CN112736244A - 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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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 15
- 239000007772 electrode material Substances 0.000 title abstract description 18
- 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 32
- 239000000463 material Substances 0.000 claims abstract description 29
- 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
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000004108 freeze drying Methods 0.000 claims abstract description 10
- 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
- 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
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000002121 nanofiber Substances 0.000 abstract description 9
- 230000001351 cycling effect Effects 0.000 abstract description 7
- 239000010405 anode material Substances 0.000 abstract description 6
- 239000010406 cathode material Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 28
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 239000000047 product Substances 0.000 description 9
- 239000005457 ice water Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000009471 action Effects 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000008569 process Effects 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
- 238000003860 storage Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction 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
- -1 Prussian blue series compounds Chemical class 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000004075 alteration Effects 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect 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
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 230000005611 electricity 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
- 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
- 239000000203 mixture Substances 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
- 239000000243 solution Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution 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
- 150000003681 vanadium Chemical class 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
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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
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- 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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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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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- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
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Abstract
The invention relates to a preparation method of a zinc ion battery anode material and the electrode material prepared by the 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 a 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 several times, and freeze-drying to obtain the product polyaniline material. The preparation method of the zinc ion battery cathode material is simple in preparation and low in preparation cost; the prepared polyaniline hydrogel zinc-ion battery positive electrode 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 anode material and an electrode material prepared by the zinc ion battery anode material.
Background
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 storage capacity and high price are significant challenges in lithium ion battery applications. For this reason, aqueous metal ion batteries with abundant elemental reserves and low prices are receiving increasing attention from researchers, and among them, zinc ion batteries composed of a zinc metal negative electrode, a zinc ion aqueous electrolyte and a positive electrode are favored by researchers, and zinc has the following remarkable advantages: the zinc metal resource is rich, the chemical stability is high, and the zinc metal has proper oxidation-reduction potential (-0.76V vs. standard hydrogen electrode) and high theoretical specific capacity (820mAh g)-1) (ii) a The neutral zinc salt aqueous solution is an electrolyte, has low cost, safety, high ionic conductivity, environmental friendliness and the like, and has great competitiveness in large-scale application as an energy storage device due to the advantages. However, for zinc ion batteries, due to Zn2+The high polarization characteristic and the narrow potential window in which the aqueous electrolyte can stably exist are important for developing a suitable positive electrode material.
Currently, research on positive electrode materials of zinc ion batteries is becoming a research focus, and there are mainly four types of reported material systems: manganese series, vanadium series, Prussian blue series compounds and organic materials. The first three electrode materials are inorganic substances and mainly come from mineral substances, so that excessive mining of the electrode materials can cause damage to the natural environment and the problem of resource shortage in the future is likely to occur; in addition, they have the problems of poor conductivity and poor cycle stability. The research on organic electrode materials is not common at present, 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 an important development direction in the future.
Among organic motor materials, polyaniline has the advantages of good conductivity, simple synthesis, environmental friendliness and the like, and is one of the most studied organic positive electrode materials of zinc ion batteries at present, and although polyaniline has ideal conductivity and electrochemical zinc storage capacity, the cycling stability in the charging and discharging process is not ideal. In order to solve the problems, Sun et al synthesizes a polyaniline copolymer anode (Angewandte chemical International Edition,2018,57, 16359) with a self-doping structure, and has a complex synthesis process; chen et al utilize a novel electrolyte (Zn (CF)3SO3)2) constructing a polyaniline based zinc ion battery (Advanced Functional Materials 2018,28, 1804975) with a composite zinc storage mechanism. Although they all achieve the desired cycle stability, there are problems that the electrolyte is expensive.
Disclosure of Invention
The technical problem solved by the invention is as follows: the preparation method of the zinc ion battery anode material and the electrode material prepared by the preparation method are provided, and used for solving the problems of complex process and high price in the prior art; the prepared polyaniline hydrogel zinc-ion battery positive electrode 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:
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 a stable polyaniline hydrogel, wherein the molar ratio of the oxidant to the aniline hydrochloride is 0.1-3.0;
and step three, washing the polyaniline hydrogel for a plurality of times by using water, and freeze-drying to obtain the product 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 circulating stability of the electrode can be effectively improved.
(3) Adding dodecyl benzene sulfonic acid as template agent, forming compound under the action of static electricity, and then forms pi-pi accumulation action after compounding, the sodium dodecyl benzene sulfonate and aniline hydrochloride are assembled to form a fiber structure under the electrostatic action and the pi-pi accumulation action, specifically, the sodium dodecyl benzene sulfonate and aniline hydrochloride are close to each other under the electrostatic action, then further assembling to form a fiber structure through the pi-pi action of benzene rings among sodium dodecyl benzene sulfonate molecules and the pi-pi action among aniline hydrochloride molecules, adding an oxidant, generating the polyaniline fiber in situ, and further winding to form stable block-shaped hydrogel, wherein the microstructure of the obtained hydrogel is formed by wound fibers, and the fiber diameter is uniform, the continuity is good, and the polyaniline material with the 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, aniline hydrochloride is used as a raw material, and the impurity HCl in the product is easy to remove by vacuum drying, so that the purity of the polyaniline material is improved, and the stability of the property of the electrode material is ensured.
On the basis of the scheme, the invention can be further 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 on a large scale, and is easy to industrially carry out.
Preferably, the oxidant is ammonium sulfate.
The ammonium persulfate does not contain metal ions, has strong oxidizing power and is convenient for post-treatment.
Further, the temperature of the standing reaction is 0-50 ℃.
Preferably, the temperature of the standing reaction is 0-25 ℃.
Under the condition, heating is not needed, and the polyaniline material with the nanofiber structure, which is regular in appearance and good in conductivity, can be obtained.
The time for further standing reaction is 1-72 h. Under these conditions, the respective raw materials can react sufficiently.
Further, the number of washing times is 5 to 10. Most impurities can be washed off under the condition, and the circulation stability of the electrode is effectively improved.
The zinc ion battery positive electrode material is prepared according to the preparation method.
The electrode material is prepared according to the method, the microstructure is a complete nanofiber structure, a continuous conductive path can be provided for the electrode, and the circulation 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 a 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 is a graph of the current density of 0.1A g for the polyaniline material prepared in example 4, comparative sample 1, and comparative sample 2-1Comparison of the cycling stability of the following.
FIG. 5 is a graph showing the current density of 0.5 A.g for the polyaniline material prepared in example 4, comparative sample 1 and comparative sample 2-1Comparison of the cycling stability of the following.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
Firstly, 2mmol of sodium dodecyl benzene sulfonate and 10mmol of aniline hydrochloride are sequentially added into 40mL of deionized water, and stirred to completely dissolve the sodium dodecyl benzene sulfonate and the aniline hydrochloride. And then, placing the mixed solution system in an ice-water bath, cooling to 0-4 ℃, adding 10mmol of ammonium persulfate, uniformly stirring, and standing at 4 ℃ for reaction for 12 hours to form the 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 product polyaniline material 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 sequentially added into 40mL of deionized water, and stirred to completely dissolve the sodium dodecyl benzene sulfonate and the aniline hydrochloride. And then, placing the mixed solution system in an ice-water bath, cooling to 0-4 ℃, adding 7mmol of potassium permanganate, uniformly stirring, and standing at 4 ℃ for reaction for 12 hours to form the 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 product polyaniline material.
Example 3
Firstly, 2mmol of sodium dodecyl benzene sulfonate and 12mmol of aniline hydrochloride are sequentially added into 40mL of deionized water, and stirred to completely dissolve the sodium dodecyl benzene sulfonate and the aniline hydrochloride. And then, placing the mixed solution system in an ice-water bath, cooling to 0-4 ℃, adding 12mmol of ammonium persulfate, uniformly stirring, and standing at 4 ℃ for reaction for 24 hours to form the 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 product polyaniline material.
Example 4
Firstly, 4mmol of sodium dodecyl benzene sulfonate and 12mmol of aniline hydrochloride are sequentially added into 40mL of deionized water, and stirred to completely dissolve the sodium dodecyl benzene sulfonate and the aniline hydrochloride. And then, placing the mixed solution system in an ice-water bath, cooling to 0-4 ℃, adding 12mmol of ammonium persulfate, uniformly stirring, and standing at 4 ℃ for reaction for 24 hours to form the 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 product polyaniline material.
Example 5
Firstly, 4mmol of sodium dodecyl benzene sulfonate and 12mmol of aniline hydrochloride are sequentially added into 40mL of deionized water, and stirred to completely dissolve the sodium dodecyl benzene sulfonate and the aniline hydrochloride. And then, placing the mixed solution system in an ice-water bath, cooling to 0-4 ℃, adding 12mmol of ferric chloride, uniformly stirring, and standing at 4 ℃ for reaction for 24 hours to form the 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 product polyaniline material.
Example 6
Firstly, 4mmol of sodium dodecyl benzene sulfonate and 12mmol of aniline hydrochloride are sequentially added into 40mL of deionized water and stirred to completely dissolve the sodium dodecyl benzene sulfonate and the aniline hydrochloride. And then, placing the mixed solution system in an ice-water bath, cooling to 0-4 ℃, adding 12mmol of ammonium persulfate, uniformly stirring, and standing at room temperature for reaction for 12 hours to form the stable polyaniline hydrogel. And finally, washing the polyaniline hydrogel for 3 times by using a large amount of deionized water, and freeze-drying to obtain the product polyaniline material.
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 in example 4 only in that: the preparation process was carried out without adding sodium dodecylbenzenesulfonate, and the other operations were identical to those of example 4.
The preparation process comprises the following steps:
12mmol aniline hydrochloride was added to 40mL deionized water and stirred until aniline hydrochloride was completely dissolved. And then, placing the mixed solution system in an ice water bath, cooling to 0-4 ℃, adding 12mmol of ammonium persulfate, uniformly stirring, and standing at 4 ℃ for reaction for 24 hours to form a suspension. Finally, the suspension was filtered and the filtrate was washed 5 times and freeze dried to give comparative sample 1.
Comparative example 2
Compared with the example 4, the specific preparation process is different only in that: the sodium dodecylbenzenesulfonate added in example 4 was replaced with sodium dodecylsulfate, and the other operations were identical to those in example 4.
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 the mixture was stirred to completely dissolve the sodium dodecyl sulfate and aniline hydrochloride. And then, placing the mixed solution system in an ice-water bath, cooling to 0-4 ℃, adding 12mmol of ammonium persulfate, uniformly stirring, and standing at 4 ℃ for reaction for 24 hours to form the 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, where 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 micro-morphology of the electrode material is a continuous nanofiber structure, which not only can provide a continuous conductive channel for the electrode, but also can effectively improve the structural stability of the electrode; fig. 2a and 2b are SEM images of a comparative sample 1 prepared in comparative example 1, and it can be clearly seen that the polyaniline material exhibits a random morphology; fig. 3a and 3b are SEM images of a comparative sample 2 prepared in comparative example 2, and the morphology of the polyaniline material is a three-dimensional porous structure formed by aggregation of nanoparticles.
The electrochemical stability test was performed on the polyaniline materials prepared in example 4, comparative example 1, and comparative example 2 by a constant current charge and discharge method, and fig. 4 and 5 were obtained. FIG. 3 shows the current density of the sample prepared in example 4 of the present invention and that of comparative samples 1 and 2 at 0.1 A.g-1The comparison of the cycling stability shows that the specific capacity of the polyaniline material prepared in example 4 is not obviously attenuated in a test interval; under low current density, after the comparative sample 1 is subjected to charge and discharge cycles for 20 times, the specific capacity is reduced sharply, and the stability of the electrode material can be improved by the three-dimensional structure in the comparative sample 2, but the stability of the nanofiber structure of the sample in the example 4 is better; FIG. 4 shows the current density of 0.5 A.g for the polyaniline material prepared in example 4 of the present invention, comparative sample 1 and comparative sample 2-1As can be seen from the comparison of the following cycle stability, at a higher current density, the specific capacity retention rate of the sample prepared in example 4 is 81% after 1500 times of charge and discharge cycles, which represents excellent cycle stability, and the specific capacity is sharply reduced after the charge and discharge cycles of the comparative sample 1 do not exceed 100 times, and the specific capacity is also significantly reduced due to the increase of the charge and discharge cycles of the comparative 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, those of ordinary skill in the art will understand that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Claims (6)
1. A preparation method of a zinc ion battery positive electrode material is characterized by comprising 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 a stable polyaniline hydrogel, wherein the molar ratio of the oxidant to the aniline hydrochloride is 0.1-3.0;
and step three, washing the polyaniline hydrogel for a plurality of times by using water, and freeze-drying to obtain the product polyaniline material.
2. The method for preparing the positive electrode material of the zinc-ion battery according to claim 1, wherein the oxidant is selected from one or more of ammonium persulfate, potassium persulfate, sodium persulfate, potassium permanganate, ferric chloride, ferric sulfate and hydrogen peroxide.
3. The method for preparing the positive electrode material of the zinc-ion battery according to claim 1, wherein the temperature of the standing reaction is 0-50 ℃.
4. The method for preparing the positive electrode material of the zinc-ion battery according to claim 1, wherein the standing reaction time is 1-72 hours.
5. The method for preparing the positive electrode material for the zinc-ion battery according to claim 1, wherein the number of washing times is 5 to 10.
6. A positive electrode material for a zinc ion battery, characterized by being produced by the production method according to any one of claims 1 to 5.
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| CN114381016A (en) * | 2021-12-28 | 2022-04-22 | 武汉工程大学 | Method for in-situ synthesis of polyaniline/manganese dioxide composite hydrogel and application thereof |
| CN114628654A (en) * | 2022-02-28 | 2022-06-14 | 武汉工程大学 | Polyimide/polyaniline composite zinc ion battery positive electrode material and preparation method thereof |
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| 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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| JPH1021921A (en) * | 1996-07-05 | 1998-01-23 | Mitsubishi Heavy Ind Ltd | Polyaniline composition and manufacture thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114381016A (en) * | 2021-12-28 | 2022-04-22 | 武汉工程大学 | Method for in-situ synthesis of polyaniline/manganese dioxide composite hydrogel and application thereof |
| CN114628654A (en) * | 2022-02-28 | 2022-06-14 | 武汉工程大学 | Polyimide/polyaniline composite zinc ion battery positive electrode material and preparation method thereof |
| CN114628654B (en) * | 2022-02-28 | 2023-12-29 | 武汉工程大学 | Polyimide/polyaniline composite zinc ion battery positive electrode material and preparation method thereof |
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