CN109524666A - A kind of novel conductive agent and preparation method thereof for lithium sulphur one-shot battery - Google Patents
A kind of novel conductive agent and preparation method thereof for lithium sulphur one-shot battery Download PDFInfo
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- CN109524666A CN109524666A CN201811155083.6A CN201811155083A CN109524666A CN 109524666 A CN109524666 A CN 109524666A CN 201811155083 A CN201811155083 A CN 201811155083A CN 109524666 A CN109524666 A CN 109524666A
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
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Abstract
The invention belongs to the technical fields of lithium sulphur one-shot battery, are specifically related to a kind of novel conductive agent and preparation method thereof for lithium sulphur one-shot battery.This kind is used for the novel conductive agent of lithium sulphur one-shot battery, based on polyethylene dioxythiophene, in conjunction with conductive black.In the case where being able to maintain satisfactory electrical conductivity, high conductivity, and the energy density of material will not be reduced, well solve the problem of common commercial conductive agent reduces material energy densities.
Description
Technical field
The invention belongs to the technical fields of lithium sulphur one-shot battery, are specifically related to a kind of for the novel of lithium sulphur one-shot battery
Conductive agent and preparation method thereof.
Background technique
Lithium-sulfur cell is a kind of lithium battery using element sulphur as anode, and elemental sulfur theoretical discharge specific capacity
It can reach 1675mAh/g, significantly larger than commercial widely applied lithium ion battery, therefore sulphur positive active material is mesh
The preceding positive electrode with highest specific capacity.Lithium is that have the smallest relative atomic mass and most negative standard electric in metallic element
Electrode potential, therefore lithium-sulfur cell has high theoretical discharge voltage, high theoretical discharge specific capacity, high theoretical specific energy, is expected to meet
The long term growth requirement of electric car, is a kind of very promising lithium battery.Most researchers are for lithium-sulfur rechargeable battery
Research it is more, but ignore lithium-sulfur cell in the application prospect in one-shot battery field.And in practical applications, lithium sulphur is secondary
The cyclical stability of battery compares with commercial Li-ion battery, and there is also certain gaps, are not able to satisfy commercialization standard still,
But the system has very high initial discharge specific capacity, and battery one is assembled i.e. in Full Power State, can be directly to negative
Power supply is carried, the requirement of one-shot battery is met.
However lithium sulphur one-shot battery still has some problems in the field applied at present, wherein most important sulphur and sulphur
Changing lithium is electronic body, active material can be made to be utilized effectively just needing to add conductive agent, conductive agent is to guarantee electricity
It is great to have good charge-discharge performance, a certain amount of conductive materials are usually added into pole piece production, between active material, are lived
Property substance and collector between play the role of collect micro-current, with reduce electrode contact resistance accelerate electronics mobile speed
Rate, while migration rate of the lithium ion in electrode material can be also effectively improved, so that the efficiency for charge-discharge of electrode is improved, and
The energy density that the addition of common business conductive agent such as conductive black etc. will lead to battery again reduces.Therefore it develops a kind of novel
Conductive material be undoubtedly effective ways solving the above problems.
Summary of the invention
It is an object of the invention to will lead to battery energy for the addition of current common commercial conductive agent such as conductive black etc.
Metric density reduce the problem of and a kind of novel conductive agent and preparation method thereof for lithium sulphur one-shot battery is provided.
The technical solution of the present invention is as follows: a kind of novel conductive agent for lithium sulphur one-shot battery, with polyethylene dioxy
Based on thiophene, in conjunction with conductive black.
The polyethylene dioxythiophene and conductive black mass ratio are 1:1~2.
A kind of preparation method of the novel conductive agent for lithium sulphur one-shot battery, first by 3,4- dioxy second
Base thiophene monomer is added into deionized water, is 1000~8000 revs/min, the case where being stirred at room temperature in revolving speed
Under conductive black is added into deionized water obtains mixed solution again；It then proceedes to stir, by second after 10~30 minutes
Nitrile is added in mixed solution, and ammonium persulfate is then added, and ultrasound simultaneously stirs 10 under the conditions of 40~60 DEG C
Minute；Black precipitate is finally collected, washes clean obtains lithium sulphur one-shot battery conductive agent.
The mass ratio of 3, the 4- ethylenedioxythiophene monomer and conductive black is 1~5:1.
3, the 4- ethylenedioxythiophene monomer of 0.2~5g is added into 30~250mL deionized water；Again by 0.1~1g
Conductive black is added into deionized water.
0.1~1g acetonitrile is added in mixed solution, 0.1~2g ammonium persulfate is then added.
The invention has the benefit that proposition polyethylene dioxythiophene (PEDOT) work that the present invention is innovative
For the main body of conductive agent, conductive agent of the bound fraction conductive black as lithium sulphur one-shot battery.
Both polyethylene dioxythiophene and conductive black cooperate with, and since polyethylene dioxythiophene energy gap is small, have height
Stability, conductivity is high；Bound fraction conductive black, conductive height, chemical stability are good, the excellent spy such as high temperature resistant
Point in the case where being able to maintain satisfactory electrical conductivity, high conductivity, and will not reduce the energy density of material, well solve
Common commercial conductive agent reduces the problem of material energy densities.
The present invention is the most preparation method employed in polyethylene dioxythiophene and conductive black composite material
Easy and high yield synthesizing mean, is easy to commercially produce.High energy density, high electric conductivity, high stable structure
Property, be conducive to the infiltration of electrolyte and the transmission of ion, and structure is not easy avalanche in cyclic process.The method is by skilful
Wonderful and meticulous design, it is easy to operate, yield is big, there is IP prospecting.
Detailed description of the invention
Fig. 1 is the discharge curve using the lithium sulphur one-shot battery of 1 gained novel conductive agent of embodiment.
Fig. 2 is the discharge curve using the lithium sulphur one-shot battery of 2 gained novel conductive agent of embodiment.
Fig. 3 is the discharge curve using the lithium sulphur one-shot battery of conductive agent described in comparative example 1.
Fig. 4 is the discharge curve using the lithium sulphur one-shot battery of conductive agent described in comparative example 2.
Specific embodiment
Below by embodiment, the present invention is described in detail.
Embodiment 1
3,4- ethylenedioxythiophene (EDOT) monomer of 1g is added into 50mL deionized water first, in revolving speed
It is 3000 revs/min, in the case where being stirred at room temperature, then 0.2g conductive black is added thereto to obtain mixed solution, then
Continue to stir, 0.2g acetonitrile is added in mixed solution after twenty minutes, 0.5g ammonium persulfate is then added, it is 10 minutes ultrasonic, and
It is stirred 10 minutes at 50 DEG C, finally collects black precipitate, after deionized water is washed 3 times, dried in 60 DEG C of baking ovens, as lithium sulphur
One-shot battery conductive agent.
Then, conductive agent made from sulfur electrode and the present embodiment and binder are set according to the ratio that mass ratio is 8: 1: 1
In mortar, ground and mixed uniformly scratches on carbon containing aluminium foil at slurry, by slurry, and drying for 24 hours, is existed using tablet press machine at 55 DEG C
5MPa pressure pushes flakiness, obtains positive plate.It is anode, metal Li piece as cathode using sulphur combination electrode or sulfur electrode, adds
Enter electrolyte, battery assembly is carried out in glove box, obtains button CR2025 half-cell.
By Fig. 1, it can be seen that, when using polyethylene dioxythiophene as the main component of conductive agent, sulfur electrode shows excellent
Different discharge capacity, specific discharge capacity are up to 1500mAhg-1, brilliant chemical property is entirely due to polyethylene dioxythiophene
(PEDOT) the features such as electric conductivity is high, chemical stability is good, high temperature resistant.
Embodiment 2
3,4- ethylenedioxythiophene (EDOT) monomer of 1.5g is added into 100mL deionized water first, in revolving speed 4000
Rev/min, it in the case where being stirred at room temperature, then is added thereto 0.3g conductive black to obtain mixed solution, then proceedes to stir,
0.3g acetonitrile is added in mixed solution after 22 minutes, 0.75g ammonium persulfate is then added, it is 10 minutes ultrasonic, and at 55 DEG C
Black precipitate is finally collected in stirring 10 minutes, after deionized water is washed 3 times, is dried in 60 DEG C of baking ovens, as lithium sulphur one-shot battery
Conductive agent.
Then, conductive agent made from sulfur electrode and the present embodiment and binder are set according to the ratio that mass ratio is 8: 1: 1
In mortar, ground and mixed uniformly scratches on carbon containing aluminium foil at slurry, by slurry, and drying for 24 hours, is existed using tablet press machine at 55 DEG C
5MPa pressure pushes flakiness, obtains positive plate.It is anode, metal Li piece as cathode using sulphur combination electrode or sulfur electrode, adds
Enter electrolyte, battery assembly is carried out in glove box, obtains button CR2025 half-cell.
From fig. 2 it can be seen that sulfur electrode shows excellent when using polyethylene dioxythiophene as the main component of conductive agent
Different cyclical stability, specific discharge capacity are up to 1590mAhg-1, it is consistent substantially with respect to 1 capacity of embodiment, this is polyethylene
Dioxy thiophene (PEDOT) good conductivity and its high structural stability, material is not easy the result of avalanche in cyclic process.
Embodiment 3
3,4- ethylenedioxythiophene (EDOT) monomer of 2g is added into 150mL deionized water first, is 5000 in revolving speed
Rev/min, it in the case where being stirred at room temperature, then is added thereto 0.4g conductive black to obtain mixed solution, then proceedes to stir,
0.4g acetonitrile is added in mixed solution after 25 minutes, 1g ammonium persulfate, ultrasound 10 minutes is then added, and stir at 50 DEG C
10 minutes, black precipitate is finally collected, after deionized water is washed 3 times, is dried in 60 DEG C of baking ovens, it is conductive as lithium sulphur one-shot battery
Agent.
Then conductive agent and binder is made in sulfur electrode and this experiment and is placed in mortar according to the ratio that mass ratio is 8: 1: 1
In, ground and mixed uniformly scratches on carbon containing aluminium foil at slurry, by slurry, and drying for 24 hours, is pressed using tablet press machine in 5MPa at 55 DEG C
Power pushes flakiness, obtains positive plate.It is anode, metal Li piece as cathode using sulphur combination electrode or sulfur electrode, electrolysis is added
Liquid carries out battery assembly in glove box, obtains button CR2025 half-cell.
Comparative example 1
0.2g conductive black is added into 50mL deionized water, is stirred after twenty minutes under the conditions of revolving speed is 3000 revs/min
Ultrasound 10 minutes in mixed solution are added in 0.2g acetonitrile, and is stirred 10 minutes at 50 DEG C, finally collects black precipitate, go from
After sub- water washing 3 times, dried in 60 DEG C of baking ovens, as lithium sulphur one-shot battery conductive agent.
Then, conductive agent made from sulfur electrode and the present embodiment and binder are set according to the ratio that mass ratio is 8: 1: 1
In mortar, ground and mixed uniformly scratches on carbon containing aluminium foil at slurry, by slurry, and drying for 24 hours, is existed using tablet press machine at 55 DEG C
5MPa pressure pushes flakiness, obtains positive plate.It is anode, metal Li piece as cathode using sulphur combination electrode or sulfur electrode, adds
Enter electrolyte, battery assembly is carried out in glove box, obtains button CR2025 half-cell.
It can be seen in figure 3 that when using simple conductive black as the main component of conductive agent, sulfur electrode show compared with
The cyclical stability of difference, specific discharge capacity only have 640mAhg-1, opposite embodiment capacity difference is away from huge, this is because not gathering
Ethene dioxythiophene (PEDOT) collaboration improves electric conductivity, causes its whole chemical property bad.
Comparative example 2
3,4- ethylenedioxythiophene (EDOT) monomer of 1g is added into 50mL deionized water first, revolving speed be 3000 turns/
It stirs under the conditions of minute and 0.2g acetonitrile is added in mixed solution after twenty minutes, 0.5g ammonium persulfate, 10 points of ultrasound is then added
Clock, and stirred 10 minutes at 50 DEG C, black precipitate is finally collected, after deionized water is washed 3 times, dries, makees in 60 DEG C of baking ovens
For lithium sulphur one-shot battery conductive agent.
Then, conductive agent made from sulfur electrode and the present embodiment and binder are set according to the ratio that mass ratio is 8: 1: 1
In mortar, ground and mixed uniformly scratches on carbon containing aluminium foil at slurry, by slurry, and drying for 24 hours, is existed using tablet press machine at 55 DEG C
5MPa pressure pushes flakiness, obtains positive plate.It is anode, metal Li piece as cathode using sulphur combination electrode or sulfur electrode, adds
Enter electrolyte, battery assembly is carried out in glove box, obtains button CR2025 half-cell.
It can be seen from figure 4 that when using simple polyethylene dioxythiophene as the main component of conductive agent, sulfur electrode table
Reveal poor cyclical stability, specific discharge capacity only has 965mAhg-1, opposite embodiment capacity difference away from huge, this is because
There is no conductive black collaboration to improve electric conductivity, causes its whole chemical property bad.
Claims (6)
1. a kind of novel conductive agent for lithium sulphur one-shot battery, which is characterized in that based on polyethylene dioxythiophene
Body, in conjunction with conductive black.
2. being used for the novel conductive agent of lithium sulphur one-shot battery according to claim 1, which is characterized in that described poly-
Ethene dioxythiophene and conductive black mass ratio are 1:1~2.
3. the preparation method described in a kind of claim 1 for the novel conductive agent of lithium sulphur one-shot battery, feature exist
In, 3,4- ethylenedioxythiophene monomer is added into deionized water first, revolving speed be 1000~8000
Rev/min, conductive black is added into deionized water again in the case where being stirred at room temperature and obtains mixed solution；So
After continue to stir, after 10~30 minutes by acetonitrile be added mixed solution in, ammonium persulfate is then added, ultrasound
And it is stirred 10 minutes under the conditions of 40~60 DEG C；Black precipitate is finally collected, it is primary that washes clean obtains lithium sulphur
Battery conductive agent.
4. the preparation method for the novel conductive agent of lithium sulphur one-shot battery according to claim 3, which is characterized in that described
The mass ratio of 3,4- ethylenedioxythiophene monomers and conductive black is 1~5:1.
5. the preparation method for the novel conductive agent of lithium sulphur one-shot battery according to claim 3, which is characterized in that will
0.2~5g3,4- ethylenedioxythiophene monomer are added into 30~250mL deionized water；0.1~1g conductive black is added again
Into deionized water.
6. the preparation method for the novel conductive agent of lithium sulphur one-shot battery according to claim 5, which is characterized in that will
0.1~1g acetonitrile is added in mixed solution, and 0.1~2g ammonium persulfate is then added.
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| CN101719545A (en) * | 2009-12-16 | 2010-06-02 | 北京理工大学 | Anode composite material of lithium sulfur battery and preparation method thereof |
| CN102447113A (en) * | 2011-12-12 | 2012-05-09 | 南开大学 | Lithium battery with polymer-coated sulfur/carbon composite material as anode |
| CN103262302A (en) * | 2010-11-04 | 2013-08-21 | 罗伯特·博世有限公司 | Cathode material for a lithium sulfur battery |
| CN106328950A (en) * | 2015-06-18 | 2017-01-11 | 苏州宝时得电动工具有限公司 | Positive electrode material and battery |
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2018
- 2018-09-30 CN CN201811155083.6A patent/CN109524666A/en active Pending
Patent Citations (6)
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| US4664991A (en) * | 1984-09-21 | 1987-05-12 | Alain Perichaud | Composition based on a electron conducting polymer and its application to a positive active material for electrochemical generators |
| CN101585907A (en) * | 2008-05-21 | 2009-11-25 | 中国科学院理化技术研究所 | The preparation method of conductive polymer poly (3,4 dioxoethyl) thiophene tiny balloon |
| CN101719545A (en) * | 2009-12-16 | 2010-06-02 | 北京理工大学 | Anode composite material of lithium sulfur battery and preparation method thereof |
| CN103262302A (en) * | 2010-11-04 | 2013-08-21 | 罗伯特·博世有限公司 | Cathode material for a lithium sulfur battery |
| CN102447113A (en) * | 2011-12-12 | 2012-05-09 | 南开大学 | Lithium battery with polymer-coated sulfur/carbon composite material as anode |
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