CN106920935B - A kind of lead storage battery and preparation method thereof that π type-conjugated oxidation reductive polymerization object is modified - Google Patents
A kind of lead storage battery and preparation method thereof that π type-conjugated oxidation reductive polymerization object is modified Download PDFInfo
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Abstract
The present invention relates to lead-acid accumulator fields, disclose a kind of lead storage battery and preparation method thereof that π type-conjugated oxidation reductive polymerization object is modified.Include in the anode lead plaster: 98.5 ~ 99.5 parts of lead powder, 0.2 ~ 0.8 part of additive, 0.3 ~ 0.7 part of mixed polymer powder；Mixed polymer powder is made of π type-conjugated oxidation reductive polymerization object, surface anti-oxidation functional group sulfonated aromatic hydrocarbon polymer and single-walled carbon nanotube.Contain the anti-oxidant functional group's conjugated oxidation reductive polymerization object of surface modification in active material of the invention, there is the electron storage ability and swift electron reaction rate of strength, there is available redox node to have relatively strong oxidable reduction activation in polymer.Therefore lead storage battery energy density with higher, battery discharge time is obviously prolonged under the conditions of battery high-multiplying power discharge, while improving the service life of battery.
Description
Technical field
The present invention relates to the modified lead storages in lead-acid accumulator field more particularly to a kind of π type-conjugated oxidation reductive polymerization object
Battery and preparation method thereof.
Background technique
Lead-acid accumulator has more than 150 years history from invention so far, and because it has, highly-safe, performance is stable, manufacture
Cost is relatively low, and has the characteristics that very high recycle value, is widely used in it in national economy and people's lives.
But that there is also cycle lives is low, energy density utilization rate is low, active material conversion not exclusively causes capacity for lead-acid accumulator simultaneously
A series of problems, such as decaying, becomes and restricts an important factor for lead storage battery occupies bigger market.
The electric conductivity of electrode is to influence a key factor of pole plate performance in lead-acid battery.Good electric conductivity contracting
The chemical synthesis technology period of short pole plate reduces positive argillization, reduces cathode sulfation, improve the utilization rate of being.Graphene is made
For novel two-dimensional material has the features such as good electric conductivity, thermal conductivity, mechanical performance, low-resistivity and is applied to battery
In, although being promoted in terms of battery high current, electric conductivity, improving energy density, there are also in terms of premature capacity loss
There is no obvious effects.The another aspect preparation structure number of plies is less and the graphene higher cost of stable structure, the life to battery
Cost is produced to have greatly increased.
To sum up, if it is possible to a kind of electron storage ability of strength be provided and swift electron reaction rate while being had available
Redox node has the substance of relatively strong oxidable reduction activation method, it will keeps the cycle life of lead-acid accumulator and energy close
Degree is greatly improved.
Summary of the invention
In order to solve the above-mentioned technical problems, the present invention provides a kind of modified lead storages of π type-conjugated oxidation reductive polymerization object
Battery and preparation method thereof.The anti-oxidant functional group's conjugated oxidation of surface modification is added in the active material of lead storage battery of the invention
Reductive polymerization object.π type-conjugated oxidation reductive polymerization object has the electron storage ability and swift electron reaction rate of strength, together
When polymer in there is available redox node to have relatively strong oxidable reduction activation.Therefore using addition π type-conjugated oxidation
The modified lead storage battery of reductive polymerization object has biggish promotion in energy density, battery discharge under the conditions of battery high-multiplying power discharge
Time is obviously prolonged, while improving the service life of battery.
The specific technical proposal of the invention is: the lead storage battery that a kind of π type-conjugated oxidation reductive polymerization object is modified, every 100
In the positive electode of lead battery lead plaster of mass parts include following substance: 98.5 ~ 99.5 parts of lead powder, 0.2 ~ 0.8 part of additive, 0.3 ~
0.7 part of mixed polymer powder；The mixed polymer powder is by π type-conjugated oxidation reductive polymerization object, surface anti-oxidation function
Group's sulfonated aromatic hydrocarbon polymer and single-walled carbon nanotube are prepared.
The anti-oxidant functional group's conjugated oxidation reductive polymerization of surface modification is added in the active material of lead storage battery of the invention
Object (utilizes the polymer-modified π type of surface anti-oxidation functional group sulfonated aromatic hydrocarbon-conjugated oxidation reductive polymerization object surface group, prevents
Strong oxidizing property changes its polymer property in positive charge and discharge process).π type-conjugated oxidation reductive polymerization object has the electricity of strength
Sub- storage capacity and swift electron reaction rate, while there is available redox node to have relatively oxidable by force go back in polymer
Former activity.Therefore there is biggish mention in energy density using addition π type-modified lead storage battery of conjugated oxidation reductive polymerization object
It rises, battery discharge time is obviously prolonged under the conditions of battery high-multiplying power discharge, while improving the service life of battery.
Preferably, the π type-conjugated oxidation reductive polymerization object be it is poly- ((N, N '-bis- (2- octyldodecyls) -1,
4,5,8- naphthalimides-diyl)-m- 5,5 '-(2,2 '-Er Sai Pin), it is poly- ((N, N '-bis- (2- octyldodecyls) -1,
4,5,8- naphthalimides-diyl)-m- 5,5 '-(2,2 '-(1,2- second diyl)-Sai Pin) or 4-(1,3- dimethyl-
2,3- dihydro -1H- benzimidazoles)-diyl-N, N- diphenylaniline doping vario-property poly- ((N, N '-bis- (2- octyldodecyls
At least one of base)-Isosorbide-5-Nitrae, 5,8- naphthalimides-diyl)-m- 5,5 '-(2,2 '-Er Sai Pin).
In the technical scheme, above-mentioned three kinds of substances have the electron hole delivering path and naphthalene diformazan in conjugated polymer
The linear pi-conjugated alternately bis- thiophene skeletons of naphthalene-, the System of Double Electrons for providing a high reversible of acid imide unit can make it
Swift electron transmission and the intact oxidised reduction activation site of non-conjugated redox polymers, can steadily store electronics and repetition
Invertibity.
Preferably, the π type-conjugated oxidation reductive polymerization object and surface anti-oxidation functional group sulfonated aromatic hydrocarbon polymer
Mass ratio is 3:1-9:4；The mass ratio of the π type-conjugated oxidation reductive polymerization object and single-walled carbon nanotube is 1.5:1 ~ 1:1.
Preferably, the surface anti-oxidation functional group sulfonated aromatic hydrocarbon polymer is that relative molecular mass 7000 ~ 15000 is high
The naphthalene sulfonic acid condensate of sulfonation degree.Above-mentioned naphthalene sulfonic acid condensate can effectively substitute the lignin sulfonic acid being easily precipitated under the high temperature conditions
Salt.
A kind of preparation method for the lead storage battery that π type-conjugated oxidation reductive polymerization object is modified comprising the steps of:
(1) π type-conjugated oxidation reductive polymerization object, surface anti-oxidation functional group sulfonated aromatic hydrocarbon polymer are dissolved in organic molten
In agent, obtained polymer dispersion liquid carries out good pressure distribution with good pressure distribution equipment instrument and handles 2 ~ 3 times, the polymer handled well point
Dispersion liquid stirs 3 ~ 5 hours under conditions of 85-95 DEG C, obtains stable mixed with polymers liquid.
Using the polymer-modified π type of surface anti-oxidation functional group sulfonated aromatic hydrocarbon-conjugated oxidation reductive polymerization object surface group,
Prevent strong oxidizing property in positive charge and discharge process from changing its polymer property.
(2) polymeric precipitate is collected by filtration in stable mixed with polymers liquid, it is dry after being washed with organic solvent,
Mixed polymer powder is obtained after mixing again with single-walled carbon nanotube.
(3) after mixing by obtained mixed polymer powder and additive, ball in ball grinder is put into after adding pure water
Mill obtains the polymer dispersion liquid of particle size uniformity.
(4) polymer dispersion liquid is added in lead powder, positive electode of lead battery lead plaster is made；According to lead storage battery manufacturing process
The modified lead storage battery of π type-conjugated oxidation reductive polymerization object is made.
Preferably, the organic solvent in step (1) is 1,2- dichloro-benzenes-chloroformic solution, π type-conjugated oxidation reduction is poly-
Object and 1 is closed, 2- dichloro-benzenes-chloroformic solution liquid-solid ratio is 1g:12 ~ 18mL；
Preferably, organic solvent in step (2) is alcohols or ethers organic solution, polymeric precipitate with it is organic
The liquid-solid ratio of solution is 1g:25 ~ 40mL.
Preferably, being 15000 ~ 18000psi, stirring under the condition of high voltage of good pressure distribution equipment instrument described in step (1)
Time is 5 ~ 8 hours, and speed of agitator is 800 ~ 1100rpm.
Preferably, method dry in step (2) be freeze-drying or 80-95 DEG C at a temperature of dry drying.
Preferably, Ball-milling Time control is 3 ~ 5 hours in step (3), particle size control is 1.4 ~ 15 microns.
It is compared with the prior art, the beneficial effects of the present invention are:
1, π type-conjugated oxidation reductive polymerization object has steady chemical structure and is not easily decomposed, lower-price characteristic；
2, π type-conjugated oxidation reductive polymerization object has two formyl of electron hole delivering path and naphthalene in conjugated polymer
The linear pi-conjugated alternately bis- thiophene skeletons of naphthalene-of imines unit, the System of Double Electrons for providing a high reversible can make it fast
Fast electron transport ability greatly promotes the electric conductivity of active material, is conducive to formation efficiency, heavy-current discharge capacity of pole plate etc.
Aspect；The electron storage ability being provided simultaneously with improves the active material conversion ratio inside battery discharge later period pole plate, battery energy
Metric density also increases accordingly, that is, improves the capacity of battery；
3, π type-conjugated oxidation reductive polymerization object has the intact oxidised reduction activation site of non-conjugated redox polymers,
Storage electronics and repetition invertibity that can be stable.Its redox efficiency is improved, premature capacity loss can be efficiently solved and asked
Topic；Using the polymer-modified π type of surface anti-oxidation functional group sulfonated aromatic hydrocarbon-conjugated oxidation reductive polymerization object surface group, prevent
Strong oxidizing property changes its polymer property in positive charge and discharge process, while can substitute in cathode and to be easily precipitated under the high temperature conditions
Lignosulfonates.
Detailed description of the invention
Fig. 1 is to be added to plate active material Electronic Speculum at the end of the electric discharge of π type-conjugated oxidation reductive polymerization object anode diachylon
Figure；
Fig. 2 is to be not added with plate active material Electronic Speculum at the end of the electric discharge of π type-conjugated oxidation reductive polymerization object anode diachylon
Figure.
Specific embodiment
The present invention will be further described with reference to the examples below.
Embodiment 1
The modified lead storage battery of a kind of π type-conjugated oxidation reductive polymerization object, in the lead storage battery lead plaster of every 100 mass parts
Include following substance: 98.5 parts of lead powder, 0.8 part of additive, 0.7 part of mixed polymer powder；The mixed polymer powder is by π
Type-conjugated oxidation reductive polymerization object, surface anti-oxidation functional group sulfonated aromatic hydrocarbon polymer and single-walled carbon nanotube are prepared.
Wherein, π type-conjugated oxidation reductive polymerization object be it is poly- ((N, N '-bis- (2- octyldodecyl)-Isosorbide-5-Nitraes, 5,
8- naphthalimide-diyl)-m- 5,5 '-(2,2 '-Er Sai Pin).The surface anti-oxidation functional group sulfonated aromatic hydrocarbon polymer
For the naphthalene sulfonic acid condensate of 15000 highly sulfonated of relative molecular mass.π type-conjugated oxidation reductive polymerization the object and surface are anti-
The mass ratio of oxygenated functional group sulfonated aromatic hydrocarbon polymer is 3:1；π type-conjugated oxidation reductive polymerization the object and single
The mass ratio of pipe is 3:2.
A kind of preparation method for the lead storage battery that π type-conjugated oxidation reductive polymerization object is modified comprising the steps of:
(1) π type-conjugated oxidation reductive polymerization object, surface anti-oxidation functional group sulfonated aromatic hydrocarbon polymer are dissolved in 1,2- bis-
In chlorobenzene-chloroformic solution, wherein π type-conjugated oxidation reductive polymerization object and 1,2- dichloro-benzenes-chloroformic solution liquid-solid ratio are 1g:
15mL；Obtained polymer dispersion liquid carries out good pressure distribution with good pressure distribution equipment instrument and handles 3 times, is under condition of high voltage
15000psi, mixing time are 5 hours, speed of agitator 1100rpm, and the polymer dispersion liquid handled well is under conditions of 90 DEG C
Stirring 5 hours, obtains stable mixed with polymers liquid.
(2) polymeric precipitate is collected by filtration in stable mixed with polymers liquid, at 85 DEG C after being washed with methanol
At a temperature of dry drying, then mixed polymer powder is obtained after mixing with single-walled carbon nanotube.Wherein, polymeric precipitate with have
The liquid-solid ratio of machine solution is 1g:40mL.
(3) after mixing by obtained mixed polymer powder and additive, ball in ball grinder is put into after adding pure water
Mill, Ball-milling Time control are 3 hours, and particle size control is 2 ~ 10 microns.The polymer of particle size uniformity is obtained after ball milling
Dispersion liquid.
(4) polymer dispersion liquid is added in lead powder, lead storage battery lead plaster is made；It is made according to lead storage battery manufacturing process
The modified lead storage battery of π type-conjugated oxidation reductive polymerization object.
Embodiment 2
The modified lead storage battery of a kind of π type-conjugated oxidation reductive polymerization object, in the lead storage battery lead plaster of every 100 mass parts
Include following substance: 99 parts of lead powder, 0.5 part of additive, 0.5 part of mixed polymer powder；The mixed polymer powder is by π
Type-conjugated oxidation reductive polymerization object, surface anti-oxidation functional group sulfonated aromatic hydrocarbon polymer and single-walled carbon nanotube are prepared.
Wherein, π type-conjugated oxidation reductive polymerization object be it is poly- ((N, N '-bis- (2- octyldodecyl)-Isosorbide-5-Nitraes, 5,
8- naphthalimide-diyl)-m- 5,5 '-(2,2 '-(1,2- second diyl)-Sai Pin).Surface anti-oxidation functional group sulphur
Change the naphthalene sulfonic acid condensate that aromatic polymer is 10000 highly sulfonated of relative molecular mass.The π type-conjugated oxidation reduction is poly-
The mass ratio for closing object and surface anti-oxidation functional group sulfonated aromatic hydrocarbon polymer is 9:4；The π type-conjugated oxidation reductive polymerization object
Mass ratio with single-walled carbon nanotube is 1:1.
A kind of preparation method for the lead storage battery that π type-conjugated oxidation reductive polymerization object is modified comprising the steps of:
(1) π type-conjugated oxidation reductive polymerization object, surface anti-oxidation functional group sulfonated aromatic hydrocarbon polymer are dissolved in 1,2- bis-
In chlorobenzene-chloroformic solution, wherein π type-conjugated oxidation reductive polymerization object and 1,2- dichloro-benzenes-chloroformic solution liquid-solid ratio are 1g:
12mL；Obtained polymer dispersion liquid carries out good pressure distribution with good pressure distribution equipment instrument and handles 2 times, is under condition of high voltage
18000psi, mixing time are 8 hours, speed of agitator 800rpm, and the polymer dispersion liquid handled well is under conditions of 90 DEG C
Stirring 4 hours, obtains stable mixed with polymers liquid.
(2) polymeric precipitate is collected by filtration in stable mixed with polymers liquid, at 90 DEG C after being washed with ether
At a temperature of dry drying, then mixed polymer powder is obtained after mixing with single-walled carbon nanotube.Wherein, polymeric precipitate with have
The liquid-solid ratio of machine solution is 1g:30mL.
(3) after mixing by obtained mixed polymer powder and additive, ball in ball grinder is put into after adding pure water
Mill, Ball-milling Time control are 5 hours, and particle size control is 1.5 ~ 8 microns.The polymer of particle size uniformity is obtained after ball milling
Dispersion liquid.
(4) polymer dispersion liquid is added in lead powder, lead storage battery lead plaster is made；It is made according to lead storage battery manufacturing process
The modified lead storage battery of π type-conjugated oxidation reductive polymerization object.
Embodiment 3
The modified lead storage battery of a kind of π type-conjugated oxidation reductive polymerization object, in the lead storage battery lead plaster of every 100 mass parts
Include following substance: 98.8 parts of lead powder, 05 part of additive, 0.7 part of mixed polymer powder；The mixed polymer powder is by π
Type-conjugated oxidation reductive polymerization object, surface anti-oxidation functional group sulfonated aromatic hydrocarbon polymer and single-walled carbon nanotube are prepared.
Wherein, π type-conjugated oxidation reductive polymerization object is 4-(1,3- dimethyl -2,3- dihydro -1H- phenylpropyl alcohol miaow
Azoles)-diyl-N, N- diphenylaniline doping vario-property poly- ((N, N '-bis- (2- octyldodecyl)-Isosorbide-5-Nitraes, 5,8- naphthalene, two formyl
Imines-diyl)-m- 5,5 '-(2,2 '-Er Sai Pin).The surface anti-oxidation functional group sulfonated aromatic hydrocarbon polymer is average molecular
The naphthalene sulfonic acid condensate of 9000 highly sulfonated of quality.π type-conjugated oxidation reductive polymerization the object and surface anti-oxidation functional group sulphur
The mass ratio for changing aromatic polymer is 9:4；The mass ratio of the π type-conjugated oxidation reductive polymerization object and single-walled carbon nanotube is
6:5.
A kind of preparation method for the lead storage battery that π type-conjugated oxidation reductive polymerization object is modified comprising the steps of:
(1) π type-conjugated oxidation reductive polymerization object, surface anti-oxidation functional group sulfonated aromatic hydrocarbon polymer are dissolved in 1,2- bis-
In chlorobenzene-chloroformic solution, wherein π type-conjugated oxidation reductive polymerization object and 1,2- dichloro-benzenes-chloroformic solution liquid-solid ratio are 1g:
18mL；Obtained polymer dispersion liquid carries out good pressure distribution with good pressure distribution equipment instrument and handles 2 times, is under condition of high voltage
16000psi, mixing time are 7 hours, speed of agitator 1000rpm, and the polymer dispersion liquid handled well is under conditions of 90 DEG C
Stirring 3 hours, obtains stable mixed with polymers liquid.
(2) polymeric precipitate is collected by filtration in stable mixed with polymers liquid, is freezed after being washed with ethyl alcohol
It is dry, then mixed polymer powder is obtained after mixing with single-walled carbon nanotube.Wherein, the liquid of polymeric precipitate and organic solution
Gu than being 1g:40mL.
(3) after mixing by obtained mixed polymer powder and additive, ball in ball grinder is put into after adding pure water
Mill, Ball-milling Time control are 4 hours, and particle size control is 3 ~ 12 microns.The polymer of particle size uniformity is obtained after ball milling
Dispersion liquid.
(4) polymer dispersion liquid is added in lead powder, lead storage battery lead plaster is made；It is made according to lead storage battery manufacturing process
The modified lead storage battery of π type-conjugated oxidation reductive polymerization object.
Embodiment 4
The modified lead storage battery of a kind of π type-conjugated oxidation reductive polymerization object, in the lead storage battery lead plaster of every 100 mass parts
Include following substance: 99 parts of lead powder, 0.5 part of additive, 0.5 part of mixed polymer powder；The mixed polymer powder is by π
Type-conjugated oxidation reductive polymerization object, surface anti-oxidation functional group sulfonated aromatic hydrocarbon polymer and single-walled carbon nanotube are prepared.
Wherein, π type-conjugated oxidation reductive polymerization object be it is poly- ((N, N '-bis- (2- octyldodecyl)-Isosorbide-5-Nitraes, 5,
8- naphthalimide-diyl)-m- 5,5 '-(2,2 '-Er Sai Pin) and 4-(1,3- dimethyl -2,3- dihydro -1H- phenylpropyl alcohol miaow
Azoles)-diyl-N, N- diphenylaniline doping vario-property poly- ((N, N '-bis- (2- octyldodecyl)-Isosorbide-5-Nitraes, 5,8- naphthalene, two formyl
Imines-diyl) mixture in-m- 5,5 '-(2,2 '-Er Sai Pin).The surface anti-oxidation functional group sulfonated aromatic hydrocarbon polymer
For the naphthalene sulfonic acid condensate of 11000 highly sulfonated of relative molecular mass.π type-conjugated oxidation reductive polymerization the object and surface are anti-
The mass ratio of oxygenated functional group sulfonated aromatic hydrocarbon polymer is 18:7；π type-conjugated oxidation reductive polymerization the object and single
The mass ratio of pipe is 1:1.
A kind of preparation method for the lead storage battery that π type-conjugated oxidation reductive polymerization object is modified comprising the steps of:
(1) π type-conjugated oxidation reductive polymerization object, surface anti-oxidation functional group sulfonated aromatic hydrocarbon polymer are dissolved in 1,2- bis-
In chlorobenzene-chloroformic solution, wherein π type-conjugated oxidation reductive polymerization object and 1,2- dichloro-benzenes-chloroformic solution liquid-solid ratio are 1g:
14mL；Obtained polymer dispersion liquid carries out good pressure distribution with good pressure distribution equipment instrument and handles 3 times, is under condition of high voltage
16000psi, mixing time are 6 hours, speed of agitator 900rpm, and the polymer dispersion liquid handled well is under conditions of 95 DEG C
Stirring 4 hours, obtains stable mixed with polymers liquid.
(2) polymeric precipitate is collected by filtration in stable mixed with polymers liquid, at 95 DEG C after being washed with ethyl alcohol
At a temperature of dry drying, then mixed polymer powder is obtained after mixing with single-walled carbon nanotube.Wherein, polymeric precipitate with have
The liquid-solid ratio of machine solution is 1g:25mL.
(3) after mixing by obtained mixed polymer powder and additive, ball in ball grinder is put into after adding pure water
Mill, Ball-milling Time control are 5 hours, and particle size control is 3 ~ 12 microns.The polymer of particle size uniformity is obtained after ball milling
Dispersion liquid.
(4) polymer dispersion liquid is added in lead powder, lead storage battery lead plaster is made；It is made according to lead storage battery manufacturing process
The modified lead storage battery of π type-conjugated oxidation reductive polymerization object.
The present invention is added to π type-conjugated oxidation reductive polymerization object battery and conventional batteries carry out after electric discharge
Point electron microscope comparison, as shown in Figure 1 and Figure 2, by active matter when ending whether there is or not the electric discharge of the pole plate of conjugated oxidation reductive polymerization object
The observation of matter electron microscope can compare, and lead sulfate particle is than normal plate when being added to the pole plate electric discharge cut-off of conjugated polymer
Particle size is small, is more evenly distributed, and illustrates that the pole plate for being added to conjugated polymer is easy to be reduced into brown lead oxide in the charging stage, right
There is facilitation in the cycle life for extending battery.
Therefore there is biggish mention in energy density using addition π type-modified lead storage battery of conjugated oxidation reductive polymerization object
It rises, battery discharge time is obviously prolonged under the conditions of battery high-multiplying power discharge, while improving the service life of battery.
Raw materials used in the present invention, equipment is unless otherwise noted the common raw material, equipment of this field；In the present invention
Method therefor is unless otherwise noted the conventional method of this field.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way, it is all according to the present invention
Technical spirit any simple modification, change and equivalent transformation to the above embodiments, still fall within the technology of the present invention side
The protection scope of case.
Claims (9)
1. a kind of modified lead storage battery of π type-conjugated oxidation reductive polymerization object, it is characterised in that: the lead electric power storage of every 100 mass parts
It include following substance: 98.5 ~ 99.5 parts of lead powder, 0.2 ~ 0.8 part of additive, 0.3 ~ 0.7 part of mixed polymer in the anode diachylon of pond
Powder；The mixed polymer powder is polymerize by π type-conjugated oxidation reductive polymerization object, surface anti-oxidation functional group sulfonated aromatic hydrocarbon
Object and single-walled carbon nanotube are prepared；
The preparation method of the modified lead storage battery of the π type-conjugated oxidation reductive polymerization object comprises the steps of:
(1) π type-conjugated oxidation reductive polymerization object, surface anti-oxidation functional group sulfonated aromatic hydrocarbon polymer are dissolved in organic solvent,
Obtained polymer dispersion liquid carries out good pressure distribution with good pressure distribution equipment instrument and handles 2 ~ 3 times, the polymer dispersion liquid handled well
It is stirred 3 ~ 5 hours under conditions of 85-95 DEG C, obtains stable mixed with polymers liquid；
(2) polymeric precipitate is collected by filtration in stable mixed with polymers liquid, it is dry after being washed with organic solvent, then with
Mixed polymer powder is obtained after single-walled carbon nanotube mixing；
(3) after mixing by obtained mixed polymer powder and additive, ball milling in ball grinder is put into after addition pure water to obtain
To the polymer dispersion liquid of particle size uniformity；
(4) polymer dispersion liquid is added in lead powder, positive electode of lead battery lead plaster is made；It is made according to lead storage battery manufacturing process
The modified lead storage battery of π type-conjugated oxidation reductive polymerization object.
2. a kind of modified lead storage battery of π type-conjugated oxidation reductive polymerization object as described in claim 1, which is characterized in that institute
The π type stated-conjugated oxidation reductive polymerization object is poly- ((N, N '-bis- (2- octyldodecyl)-Isosorbide-5-Nitraes, 5,8- naphthalimides-
Diyl)-m- 5,5 '-(2,2 '-Er Sai Pin), poly- ((N, N '-bis- (2- octyldodecyl)-Isosorbide-5-Nitraes, 5,8- naphthalimides-
Diyl)-m- 5,5 '-(2,2 '-(1,2- second diyl)-Sai Pin) or 4-(1,3- dimethyl -2,3- dihydro -1H- phenylpropyl alcohol miaow
Azoles)-diyl-N, N- diphenylaniline doping vario-property poly- ((N, N '-bis- (2- octyldodecyl)-Isosorbide-5-Nitraes, 5,8- naphthalene, two formyl
At least one of imines-diyl)-m- 5,5 '-(2,2 '-Er Sai Pin).
3. a kind of modified lead storage battery of π type-conjugated oxidation reductive polymerization object as described in claim 1, which is characterized in that institute
The mass ratio for stating π type-conjugated oxidation reductive polymerization object and surface anti-oxidation functional group sulfonated aromatic hydrocarbon polymer is 3:1-9:4；Institute
The mass ratio for stating π type-conjugated oxidation reductive polymerization object and single-walled carbon nanotube is 1.5:1 ~ 1:1.
4. a kind of modified lead storage battery of π type-conjugated oxidation reductive polymerization object as described in claim 1, which is characterized in that institute
State the naphthalene-sulfonic acid condensation that surface anti-oxidation functional group sulfonated aromatic hydrocarbon polymer is 7000 ~ 15000 highly sulfonated of relative molecular mass
Object.
5. a kind of modified lead storage battery of π type-conjugated oxidation reductive polymerization object as described in claim 1, which is characterized in that step
Suddenly the organic solvent in (1) is 1,2- dichloro-benzenes-chloroformic solution, π type-conjugated oxidation reductive polymerization object and 1,2- dichloro-benzenes-chlorine
The solid-to-liquid ratio of imitative solution is 1g:12 ~ 18mL.
6. a kind of modified lead storage battery of π type-conjugated oxidation reductive polymerization object as described in claim 1, which is characterized in that step
Suddenly the organic solvent in (2) is alcohols or ethers organic solution, and the solid-to-liquid ratio of polymeric precipitate and organic solution is 1g:25
~40mL。
7. a kind of modified lead storage battery of π type-conjugated oxidation reductive polymerization object as described in claim 1, which is characterized in that step
It suddenly is 15000 ~ 18000psi under the condition of high voltage of good pressure distribution equipment instrument described in (1), mixing time is 5 ~ 8 hours, stirring
Revolving speed is 800 ~ 1100rpm.
8. a kind of modified lead storage battery of π type-conjugated oxidation reductive polymerization object as described in claim 1, which is characterized in that step
Suddenly method dry in (2) be freeze-drying or 80-95 DEG C at a temperature of dry drying.
9. a kind of modified lead storage battery of π type-conjugated oxidation reductive polymerization object as described in claim 1, which is characterized in that step
Suddenly Ball-milling Time control is 3 ~ 5 hours in (3), and particle size control is 1.4 ~ 15 microns.
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| CN101320800A (en) * | 2008-03-04 | 2008-12-10 | 浙江大学 | Anode material of lead accumulator and preparation method thereof |
| CN101926031A (en) * | 2008-06-25 | 2010-12-22 | 松下电器产业株式会社 | Electricity storage material and electricity storage device |
| CN105826567A (en) * | 2016-05-13 | 2016-08-03 | 超威电源有限公司 | Dispersant and lead plaster for power lead-acid storage battery |
| CN105845940A (en) * | 2016-04-22 | 2016-08-10 | 超威电源有限公司 | Aqueous carbon nanotube dispersion liquid used for lead-acid storage battery, and preparation method and application for aqueous carbon nanotube dispersion liquid |
| CN106410190A (en) * | 2016-11-16 | 2017-02-15 | 双登集团股份有限公司 | Lead-acid storage battery positive lead paste preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101320800A (en) * | 2008-03-04 | 2008-12-10 | 浙江大学 | Anode material of lead accumulator and preparation method thereof |
| CN101926031A (en) * | 2008-06-25 | 2010-12-22 | 松下电器产业株式会社 | Electricity storage material and electricity storage device |
| CN105845940A (en) * | 2016-04-22 | 2016-08-10 | 超威电源有限公司 | Aqueous carbon nanotube dispersion liquid used for lead-acid storage battery, and preparation method and application for aqueous carbon nanotube dispersion liquid |
| CN105826567A (en) * | 2016-05-13 | 2016-08-03 | 超威电源有限公司 | Dispersant and lead plaster for power lead-acid storage battery |
| CN106410190A (en) * | 2016-11-16 | 2017-02-15 | 双登集团股份有限公司 | Lead-acid storage battery positive lead paste preparation method |
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