CN101599369B - Doped polyaniline electrode material for super-capacitor and preparation method thereof - Google Patents
Doped polyaniline electrode material for super-capacitor and preparation method thereof Download PDFInfo
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- CN101599369B CN101599369B CN2009103038635A CN200910303863A CN101599369B CN 101599369 B CN101599369 B CN 101599369B CN 2009103038635 A CN2009103038635 A CN 2009103038635A CN 200910303863 A CN200910303863 A CN 200910303863A CN 101599369 B CN101599369 B CN 101599369B
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- polyaniline
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- transition metal
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a doped polyaniline electrode material for a super-capacitor and a preparation method thereof. The method comprises the following steps of: firstly, preparing acid doped polyaniline; then, obtaining eigenstate by contra doping of alkali liquor; and finally, obtaining transition metal ion doped polyaniline by re-doping of transition metal salt solution. The specific capacity of the material in an aqueous electrolyte reaches 350 F/g and the specific capacity reaches 100 F/g in an organic electrolyte, so that the problems that a polyaniline material has small specific capacity and low energy density are effectively solved.
Description
Technical field
The present invention relates to a kind of doped polyaniline electrode material that is used for ultracapacitor and preparation method thereof.
Technical background
Ultracapacitor, the electrochemical capacitor that is otherwise known as are a kind of model electrochemical energy storage devices that grew up in recent years.Have the power density height, charging rate is fast, has extended cycle life, and security performance is good, and the electric charge hold facility is strong, and leakage current is little, and low price is convenient to safeguard characteristics such as environmental friendliness.These characteristics make ultracapacitor have broad application prospects in fields such as electric automobile, fuel combination automobile, electronic communication, space flight and aviation, national defence.
Ultracapacitor can be divided into two kinds according to the mechanism of store charge: double electric layer capacitor and pseudo capacitance device.Pseudo capacitance device electrode material mainly contains: metal oxide materials and conducting polymer materials.In numerous conducting polymer materials; Electrically conductive polyaniline is owing to have good chemical stability, conductivity and high fake capacitance energy storage characteristic; And its raw material is easy to get, synthetic advantage easy, with low cost, thereby polyaniline has extraordinary actual application prospect as electrode material for super capacitor.The chemical constitution of polyaniline is represented as follows:
Wherein the value of (1-y) has been represented the state of oxidation of polyaniline.When y=1, be full reduced form polyaniline; When y=0, be full oxidized form polyaniline; When y=0.5, be the polyaniline in eigenstate of half oxidized form semi-reduction type.
The polyaniline in eigenstate conductivity is very low, must after mixing, improve its conductivity, could be used as electrode material.What present dopant generally adopted is various inorganic acids, organic acid and lithium salt solution.
The protonic acid doping of polyaniline does not change the number of electrons on the main chain, and just proton gets on the high polymer chain and makes the chain positively charged, for keeping electric neutrality, anion is also got into the high polymer chain.The skeleton symbol of electrically conductive polyaniline is:
Polyaniline has good redox reversible property under acid condition, can between different oxidation state, carry out reversible redox reaction.Therefore protonic acid doping attitude polyaniline can be applied to electrode material for super capacitor.
In organic electrolyte, also have good electric capacity behavior with the PANI material behind the lithium salt doping, be fit to do electrode of super capacitor, its advantage is that mainly the operating potential of PANI electrode is largely increased.(Kwang SunRyu, Kwang Man Kim, Yong Joon Park such as Kwang Sun Ryu; Et al.Redox supercapacitor usingpolyaniline doped with Li salt as electrode [J] .Solid State Ionics, 2002, (152-153): 861-866) (Kwang Sun Ryu; Young-Sik Hong; Yong Joon Park, et al.Polyaniline doped with dimethylsulfate as a polymer electrode for all sold-statepower source system [J] .Solid State Ionics 2004,175 (1-4); 759-763) polyaniline material is obtained the lithium salt doping state polyaniline material with the lithium salt solution doping; Make electrode of super capacitor with it, in organic electrolyte, have than the better electrochemical behavior of doped hydrochloride attitude material, but its specific capacity is little; Electro-chemical activity in that high potential is interval is less, and energy density is lower.
Summary of the invention
The object of the present invention is to provide a kind of height ratio capacity that has, doped transition metal ions attitude polyaniline electrode material of high-energy-density and preparation method thereof.
Material of the present invention is a kind of doped polyaniline electrode material that is used for ultracapacitor, is doped with transition metal ions in the polyaniline electrode material, and said transition metal ions is Mn
2+, Fe
2+, Fe
3+, Co
2+, Cu
+, Cu
2+, Ni
2+, Zn
2+In at least a.
Preparation method of the present invention may further comprise the steps:
(1) the sour doped polyaniline material of preparation: aniline monomer is dissolved in the inorganic acid of 0.5～2mol/L, under-5～30 ℃, the inorganic acid solution of the 0.5～2mol/L that is dissolved with oxidant is splashed in the reaction bulb, stir, at room temperature react 5～30h; Filter, product is washed till colourless successively with distilled water, acetone, and vacuumize promptly gets sour doped polyaniline material;
(2) the above-mentioned sour doped polyaniline nano-fiber material that makes is handled 12～48h with 0.1～1mol/L alkali lye under stirring condition, washing, vacuumize obtains the polyaniline in eigenstate material;
(3) the above-mentioned polyaniline in eigenstate material that makes is soaked 49～72h in the organic solvent of 0.05～0.1mol/L transition metal salt; Wherein the mol ratio of polyaniline in eigenstate and transition metal ions is 1/1～1/3; Washing, vacuumize obtains transition metal salt dopping attitude polyaniline material.
Said inorganic acid is a hydrochloric acid, perchloric acid, sulfuric acid, nitric acid, at least a in the phosphoric acid.
Said oxidant is an ammonium persulfate, hydrogen peroxide, potassium bichromate, at least a in the iron chloride
Said alkali lye is NaOH, KOH, NH
4OH, LiOH, at least a in the tetraethyl ammonium hydroxide.
Said transition metal ions is Mn
2+, Fe
2+, Fe
3+, Co
2+, Cu
+, Cu
2+, Ni
2+, Zn
2+In at least a.Preferred especially Zn
2+, Cu
+In a kind of.
Said transition metal salt anionic is Cl
-, SO
4 2-, ClO
4 -, BF
4 -, PF
6 -In at least a.
Said organic solvent is an acetone, carbon tetrachloride, chloroform, carbon disulfide, at least a in the carrene.
The inventor is through discovering; Transition metal ions is because it has many to lone pair electrons; Can combine to form the ∏ key with a plurality of nitrogen-atoms on the polyaniline chain, constitute a type octahedra or type tetrahedral structure (deciding) according to the number of transition metal ions outermost layer lone pair electrons.The free charge density on the polyaniline chain be can effectively increase like this, polyaniline ionic conductivity and electronic conductivity improved.And transition metal ions can combine with nitrogen-atoms on different polyaniline chain or the same polyaniline chain, realize interchain connect with chain in be connected to form network structure, thereby the intensity of raising polyaniline chain, the cyclical stability of raising polyaniline material.
The present invention at first utilizes chemical polymerization to prepare sour doped polyaniline; Obtain its eigenstate with the alkali lye contra-doping again; Mix again with transition metal salt solution at last and promptly get doped transition metal ions attitude polyaniline material; That technical process has is simple to operate, need not template, applicability extensively, can prepare in a large number, be fit to the advantage of suitability for industrialized production.And do not see that at present the someone attempts using the doped transition metal ions polyaniline electrode material.The present invention has been owing to adopted this kind mode, make polyaniline material different ions in charge and discharge process embed/deviate to have different corresponding current potentials, help improving the electro-chemical activity of polyaniline material, obtain to have the polyaniline electrode material of height ratio capacity.The doped transition metal ions attitude polyaniline material of the present invention's preparation is done the active material of ultracapacitor, and specific capacity reaches 350F/g in aqueous electrolyte, and specific capacity reaches 100F/g in organic electrolyte.
Description of drawings
Fig. 1 is the Zn of embodiment 1 preparation
2+Doped polyaniline is at 1mol/L H
2SO
4In, cyclic voltammetry curve figure is (0.2-1.0V) under the different scanning rates of three-electrode system.
Fig. 2 is the Zn of embodiment 1 preparation
2+Doped polyaniline electrode material is at 1mol/L H
2SO
4In, the ac impedance spectroscopy of three-electrode system.
Fig. 3 is the Zn of embodiment 1 preparation
2+Doped polyaniline electrode material is at 1mol/L H
2SO
4In the different electric current density under the constant current charge-discharge curve chart.
Fig. 4 is the Zn of embodiment 1 preparation
2+Doped polyaniline electrode material is at 1mol/L H
2SO
4In the cycle life curve chart.
The Zn of Fig. 5 embodiment 1 preparation
2+Doped polyaniline electrode material is at the LiPF of 1mol/L
6EC/EMC/DMC (1: 1: 1) in the constant current charge-discharge curve chart.
Embodiment
Below in conjunction with embodiment, the present invention is done further explain, but must not these embodiment be interpreted as the restriction to protection range of the present invention.
(1) 5mL aniline is dissolved in wiring solution-forming A among the 1mol/L hydrochloric acid 50mL, the ammonium persulfate of 12.517g is dissolved in wiring solution-forming B among the 1mol/L hydrochloric acid 100mL, and solution B is dripped in the solution A, stirs, and reacts 5h under the room temperature; (2) in the G3 sand core funnel, filter, product is washed till colourless successively with distilled water, acetone, and vacuumize 24h obtains doped hydrochloride attitude polyaniline material; (3) with doped hydrochloride attitude polyaniline material under stirring condition with 1mol/L WITH AMMONIA TREATMENT 24h, washing, vacuumize 24h obtains the polyaniline in eigenstate material; (4) with the ZnCl of polyaniline in eigenstate material at 0.0835mol/L
2Soak 24h in the acetone soln, wherein polyaniline in eigenstate and ZnCl
2Mol ratio be 1/1, the washing, vacuumize 48h promptly obtains Zn
2+The doped polyaniline material.
With the Zn that makes
2+The doped polyaniline material is ultrasonic dispersion in alcohol, then it is dripped at graphite electrode surface drying at room temperature.This process repeats two to three times, obtains more smooth film.With the graphite electrode is work electrode, and platinum electrode is to electrode, and saturated calomel electrode is a reference electrode, and 1mol/L sulfuric acid is electrolyte, is assembled into three-electrode system, carries out cyclic voltammetric and ac impedance measurement.
With prepared Zn
2+Doped polyaniline material, nanometer carbon black (conductive agent), PTFE (binding agent) mix with 8: 1: 1 mass ratio, add small quantity of deionized water and absolute ethyl alcohol in the mixed process.Then water-bath heating demulsification type a period of time, process thick slurry.With slurry be rolled into repeatedly on the twin rollers have certain intensity thin slice (thickness is about 1mm), striking out area again is 0.785cm
2Single electrode slice.With two Zn
2+The doped polyaniline electrode slice is done positive and negative electrode respectively, and therebetween layer of glass film is made barrier film, does electrolyte with the aqueous sulfuric acid of 1mol/L, is assembled into the aqueous super capacitor sample of sandwich form, carries out the test of constant current charge-discharge and cycle life.
With prepared Zn
2+Doped polyaniline material and nanometer carbon black (conductive agent), PVDF (binding agent) mix under the condition that adds little amount of N-methyl pyrrolidone (NMP) with 8: 1: 1 mass ratio; Then thick substances is coated with and is pressed on the metal aluminum foil; After 60 ℃ of vacuumizes, striking out area again is 0.785cm
2Single electrode slice.With two Zn
2+The doped polyaniline electrode slice is done positive and negative electrode respectively, makees barrier film with the Celgard2300 microporous barrier, with the LiPF of 1mol/L
6, EC/EMC/DMC (1: 1: 1) is an electrolyte, is assembled into the organic system ultracapacitor sample of sandwich form, carries out the test of constant current charge-discharge and cycle life.
Zn
2+The first charge-discharge specific capacity is 350F/g under the doped polyaniline material water system, and 1000 times circulation back specific capacity still keeps 323F/g.Specific capacity reaches 105F/g under the organic system.
(1) 3mL aniline is dissolved in wiring solution-forming A among the 2mol/L perchloric acid 50mL, the ammonium persulfate of 7.5g is dissolved in wiring solution-forming B among the perchloric acid 50mL of 2mol/L, and solution B is dripped in the solution A, stirs, and reacts 8h under the room temperature; (2) filter in the G3 sand core funnel, product is washed till colourless successively with distilled water, acetone, and vacuumize 24h obtains perchloric acid doped polyaniline material; (3) with perchloric acid doped polyaniline material under stirring condition with 2mol/L potassium hydroxide treatment 24h, washing, vacuumize 24h obtains the polyaniline in eigenstate material; (4) with the polyaniline in eigenstate material at the Zn of 0.1mol/L (ClO
4)
2Soak 24 h, wherein polyaniline in eigenstate and Zn (ClO in the chloroformic solution
4)
2Mol ratio be 3/4, the washing, vacuumize 48h promptly obtains Zn
2+The doped polyaniline material.Method of testing such as embodiment 1.Under the water system, specific capacity is 340F/g, and 1000 times the circulation back keeps 311F/g; Under the organic system, specific capacity is 105F/g.
(1) 10mL aniline is dissolved in wiring solution-forming A among the 2mol/L sulfuric acid 100mL, the ammonium persulfate of 25.034g is dissolved in wiring solution-forming B among the sulfuric acid 100mL of 2mol/L, and solution B is dripped in the solution A, stirs, and reacts 10h under the room temperature; (2) filter in the G3 sand core funnel, product is washed till colourless successively with distilled water, acetone, and vacuumize 24h obtains sulfuric acid doped polyaniline material; (3) with sulfuric acid doped polyaniline material under stirring condition with 1mol/L naoh treatment 24h, washing, vacuumize 24h obtains the polyaniline in eigenstate material; (4) with the FeSO of polyaniline in eigenstate material at 0.05mol/L
4Soak 24h in the dichloromethane solution, wherein polyaniline in eigenstate and FeSO
4Mol ratio be 2/3, the washing, vacuumize 48h promptly obtains Fe
2+The doped polyaniline material.Method of testing such as embodiment 1.Under the water system, specific capacity is 345F/g; In the organic electrolyte, specific capacity reaches 110F/g.
Embodiment 4
(1) 5mL aniline is dissolved in wiring solution-forming A among the 1mol/L hydrochloric acid 50mL, the ammonium persulfate of 12.517g is dissolved in wiring solution-forming B among the 1mol/L hydrochloric acid 100mL, and solution B is dripped in the solution A, stirs, and reacts 8h under the room temperature; (2) in the G3 sand core funnel, filter, product is washed till colourless successively with distilled water, acetone, and vacuumize 24h obtains doped hydrochloride attitude polyaniline material; (3) with doped hydrochloride attitude polyaniline material under stirring condition with 1mol/L WITH AMMONIA TREATMENT 24h, washing, vacuumize 24h obtains the polyaniline in eigenstate material; (4) with the NiCl of polyaniline in eigenstate material at 0.0835mol/L
2Soak 30h in the ethanolic solution, wherein polyaniline in eigenstate and NiCl
2Mol ratio be 1/2, the washing, vacuumize 48h promptly obtains Ni
2+The doped polyaniline material.Method of testing such as embodiment 1, under the water system, specific capacity is 332F/g; Under the organic system, specific capacity is 100F/g.
10mL aniline is dissolved in wiring solution-forming A among the 2mol/L perchloric acid 100mL, and the ammonium persulfate of 25.034g is dissolved in wiring solution-forming B among the perchloric acid 100mL of 2mol/L, and solution B is dripped in the solution A, stirs, and reacts 10h under the room temperature; (2) filter in the G3 sand core funnel, product is washed till colourless successively with distilled water, acetone, and vacuumize 24h obtains perchloric acid doped polyaniline material; (3) with perchloric acid doped polyaniline material under stirring condition with 1.5mol/L WITH AMMONIA TREATMENT 24h, washing, vacuumize 24h obtains the polyaniline in eigenstate material; (4) with the CuClO of polyaniline in eigenstate material at 0.01mol/L
4Soak 48h in the acetone soln, wherein polyaniline in eigenstate and CuClO
4Mol ratio be 1/3, the washing, vacuumize 48h promptly obtains Cu
+The doped polyaniline material.Method of testing such as embodiment 1.Under the water system, specific capacity is 334F/g; In the organic electrolyte, specific capacity reaches 102F/g.
Claims (7)
1. a preparation method who is used for the doped polyaniline electrode material of ultracapacitor is characterized in that, may further comprise the steps:
(1) the sour doped polyaniline material of preparation: aniline monomer is dissolved in the inorganic acid of 0.5～2mol/L, under-5～30 ℃ of conditions, the inorganic acid solution of the 0.5～2mol/L that is dissolved with oxidant is splashed in the reaction bulb, stir, reaction 5～30h; Filter, product is washed till colourless successively with distilled water, acetone, and vacuumize promptly gets sour doped polyaniline material;
(2) the above-mentioned sour doped polyaniline material that makes is handled 12～48h with 0.1～1mol/L alkali lye under stirring condition, washing, vacuumize obtains the polyaniline in eigenstate material;
(3) the above-mentioned polyaniline in eigenstate material that makes, 0.05～0.1mol/L is soaked 49～72h in containing the organic solvent of transition metal salt; Wherein the mol ratio of polyaniline in eigenstate and transition metal ions is 1/1～1/3; Washing, vacuumize obtains transition metal salt dopping attitude polyaniline material.
2. preparation method according to claim 1 is characterized in that: said inorganic acid is a hydrochloric acid, perchloric acid, and sulfuric acid, nitric acid, phosphoric acid is at least a.
3. preparation method according to claim 1 is characterized in that: said oxidant is an ammonium persulfate, hydrogen peroxide, potassium bichromate, at least a in the iron chloride.
4. preparation method according to claim 1 is characterized in that: said alkali lye is NaOH, KOH, NH
4OH, LiOH, at least a in the tetraethyl ammonium hydroxide.
5. preparation method according to claim 1 is characterized in that: the cation in the said transition metal salt is Mn
2+, Fe
2+, Fe
3+, Co
2+, Cu
+, Cu
2+, Ni
2+, Zn
2+In at least a.
6. preparation method according to claim 1 is characterized in that: anion is Cl in the said transition metal salt
-, SO
4 2-, ClO
4 -, PO
4 3-, BF
4 -, PF
6 -In at least a.
7. preparation method according to claim 1 is characterized in that: said organic solvent is at least a in acetone, carbon tetrachloride, chloroform, carbon disulfide, carrene, the ethanol.
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| CN102074375B (en) * | 2011-01-02 | 2012-04-25 | 桂林理工大学 | Preparation method for high-cyclical-stability composite capacitor material |
| CN103066314B (en) * | 2012-12-25 | 2015-01-07 | 武汉纺织大学 | Fabric morphological polymer battery and preparation method thereof |
| CN104448302B (en) * | 2013-09-17 | 2016-09-07 | 中国石油化工股份有限公司 | A kind of preparation method of high purity polyaniline in eigenstate |
| CN104845492A (en) * | 2015-05-13 | 2015-08-19 | 贵州师范学院 | Sulfuric acid/aluminum triphosphate doped poly-o-toluidine anticorrosive coating |
| CN107434849A (en) * | 2017-09-04 | 2017-12-05 | 佛山杰致信息科技有限公司 | The synthetic method of divalence cobalt molybdenum salt dopping polyaniline |
| CN107768150B (en) * | 2017-10-26 | 2019-10-11 | 吉林大学 | Copper ion doped polyaniline electrode with carbon cloth as substrate and preparation method thereof |
| CN110265229B (en) * | 2019-06-18 | 2021-09-28 | 兰州理工大学 | Preparation method of paper fiber/eigenstate polyaniline super capacitor composite electrode material |
| CN114005971B (en) * | 2021-10-22 | 2024-04-19 | 陕西红马科技有限公司 | Positive electrode material with p-type doped conductive polymer coating and preparation method thereof |
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| CN1958852A (en) * | 2006-10-11 | 2007-05-09 | 扬州大学 | Electrochemical method for synthesizing Nano particles of polyaniline with transition metal being doped |
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