hydrogen peroxide.
2. The method for preparing a positive electrode material for a zinc-ion battery according to claim 1, wherein the temperature of the standing reaction is 0 to 50 ℃.
3. The method for preparing a zinc ion battery positive electrode material according to claim 1, wherein the time of the standing reaction is 1 to 72 hours.
4. The method for preparing a positive electrode material for a zinc ion battery according to claim 1, wherein the number of washing is 5 to 10.
5. A zinc ion battery cathode material prepared according to the preparation method of any one of claims 1 to 4.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1021921A (en) * | 1996-07-05 | 1998-01-23 | Mitsubishi Heavy Ind Ltd | Polyaniline composition and manufacture thereof |
| CN106496602A (en) * | 2016-10-27 | 2017-03-15 | 山东科技大学 | A kind of preparation method of flexible compound hydrogel |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1021921A (en) * | 1996-07-05 | 1998-01-23 | Mitsubishi Heavy Ind Ltd | Polyaniline composition and manufacture thereof |
| CN106496602A (en) * | 2016-10-27 | 2017-03-15 | 山东科技大学 | A kind of preparation method of flexible compound hydrogel |
Non-Patent Citations (3)
| Title |
|---|
| Huabo Huang.Reinforced conducting hydrogels prepared fromthe in situ polymerization of aniline in an aqueous solution of sodium alginate.《Journal of Materials Chemistry A》.2014,第16516-16522页. * |
| Hua-Yu Shi.A Long-Cycle-Life Self-Doped Polyaniline Cathode for Rechargeable Aqueous Zinc Batteries.Angewandte Chemie international Edition》.2018, 第16359-16363页. * |
| LIN You-Cheng.Preparation and Application of Polyaniline Doped with DifferentSulfonic Acids for Supercapacitor.《Acta Phys. -Chim. Sin.》.2015,第474-480页. * |
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