CN104650354B - Aniline/N methyl thionins copolymer and zinc aniline/N methyl thionin copolymer secondary cells - Google Patents
Aniline/N methyl thionins copolymer and zinc aniline/N methyl thionin copolymer secondary cells Download PDFInfo
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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
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Abstract
The invention discloses a kind of aniline/N methyl thionins copolymer and zinc aniline/N methyl thionin copolymer secondary cells.In the electrolytic cell of three electrodes composition, at normal temperatures and pressures, the electrolyte of aniline, N methyl thionins, sulfuric acid composition is electrolysed using cyclic voltammetry, electrolysate is obtained on the working electrode (s, with the second distillation water washing electrolysate, and dried at 60~90 DEG C, produce aniline/N methyl thionin copolymers.The copolymer is made into negative electrode, zinc metal sheet is anode, electrolyte ZnCl2With NH4Cl, Wei Nilunbu are barrier film, build secondary cell.The secondary cell of the present invention has good charge-discharge performance, when current density is 2mAcm‑2When, secondary cell coulombic efficiency is up to 96.62%；The secondary cell is after 150 discharge and recharges, coulombic efficiency 99.16%, and specific capacity only have dropped 3.43%, therefore the battery has a good application prospect.
Description
Technical field
The invention discloses a kind of aniline/N- methyl thionin copolymers, and the zinc-aniline prepared using the copolymer/
N- methyl thionin copolymer secondary cells, belong to the technical field of secondary cell.
Background technology
Conducting polymer is a kind of new high polymer material, has good redox reversible, electric conductivity, proton
Exchangeability and environmental stability, compare and are suitable as battery cathode material.In conducting polymer, polyaniline is again with synthesis material
Compared be generally easy to get, synthetic method it is single it is simple, production cost is relatively low, highly stable in the aqueous solution and air, and when electricity
After tank discharge, the polyaniline spontaneous protonation of energy and oxidation in acidic aqueous solution of reduced form is now in, this is remarkably contributing to
The recovery of battery capacity, so that polyaniline, which turns into, most one of electrode material of application prospect.At present, relevant polyaniline is made
For very more, such as zinc-Polyaniline Cell, magnesium-Polyaniline Cell, lithium-Polyaniline Cell etc. of the report of battery cathode material.
Although though polyaniline is influenceed by pH value deeply with many excellent performances, its electrochemical properties.Low pH's
In electrolyte, zinc electrode is easy to corrode, and produces zinc branch, this is very unfavorable to battery, works as pH value of solution>When 4.0, polyaniline will lose
Electro-chemical activity, this weakness seriously constrain the application of polyaniline.
The content of the invention
Goal of the invention：The first object of the present invention provides one kind in pH>Still have in 4.0 solution compared with high electrochemical activity
Aniline/N- methyl thionin copolymers；
The second object of the present invention is to make zinc-benzene with higher battery capacity of cathode material composition using the copolymer
Amine/N- methyl thionin copolymer secondary cells.
The content of the invention：Aniline of the present invention/N- methyl thionin copolymers, it is prepared by following methods：
In the electrolytic cell of three electrodes composition, at normal temperatures and pressures, aniline, N- methyl thionins, sulfuric acid are formed using cyclic voltammetry
Electrolyte be electrolysed, the electrolysate obtained on the working electrode (s is one layer of thicker black film, is washed with second distillation
The electrolysate is washed, and is dried at 60~90 DEG C, produces aniline/N- methyl thionin copolymers.
Wherein, the concentration of the aniline is 0.1~0.4moldm-3, the concentration of N- methyl thionins for 1.5~
3.0mmol·dm-3, the concentration of sulfuric acid is 0.3~0.8moldm-3.When being electrolysed using the cyclic voltammetry, sweep
It is -0.1~1.1V to retouch potential range, and sweep speed is 40~100mVs-1, the electric potential scanning number of turns is 20-60 circles.Three electricity
In the electrolytic cell of pole composition, working electrode and auxiliary electrode are platinum electrode, and reference electrode is saturated calomel electrode.
Aniline of the present invention/N- methyl thionin copolymers make zinc-aniline/N- methyl thionins copolymer two of negative electrode composition
Primary cell, the negative electrode of the secondary cell is aniline/N- methyl thionin copolymers, and anode is zinc metal sheet, and electrolyte is by ZnCl2With NH4Cl
The solution of composition.
Wherein, ZnCl in the electrolyte2Concentration be 1.5~2.5moldm-3, NH4Cl concentration be 2.0~
3.5mol·dm-3.The pH value that the electrolyte can be controlled is 4.2~5.2.Used in secondary cell Wei Nilunbu be used as every
Film.The open-circuit voltage of secondary cell is 1.41V.In addition, the zinc metal sheet can be first through α-Al before use2O3Polishing, then successively
It is cleaned by ultrasonic in ethanol, redistilled water.
Beneficial effect：Compared with prior art, its remarkable advantage is the present invention：Firstth, aniline/N- first that the present invention synthesizes
Base thionine copolymer, works as pH value of solution>When 4.0, the copolymer still possesses higher electro-chemical activity；Secondth, the present invention, which utilizes, is somebody's turn to do
Copolymer forms zinc-aniline/N- methyl thionin copolymer secondary cells as cathode material, and experimental result confirms, the secondary electricity
In pH 4.7 electrolyte, its battery capacity significantly improves in pond；When secondary cell is with 5mAcm-2It is reduced to 1mAcm-2,
Now battery specific capacity is by 70.06mAhg-1Increase to 92.75mAhg-1；When current density is 2mAcm-2When, now two
Primary cell coulombic efficiency is up to 96.62%；After 150 discharge and recharges, its coulombic efficiency is the secondary cell
99.16%, specific capacity only have dropped 3.43%.The secondary cell of the present invention has good charge-discharge performance, preparation method
Practical operation that is simple and easy, being easy in production, has a good application prospect.
Brief description of the drawings
Fig. 1 a are the scanning electron microscope (SEM) photograph of poly- (N- methyl thionins)；
Fig. 1 b are the scanning electron microscope (SEM) photograph of polyaniline；
Fig. 1 c are the scanning electron microscope (SEM) photograph for aniline/N- methyl thionin copolymers that the present invention synthesizes；
Fig. 2 is aniline of the present invention/N- methyl thionin copolymers in 2.0moldm-3ZnCl2With 3.0moldm-3NH4Cl
Cyclic voltammogram in solution, wherein, curve 1：PH 4.2, curve 2：PH 4.7, curve 3：pH 5.2；
Fig. 3 is ZnCl of the aniline of the present invention/N- methyl thionins copolymer in various concentrations2With 3.0moldm-3NH4Cl is molten
Cyclic voltammogram in liquid, the pH 4.7 of solution, wherein, curve 1：1.5mol·dm-3ZnCl2, curve 2：2.0mol·dm- 3ZnCl2, curve 3：2.5mol·dm-3ZnCl2；
Fig. 4 is 2.0moldm of the aniline of the present invention/N- methyl thionins copolymer in different pH-3ZnCl2With 3.0mol
dm-3NH4AC impedance figure in Cl solution, polarizing voltage are the open-circuit voltage of copolymer；
Fig. 5 is ZnCl of the aniline of the present invention/N- methyl thionins copolymer in various concentrations2With 3.0moldm-3NH4Cl is molten
AC impedance figure in liquid, wherein, the pH 4.7 of solution, polarizing voltage is the open-circuit voltage of copolymer；
Fig. 6 is charging and discharging curve of the secondary cell of the present invention under different current densities；
Fig. 7 is charging and discharging curve of the secondary cell of the present invention under different numbers.
Embodiment：
Technical scheme is described further below.
In the electrolytic cell of three electrodes composition (such as working electrode and auxiliary electrode are naked platinized platinum, reference electrode is full
And calomel electrode), at normal temperatures and pressures, the electrolyte of aniline, N- methyl thionins, sulfuric acid composition is carried out using cyclic voltammetry
Electrolysis, the composition of electrolyte for example can be 0.1~0.4moldm-3Aniline, 1.5~3.0mmoldm-3N- methyl
Thionine, 0.3~0.8moldm-3Sulfuric acid, it is -0.1~1.1V (vs.SCE) that can control combined potential during electrolysis, scanning speed
Rate is 40~100mV.s-1, the circle of polymerization 20~60, the electrolysate obtained on the working electrode (s is one layer of thicker black film,
With the second distillation water washing electrolysate, and (can be drying box) be dried at 60~90 DEG C, produce aniline/N- methyl sulphur
Violet copolymer.The copolymer not only remains the excellent characteristic of polyaniline, and in pH 4.2 to 5.2 by ZnCl2With NH4Cl groups
Into solution in remain to keep good electro-chemical activity.Then using the aniline of above-mentioned synthesis/N- methyl thionins copolymer as
The negative electrode of secondary cell, zinc metal sheet are anode, and electrolyte is by ZnCl2With NH4Cl is formed, and pH can be 4.7, barrier film Wei Nilunbu.
To secondary cell respectively with 5mAcm-2、2mA·cm-2、1mA·cm-2Carry out constant current charge-discharge experiment, the results showed that, work as electricity
Current density is 2mAcm-2When, now secondary cell coulombic efficiency is up to 96.62%；The secondary cell passes through 150 charge and discharges
After electricity, its coulombic efficiency is 99.16%, and specific capacity only have dropped 3.43%.
Embodiment 1：
(1), the basic composition of battery
Electrode material is respectively aniline/N- methyl thionins copolymer and zinc metal sheet, and electrolyte is by ZnCl2With NH4Cl aqueous solution groups
Into barrier film Wei Nilunbu.
(2), the preparation of aniline/N- methyl thionin copolymers
1st, the preparation of raw material
Aniline, N- methyl thionins, sulfate；Wherein, aniline saves backup after vacuum distillation at 4 DEG C.
2nd, polymer electrolyte liquid is configured
The concentration of aniline is 0.2moldm-3, N- methyl thionins concentration is 2.5mmoldm-3, the concentration of sulfuric acid is
0.5mol·dm-3
3rd, the preparation of electrolytic cell
Electrolytic cell uses three-electrode system, and working electrode and auxiliary electrode are platinized platinum, reference electrode saturated calomel electrode.
4th, electrochemical polymerization
Cyclic voltammetry scanning current potential is -0.1-1.1V (vs.SCE) during polymerization, sweep speed 60mV/s, electric potential scanning
The number of turns is 30 circles.
5th, washing is with drying
One layer of thicker black film (electrolysate) is obtained after electrolysis, on working electrode, with the second distillation water washing electricity
Product is solved, is dried at 60~90 DEG C and (dries product at such a temperature), you can obtains aniline and N- methyl thionin copolymers.
(3), the processing of zinc metal sheet
Zinc metal sheet is before use through α-Al2O3Polishing, is then cleaned by ultrasonic, it is therefore an objective to make in ethanol, redistilled water successively
Zinc metal sheet clean surface, zinc ion can uniformly be dissolved on zinc metal sheet surface and deposition.
(4), the configuration of battery electrolyte
Battery electrolyte is configured using redistilled water, wherein, ZnCl2Concentration be 2.0moldm-3, NH4Cl's is dense
Spend for 3.0moldm-3, the pH 4.7 of electrolyte.
(5), above-mentioned two electrodes, electrolyte solution and barrier film are put into a glass container together, form an envelope
Zinc-the aniline closed /N- methyl thionin copolymer secondary cells, wherein, "/" expression " and ".
The expression formula of above-mentioned secondary cell is：
Zinc ▏ zinc chloride, ammonium chloride (solution) ▏ aniline/N- methyl thionin copolymers
Battery electrode reaction is as follows：
Negative electrode：
Wherein, A represents the anion SO being doped in co-polymer membrane4 2-Or Cl-。
Anode：
Aniline/N- methyl thionins copolymer and secondary cell are analyzed below.
1st, the morphology analysis of copolymer
Fig. 1 a represent the scanning electron microscope (SEM) photograph of poly- (N- methyl thionins), and the surface topography of poly- (N- methyl thionins) film is by nanometer
The smooth particle and its aggregation of size are formed, and particle diameter is at 4 μm or so；Fig. 1 b represent that the scanning electron microscope (SEM) photograph of polyaniline is
The tufted structure being made up of fiber, the diameter of fiber is at 2 μm or so；Fig. 1 c are the electron microscopes of aniline/N- methyl thionin copolymers,
Its surface topography is by fiber and the molecular micro-structural of grain, and the diameter of these fibers is generally more than 2 μm.Can from polymer morphology
To find out, adding N- methyl thionins contributes to the generation of fibre structure, and the film for also demonstrating copolymer is not polyaniline and poly- (N-
Methyl thionin) mixing.
2nd, the electrochemical property of copolymer
Fig. 2 represents that the copolymer contains 2.0moldm in pH 4.2, pH 4.7 and pH 5.2-3ZnCl2With
3.0mol·dm-3NH4Cyclic voltammogram in Cl solution.As seen from the figure, there are three pairs of redox peaks on curve 1, be respectively
0.14V and -0.08V, 0.42V and 0.12V, 0.71V and 0.53V, show that now copolymer has good electrochemical activity, works as pH
Increase to 4.7, the oxidation peak under high potential reduces, and continues to increase to 5.2, and the oxidation peak under high potential disappears, and with
The increase of pH value, the area of cyclic voltammogram have declined, and this shows, the pH value of solution has one to the electro-chemical activity of copolymer
Fixed influence, when the pH value of solution>When 4, the copolymer still has electro-chemical activity.
Fig. 3 represents ZnCl of the copolymer in various concentrations2With 3.0moldm-3NH4Cyclic voltammogram in Cl solution, it is molten
The pH 4.7 of liquid.As seen from the figure, with ZnCl2The increase of concentration, the area of cyclic voltammetry curve slowly reduce, and show ZnCl2It is dense
Spend the influence very little to the electrochemical properties of copolymer.
Curve 1,2,3 represents copolymer under open-circuit voltage respectively in Fig. 4, respectively containing in pH 4.2,4.7 and 5.2
2.0mol·dm-3ZnCl2With 3.0moldm-3NH4AC impedance figure in Cl solution.All AC impedance figures have
One semicircle (Rct) formed with straight line.This shows that copolymer reaction is controlled by kinetics in high frequency, in low frequency
Under be to be spread to control by material, and with the increase of pH value, the charge-transfer resistance of copolymer increases, and this is followed with copolymer
Ring volt-ampere result is consistent.
Curve 1,2,3 represents copolymer under open-circuit voltage respectively in Fig. 5,1.5,2.0,2.5moldm-3ZnCl2
With 3.0moldm-3NH4AC impedance figure in Cl solution, the pH 4.7 of solution.All AC impedance figures are to have one
Semicircle (Rct) formed with straight line, this shows that copolymer reaction is controlled by kinetics in high frequency, is at low frequency
Spread and controlled by material.As illustrated, work as ZnCl2When concentration is relatively low, the charge-transfer resistance of copolymer is smaller, this show with
ZnCl2Concentration increases, and the electro-chemical activity of copolymer reduces.
3rd, secondary cell performance evaluation
Curve 1,2,3 represents with 5,2 and 1mAcm respectively in Fig. 6-2Constant current carry out discharge and recharge.Battery is filled first
To upper voltage limit 1.5V, this equivalent to copolymer current potential 0.5V (vs.SCE), according to the cyclic voltammogram of copolymer and exchange
Impedance diagram, voltage now will not cause copolymer peroxidating and larger degraded, then battery discharged with constant current,
Now copolymer will be gradated by oxidation state as complete reduction-state.Three curves are closely similar in Fig. 6, and with 2mAcm-2With
1mA·cm-2Constant current when carrying out discharge and recharge curve have one section of electric discharge slope at 1.2~1.3V, this is put with polyaniline
Electrical characteristics match, compared with lithium ion battery, without obvious discharge platform.When current density is from 5mAcm-2It is reduced to
1mA·cm-2, now battery specific capacity is by 70.06mAhg-183.93,92.75mAhg is increased to respectively-1, coulombic efficiency point
Not Wei 85.10%, 96.62%, 95.52%, show that battery issues in low current density and be born from electric discharge, and in view of actually making
With, therefore we select 2mAcm-2Constant current carry out discharge and recharge.
Curve 1 and curve 2 represent the 1st circulation and charging and discharging curve during the 150th circulation respectively in Fig. 7.For the first time
During discharge and recharge, specific discharge capacity 83.49mAhg-1, coulombic efficiency 96.0%, its result be less than Fig. 6 in 2mAcm-2
Specific capacity and coulombic efficiency during discharge and recharge are carried out, because after discharge and recharge for several times, electro-chemical activity slightly reduces, it
Keep afterwards stable.After carrying out 150 discharge and recharges to battery, now specific capacity is 80.63mAhg-1, coulombic efficiency reaches
99.16%, this shows that the secondary cell has good charge-discharge performance.
Embodiment 2：
Basic practice is same as Example 1, and difference is the preparation process of aniline/N- methyl thionin copolymers.
1st, the preparation of raw material
Aniline, N- methyl thionins, sulfate
Wherein aniline saves backup after vacuum distillation at 4 DEG C
2nd, polymer electrolyte liquid is configured
The concentration of aniline is 0.1moldm-3, N- methyl thionins concentration is 1.5mmoldm-3, the concentration of sulfuric acid is
0.5mol·dm-3
3rd, the preparation of electrolytic cell
Electrolytic cell uses three-electrode system, and working electrode and auxiliary electrode are platinized platinum, reference electrode saturated calomel electrode.
4th, electrochemical polymerization
Cyclic voltammetry scanning current potential is -0.1~1.1V (vs.SCE) during polymerization, and sweep speed 60mV/s, current potential is swept
The number of turns is retouched as 60 circles.
5th, washing is with drying
One layer of thicker black film (electrolysate) is obtained after electrolysis, on working electrode, with the second distillation water washing electricity
Product is solved, is dried at 60~90 DEG C, you can obtain aniline and N- methyl thionin copolymers.
Embodiment 3：
Basic practice is same as Example 1, and difference is the preparation process of aniline/N- methyl thionin copolymers.
1st, the preparation of raw material
Aniline, N- methyl thionins, sulfate
Wherein aniline saves backup after vacuum distillation at 4 DEG C.
2nd, polymer electrolyte liquid is configured
The concentration of aniline is 0.4moldm-3, N- methyl thionins concentration is 3.0mmoldm-3, the concentration of sulfuric acid is
0.5mol·dm-3。
3rd, the preparation of electrolytic cell
Electrolytic cell uses three-electrode system, and working electrode and auxiliary electrode are platinized platinum, reference electrode saturated calomel electrode.
4th, electrochemical polymerization
Cyclic voltammetry scanning current potential is -0.1-1.1V (vs.SCE) during polymerization, sweep speed 60mV/s, electric potential scanning
The number of turns is 20 circles.
5th, washing is with drying
One layer of thicker black film (electrolysate) is obtained after electrolysis, on working electrode, with the second distillation water washing electricity
Product is solved, is dried at 60~90 DEG C, you can obtain aniline and N- methyl thionin copolymers.
Embodiment 4：
Basic practice is same as Example 1, and difference is the preparation process of aniline/N- methyl thionin copolymers.
1st, the preparation of raw material
Aniline, N- methyl thionins, sulfate
Wherein aniline saves backup after vacuum distillation at 4 DEG C
2nd, polymer electrolyte liquid is configured
The concentration of aniline is 0.2moldm-3, N- methyl thionins concentration is 2.5mmoldm-3, the concentration of sulfuric acid is
0.3mol·dm-3
3rd, the preparation of electrolytic cell
Electrolytic cell uses three-electrode system, and working electrode and auxiliary electrode are platinized platinum, reference electrode saturated calomel electrode.
4th, electrochemical polymerization
Cyclic voltammetry scanning current potential is -0.1-1.1V (vs.SCE) during polymerization, sweep speed 60mV/s, electric potential scanning
The number of turns is 50 circles.
5th, washing is with drying
One layer of thicker black film (electrolysate) is obtained after electrolysis, on working electrode, with the second distillation water washing electricity
Product is solved, is dried at 60~90 DEG C, you can obtain aniline and N- methyl thionin copolymers.
Embodiment 5：
Basic practice is same as Example 1, and difference is the preparation process of aniline/N- methyl thionin copolymers.
1st, the preparation of raw material
Aniline, N- methyl thionins, sulfate
Wherein aniline saves backup after vacuum distillation at 4 DEG C
2nd, polymer electrolyte liquid is configured
The concentration of aniline is 0.2moldm-3, N- methyl thionins concentration is 2.5mmoldm-3, the concentration of sulfuric acid is
0.8mol·dm-3
3rd, the preparation of electrolytic cell
Electrolytic cell uses three-electrode system, and working electrode and auxiliary electrode are platinized platinum, reference electrode saturated calomel electrode.
4th, electrochemical polymerization
Cyclic voltammetry scanning current potential is -0.1-1.1V (vs.SCE) during polymerization, sweep speed 60mV/s, electric potential scanning
The number of turns is 25 circles.
5th, washing is with drying
One layer of thicker black film (electrolysate) is obtained after electrolysis, on working electrode, with the second distillation water washing electricity
Product is solved, is dried at 60~90 DEG C, you can obtain aniline and N- methyl thionin copolymers.
Polymer and the battery performance of composition prepared by embodiment 2-5 is close with embodiment 1.
Claims (8)
1. a kind of aniline/N- methyl thionin copolymers, it is characterised in that it is prepared by following methods：In three electrode groups
Into electrolytic cell in, at normal temperatures and pressures, using cyclic voltammetry to aniline, N- methyl thionins, sulfuric acid composition electrolyte enter
Row electrolysis, the electrolysate obtained on the working electrode (s is one layer of thicker black film, and with second distillation water washing, the electrolysis is produced
Thing, and dried at 60~90 DEG C, produce aniline/N- methyl thionin copolymers；Wherein, the concentration of the aniline be 0.1~
0.4mol·dm-3, the concentration of N- methyl thionins is 1.5~3.0mmoldm-3, the concentration of sulfuric acid is 0.3~0.8moldm-3。
2. aniline according to claim 1/N- methyl thionin copolymers, it is characterised in that：Utilize the cyclic voltammetry
When being electrolysed, scanning potential range is -0.1~1.1V, and sweep speed is 40~100mVs-1, the electric potential scanning number of turns is 20-
60 circles.
3. aniline according to claim 1/N- methyl thionin copolymers, it is characterised in that：The electricity of the three electrodes composition
In Xie Chi, working electrode and auxiliary electrode are platinum electrode, and reference electrode is saturated calomel electrode.
4. zinc-aniline/N- the methyl thionins for being made negative electrode composition using aniline/N- methyl thionin copolymers described in claim 1 are total to
Polymers secondary cell, it is characterised in that：The negative electrode of the secondary cell is aniline/N- methyl thionin copolymers, and anode is zinc metal sheet, electricity
Liquid is solved by ZnCl2With NH4The solution of Cl compositions.
5. zinc-aniline according to claim 4/N- methyl thionin copolymer secondary cells, it is characterised in that：The electrolysis
ZnCl in liquid2Concentration be 1.5~2.5moldm-3, NH4Cl concentration is 2.0~3.5moldm-3。
6. zinc-aniline/N- methyl thionin copolymer secondary cells according to claim 4 or 5, it is characterised in that：Control
The pH value of the electrolyte is 4.2~5.2.
7. zinc-aniline according to claim 4/N- methyl thionin copolymer secondary cells, it is characterised in that：The zinc-
Wei Nilunbu is used as barrier film in aniline/N- methyl thionin copolymer secondary cells.
8. zinc-aniline according to claim 4/N- methyl thionin copolymer secondary cells, it is characterised in that：The zinc metal sheet
First through α-Al before use2O3Polishing, is then cleaned by ultrasonic in ethanol, redistilled water successively.
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