CN1280318C - Nano composite of polypyrrole / carbon black and preparation process thereof - Google Patents
Nano composite of polypyrrole / carbon black and preparation process thereof Download PDFInfo
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- CN1280318C CN1280318C CNB2004100203040A CN200410020304A CN1280318C CN 1280318 C CN1280318 C CN 1280318C CN B2004100203040 A CNB2004100203040 A CN B2004100203040A CN 200410020304 A CN200410020304 A CN 200410020304A CN 1280318 C CN1280318 C CN 1280318C
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Abstract
The present invention relates to a composite polypyrrole / carbon black nanometer material and a preparation method thereof, which belongs to a technology for preparing the composite polypyrrole / inorganic nanometer material by using a process of original position adsorption and polymerization and particularly relates to a composite polypyrrole / carbon black nanometer material and a preparative technology thereof. The present invention overcomes the problems of difficulty in stripping electrodes from products and unsuitability for mass industrialized production existing in an electrolysis method, simplifies a polymerization process and raw materials of the existing original position adsorption method, and can synthesize the composite polypyrrole / carbon black nanometer material by one step without a process step for modifying the surfaces of inorganic particles by a silane coupling agent. The preparation method comprises the following steps: polypyrrole is used as a substrate, and carbon black is used as a reinforcing body; an oxidation agent, a doping agent and the carbon black are added to deionized water, and pyrrole is injected while stirring, stirred in nitrogen for polymerization before separation, and is dried to obtain the composite nanometer material. The present invention has the advantages of simple technology and suitability for bulk production; the composite nanometer material can be used as an active material for the anodes of secondary cells and can also be used in the fields, such as electrolytic condensers, polymer electronic devices, photoelectrochemical cells, etc.
Description
Technical field
The invention belongs to original position adsorpting polymerization prepared polypyrrole/inorganic composite materials and technology of preparing thereof, particularly a kind of polypyrrole/carbon black nano composite material and technology of preparing thereof.
Background technology
Polymkeric substance has been compared following advantage as secondary battery positive electrode material with other secondary battery positive electrode material: 1. processibility is good.Can be processed into suitable shape to battery as required, also can be made into hull cell; 2. weight specific energy maximum; 3. do not resemble easy generation dendrite the metal electrode and internal short-circuit takes place; 4. the electrode of polymkeric substance making is that so the specific surface area of electrode is big, specific power is big in the inner generating electrodes reaction of whole porous macromolecule matrix.
Lithium/polymer secondary battery is to be positive active material with the polymkeric substance.From its developing history, inseparable with the research of electric conductive polymer.Polypyrrole (PPy) have air stability good, be easy to film forming, be easy to mix, advantage such as nontoxic, have broad application prospects in fields such as polymer battery, electrolytic condenser, polymer-electronics device, conducting polymer composite material and photoelectrochemical cells, thereby be subjected to extensive attention closely during the last ten years.
At " Matsuhilo Nishzawa, Kiyoshi Mukai, Susumu Kuwabata.Template synthesisof polypyrrole-coated spinel LiMn
2O
4Nanotubules and their properties ascathode active materials for lithium batteries. Electroanal. Soc., 1997,6,144 (6), 1923-1927 " in reported with the template electrochemical method and prepared PPy coating spinelle type LiMn2O4 nanotube positive electrode material that cell container improves a lot.At " Susumu Kuwabata, AkiraKishmoto, Takayoshi Tanaka.Electrochemical synthesis of composite films ofmanganese dioxide and polypyrrole and their properties as an active materialin lithium secondary batteries.J.Electrochem.Soc., 1994,141 (1): 10-15 " reported in electrochemical process to prepare polypyrrole and the manganese dioxide composites film is made cathode plate for lithium secondary battery, obtained higher specific energy density.At " Jong Hyeok Park, Jang Myoun Ko, O.Ok Park.Capacitance propertiesof graphite/polypyrrole composite electrode prepared by chemical polymeri--zation of pyrrole on graphite fiber.Journal of Power Sources, 2002,105:20-25 " in reported that electrochemical polymerization method prepares the PPy/ graphite fiber composite materials and makes electrode of super capacitor, show specific storage preferably.Above bibliographical information all is that matrix material and stripping electrode difficulty are not suitable for industrial production in enormous quantities with the electrochemical process preparation.
We are in 01136948.5 patent application, adopt the organic/inorganic nano compound system, with chemical oxidization method original position adsorpting polymerization technology, prepared the nano composite material of polypyrrole and silicon-dioxide inorganic particulate, obtain the higher polypyrrole/silicon dioxide matrix material of specific conductivity.But in preparation process, need materials such as silane coupling agent, silicon dioxide granule carried out the surface adsorption coating modification, increasing the interface binding power of nanoparticle and polymkeric substance, and then with pyrroles's original position adsorpting polymerization.When making secondary battery positive electrode material, must add graphitized carbon black to increase its electroconductibility with this material.Adopt pyrroles and carbon black, with chemical oxidization method, the original position adsorpting polymerization becomes nano composite material and is used to make the anode of secondary battery coating material, does not appear in the newspapers as yet.
Summary of the invention
The problem that solves:
At above problem, the present invention has avoided in the electrochemical process preparation, and matrix material and stripping electrode difficulty are not suitable for the mass industrial production problem.Be the development of new nano composite material, we select original position adsorpting polymerization method, further simplify technology and raw material.This method has been simplified materials such as inorganic particulate interpolation silane coupling agent, the operation of carrying out the surface adsorption coating modification; When making the anode of secondary battery coating material with the polypyrrole/silicon dioxide matrix material in the past, also need add graphitized carbon black for increasing its electroconductibility, the present invention can save, thereby provide a kind of to need one-step synthesis, can obtain the Technology of the higher polypyrrole of specific conductivity/carbon black nano composite material.
Technical scheme:
Polypyrrole/carbon black nano composite material adopts the organic/inorganic nano compound system, and matrix material is that matrix is a polypyrrole, and strengthening body is sooty original position adsorpting polymerization thing, and polypyrrole and carbon black ratio of weight and number are 1 in this polymkeric substance: 0.01-0.15.Each component sum is 100% in this polymkeric substance.
The method of polypyrrole/carbon black nano composite material preparation, each composition weight umber of its used material is:
The pyrroles 1
Carbon black 0.01-0.15
Oxygenant 7-11
Doping agent 4-6
Deionized water 100
Need to prove:
Above-mentioned particle size carbon black is 33nm; Its parts by weight also can be 0.05-0.09; Oxygenant is FeCl
36H
2O; Doping agent is a benzene sulfonic acid sodium salt.
Concrete preparation process is as follows:
25 ℃ down by above-mentioned formula ratio, with oxygenant FeCl
36H
2Add deionized water in O, doping agent benzene sulfonic acid sodium salt and the carbon black; inject the pyrroles with needle tubing after stirring; polymerization centrifugation after 12 hours is stirred in nitrogen protection down; the gained precipitation is through ultrasonic wave repeating dispersion in deionized water; be neutral until system; 50 ℃ of following vacuum-drying 24 hours promptly obtains polypyrrole/carbon black nano composite material.
Polypyrrole/carbon black nano composite material can be used for the preparation of anode coating material, concrete grammar is: with polypyrrole/carbon black nano composite material and tackiness agent polyvinylidene difluoride (PVDF) and N-Methyl pyrrolidone, ratio of weight and number by 1: 0.1: 10 mixes, and makes the anode coating material.
Polypyrrole/carbon black nano composite material also can be used for fields such as polymer battery, electrolytic condenser, polymer-electronics device, conducting polymer composite material and photoelectrochemical cell; And be expected to be used for ionization sensor, solar energy materials and information processing material etc.
Beneficial effect:
The present invention adopts the organic and inorganic compound system, selects original position adsorpting polymerization technology, and it is compound to carry out nano carbon black, obtains the higher polypyrrole of specific conductivity/carbon black nano composite material.Compare with electrolytic process, this method has overcome in the electrolytic process, prepared matrix material and stripping electrode difficulty, be not suitable for the mass industrial production problem, and the polymerization technique and the raw material of original position absorption method have further been simplified, need not use silane coupling agent, inorganic particulate be carried out operations such as surface modification, one-step synthesis polypyrrole/carbon black nano composite material.Not only simplified processing step, and respond well, be suitable for producing in enormous quantities.Gained polypyrrole of the present invention/carbon black nano composite material specific conductivity height optimizes the negative pole and the ionogen that are complementary with it, can be assembled into lithium/polypyrrole secondary button cell used as positive electrode active materials.After tested, make positive pole with the polypyrrole nano composite material that specific conductivity is high, higher specific discharge capacity is arranged, cycle performance is good, is a kind of more satisfactory lithium secondary battery positive active material.In addition, this material also can be used for fields such as electrolytic condenser, polymer-electronics device and photoelectrochemical cell.
Description of drawings
Fig. 1: for the present invention tests 10,000 times of scanning electron microscope of used sooty (SEM) photo;
Fig. 2: be 10,000 times of SEM photos of polypyrrole (PPy);
Fig. 3: be the SEM photo of polypyrrole of the present invention/carbon black nano-complex;
Fig. 4: be the curve of carbon black loading to polypyrrole/carbon black nano-complex specific conductivity influence;
Embodiment
Embodiment 1:
Under 25 ℃ with 7.0g oxygenant FeCl
36H
2O, 4.0g doping agent benzene sulfonic acid sodium salt and 0.01g particle diameter are to add the 100ml deionized water in the carbon black of 33nm; inject 1ml pyrroles with needle tubing after stirring; under nitrogen protection, stir polymerization centrifugation after 12 hours; the gained precipitation is through ultrasonic wave repeating dispersion in deionized water; be neutral until system; 50 ℃ of following vacuum-drying 24 hours promptly obtains polypyrrole/carbon black nano composite material.
The gained performance of composites is as shown in the figure: Fig. 1 is 10,000 times of SEM photos of used sooty for the present invention tests.Therefrom as can be seen, used sooty structure is a granulous, and very big specific surface area is arranged, and this form is favourable for conductive effect.Fig. 2 is 10,000 times a SEM photo of polypyrrole, and from its form, polypyrrole is fluffy granular texture, and its form is disadvantageous for conduction.Fig. 3 is the SEM photo of polypyrrole of the present invention/carbon black nano-complex, can see that carbon black fine particle is well coated by polypyrrole, and it is tightr to mutually combine, and its structure is greatly improved, and helps specific conductivity and improves.Fig. 4 is that carbon black loading is to polypyrrole/carbon black nano-complex specific conductivity influence curve.The polypyrrole that present method makes/carbon black nano-complex specific conductivity is 18S/cm.This material can be used as polymer battery, electrolytic condenser, polymer-electronics device, conducting polymer composite material or photoelectrochemical cell.
Embodiment 2:
Adopt oxygenant FeCl
36H
2O 9.0g, doping agent benzene sulfonic acid sodium salt 5.0g and particle diameter are the carbon black 0.07g of 33nm; Other is with embodiment 1.As shown in Figure 4, polypyrrole/carbon black nano-complex specific conductivity of making of present method can reach 36S/cm.
Embodiment 3:
Adopt oxygenant FeCl
36H
2O 11.0g, doping agent benzene sulfonic acid sodium salt 6.0g, particle diameter are the carbon black 0.15g of 33nm; Other is with embodiment 1.As shown in Figure 4, polypyrrole/carbon black nano-complex specific conductivity of making of present method is 26S/cm.
Embodiment 4
Adopt oxygenant FeCl
36H
2O 9.1g, doping agent benzene sulfonic acid sodium salt 4.4g, particle diameter are 33nm carbon black 0.05g, other is with embodiment 1.As shown in Figure 4, polypyrrole/carbon black nano-complex specific conductivity of making of present method is 30S/cm.
Embodiment 5:
Adopt oxygenant FeCl
36H
2O 10g, doping agent benzene sulfonic acid sodium salt 5.0g, particle diameter are the carbon black 0.09g of 33nm, other is with embodiment 1.As shown in Figure 4, polypyrrole/carbon black nano-complex specific conductivity of making of present method is 31S/cm.
Embodiment 6 (application experiment):
The preparation of anode coating material:
With mixing in 1 gram polypyrrole/carbon black nano composite material and the 0.1 gram tackiness agent polyvinylidene difluoride (PVDF) adding 10ml N-Methyl pyrrolidone (NMP), make slurry, promptly the anode coating material is coated on the collector electrode.
Claims (7)
1. polypyrrole/carbon black nano composite material is characterized in that, this matrix material is that matrix is a polypyrrole, and strengthening body is sooty original position adsorpting polymerization thing; Polypyrrole and carbon black ratio of weight and number are in this polymkeric substance: 1: 0.01-0.15.
2. the preparation method of the described polypyrrole of claim 1/carbon black nano composite material is characterized in that, each composition weight umber of its used material is:
The pyrroles 1
Carbon black 0.01-0.15
Oxygenant 7-11
Doping agent 4-6
Deionized water 100
Preparation process is as follows:
25 ℃ down by above-mentioned formula ratio; oxygenant, doping agent and carbon black are added in the deionized water; inject the pyrroles with needle tubing after stirring; polymerization centrifugation after 12 hours is stirred in nitrogen protection down; the gained precipitation is through ultrasonic wave repeating dispersion in deionized water; be neutral until system, 50 ℃ of following vacuum-drying 24 hours promptly obtains polypyrrole/carbon black nano composite material.
3. the preparation method of the described polypyrrole of claim 2/carbon black nano composite material is characterized in that, particle size carbon black is 33nm; The carbon black parts by weight are 0.05-0.09.
4. according to the preparation method of the described polypyrrole of claim 2/carbon black nano composite material, it is characterized in that described oxygenant is FeCl
36H
2O.
5. according to the preparation method of the described polypyrrole of claim 2/carbon black nano composite material, it is characterized in that described doping agent is a benzene sulfonic acid sodium salt.
6. the purposes of the described polypyrrole of claim 1/carbon black nano composite material, it is characterized in that, polypyrrole/carbon black nano composite material can be used for the preparation of anode coating material, concrete grammar is: polypyrrole/carbon black nano composite material and tackiness agent polyvinylidene difluoride (PVDF) and the N-Methyl pyrrolidone ratio of weight and number by 1: 0.1: 10 is mixed, make the anode coating material.
7. the purposes of the described polypyrrole of claim 1/carbon black nano composite material is characterized in that, is used for polymer battery, electrolytic condenser, polymer-electronics device, conducting polymer composite material and photoelectrochemical cell field.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10074453B2 (en) | 2014-08-21 | 2018-09-11 | Council Of Scientific & Industrial Research | P-toluenesulfonate doped polypyrrole/carbon composite electrode and a process for the preparation thereof |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1741214A (en) * | 2005-07-15 | 2006-03-01 | 复旦大学 | Electrochemical super capacitor with organic polymer free radical/carbon composite material as anode |
| CN104409689A (en) * | 2014-11-17 | 2015-03-11 | 天津大学 | Polypyrrole coated hard carbon cathode material and preparation method thereof |
| CN104558979B (en) * | 2014-12-26 | 2016-08-24 | 中北大学 | The method preparing carbon back filler/polymer matrix composite by electric conductivity macromolecular coupling agent |
| CN116144097A (en) * | 2023-02-17 | 2023-05-23 | 四川大学 | Preparation method and application of semiconductive shielding material for high-voltage alternating-current cable |
| CN116285504B (en) * | 2023-03-24 | 2024-04-02 | 北京印刷学院 | Polypyrrole/conductive carbon black/polyvinyl alcohol conductive ink and preparation method and application thereof |
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2004
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10074453B2 (en) | 2014-08-21 | 2018-09-11 | Council Of Scientific & Industrial Research | P-toluenesulfonate doped polypyrrole/carbon composite electrode and a process for the preparation thereof |
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