CN102088075A - Electrode material of conductive polyaniline composite membrane and preparation method thereof - Google Patents
Electrode material of conductive polyaniline composite membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an electrode material of conductive polyaniline composite membrane of a secondary lithium ion battery and a preparation method thereof. The electrode material is a composite membrane made of aniline and a polymer porous membrane (such as polypropylene, polyethylene, polyvinylidene fluoride and the like), and can be obtained through polymerization and mixing of solution. The aperture of the conductive polyaniline composite membrane is 20 to 80 nanometers, the porosity is smaller than 20 percent, the surface conductivity is 10 to 50 S/cm, the tensile strength is 100 to 140 MPa, the breaking elongation is 40 to 80 percent, and the modulus of elasticity is 800MPa to 1GPa. When the electrode material is used as the anode of the secondary lithium ion battery, the specific capacity is 60 to 90 Ah/kg; when the electrode material is used as the electrode of a super capacitor, the specific discharge capacity is 280-335F/g; and the electrode material has good stability in the charging and discharging process. The electrode material of conductive polyaniline composite membrane has good chemical stability, high specific capacity, simple preparation method, and is suitable for being used as the anode of the secondary lithium ion battery and the electrode material of the super capacitor.
Description
Technical field
The present invention relates to field of functional materials, be specifically related to a kind of compliant conductive polyaniline composite film material that is mainly used in as lithium ion secondary battery positive electrode and electrode of super capacitor.
Background technology
Lithium rechargeable battery is because its high working voltage, as mobile phone, be used widely on the electronic equipments such as notebook computer by camera on multiple electronic product for advantages such as high energy storage density, and can be used as green energy resource and be applied to the vehicles such as automobile, on the electric bicycle.The positive electrode that lithium ion battery is commonly used has LiCoO
2, LiMn
2O
4, LiFeO
4Deng.Though this class electrode material has better electrochemical performance, expensive, capacity is low, preparation purge process complexity, and especially the factors such as capacity attenuation problem of battery have restricted its better development.Ultracapacitor is as a kind of novel energy-storage travelling wave tube, with its excellent power characteristic and cycle performance and be widely used in fields such as electric automobile, communication, toy, intelligent instrument.And electrode material is just becoming the emphasis of present research as the deciding factor of decision ultracapacitor performance.
A lot of in recent years results of study show that conducting polymer composite can well be applied to lithium rechargeable battery as electrode material.Conducting polymer composite has low quality, low cost, and low the pollution can be carried out advantages such as MOLECULE DESIGN.The good conducting polymer of environmental stability mainly contains polyaniline, polypyrrole, polythiophene three major types at present.Compare with other conducting polymer composite, polyaniline has: the structure variation, and good electrical conductivity and stability, special mechanism of doping effect, by protonic acid doping, raw material is inexpensive, synthetic simple, advantages such as potential solution, melt-processed possibility.Since MacDiamid found the conductive characteristic of polyaniline in 1984, go through 20 years of development, electrically conductive polyaniline has been widely used in many fields such as electrochromism, secondary cell, sound wave shielding.In recent years, along with to the research of ultracapacitor and electrode material thereof further deeply, polyaniline is with its good chemical stability, dedoping ability and having caused is widely paid close attention to fast.A lot of documents show, in charge and discharge cycles process repeatedly, polyaniline has good electrochemical stability, its discharge capacity reaches 95Ah/Kg simultaneously, polyaniline film, the carbon nano-tube of polyaniline nano fiber or polyaniline blend can be used (Oyamaet al.Nature 373,6515,598-600 (1995) as lithium ion secondary battery positive electrode; Dias et al.J Power Sour 88,169-191 (2000); Sivakkumaret al.J Power Sour 163573-577 (2006); ).Yet because the strong interaction of the strong rigidity of polyaniline chain and interchain makes its dissolubility extreme difference, machinability is also poor, be difficult to directly preparation polyaniline conductive polymer film, if but the macromolecule membrane (as polyurethane) of employing and other satisfactory mechanical properties carries out copolymerization or compound, can prepare film macromolecule electrode equally.Prepare the film ultracapacitor with the coupling of film polyelectrolyte, will further expand the application of ultracapacitor at microelectronics such as integrated circuits.Therefore, in a lot of processing modes, adopt the rigid chain high polymer is swollen to the method for then using chemical oxidation (or electrochemical oxidation) in the flexible chain polymer matrix, make monomer in-situ polymerization in matrix formation molecular composite material to improve its processing characteristics.But in this method, polyaniline is in the distribution of body in mutually, and blending structure is difficult to control, and then causes the inhomogeneous of its electric conductivity.The diligent grade of Xu uses polypropylene porous film to be matrix, by the method that two kinds of solution (monomer and oxidant) mix after the perforated membrane interfacial diffusion, prepared main chain and contained heteroatomic conductive polymer composite film (CN Patent93117930).To prepare its diffusion rate of conductive polymer composite film in this way uncontrollable but make, and the polyaniline loading is on the low side, and then makes that its conductivity is on the low side, can't be applied to use as positive electrode in the lithium rechargeable battery.Therefore, be necessary to provide a kind of new method, to obtain a kind of have good circulation charge-discharge performance and height ratio capacity (60-90Ah/Kg), high surface conductivity (10-50S/cm), has excellent mechanical performances simultaneously, hot strength the conductive polymer composite film material, can be applied to lithium ion secondary battery positive electrode.
Summary of the invention
The objective of the invention is to prepare a kind of good flexibility that has, high conductivity, height ratio capacity, the novel flexible conductive type polyaniline composite film material that loading is controlled.
This conductive type polyaniline composite film electrode material is gone up the composite membrane that constitutes in the hole that is incorporated into porous polymer film by polyaniline and surface, the thickness of described porous polymer film is between the 10-30 micron, the aperture between the 100-200 nanometer, porosity 50～70%.
Preferably, the porosity of described composite membrane is less than 20%, and the thickness of the polyaniline of combination is the 3-10 micron on the every side surface of described porous polymer film.
The material of described porous polymer film can be polyolefin.For example for being selected from a kind of in polypropylene, polyethylene and the Kynoar.
Preferably, make the surface conductivity of described composite membrane between 10-50S/cm, hot strength is between 100-140Mpa, and elongation at break is between 40-80%, and modulus of elasticity is between 800Mpa-1Gpa.
Another object of the present invention is to provide a kind of polymer porous film that uses as template, but large-scale low-cost is produced the preparation method of above-mentioned conductive polymer composite film.
Compound film electrode preparation methods provided by the invention comprises the step of utilizing porous polymer film dipping aniline monomer and the step of utilizing doped hydrochloride to handle.
Specifically, this method may further comprise the steps:
1) the preparation porous polymer film flooded aniline monomer .5-20 hour with it, took out after-purification remained on surface monomer;
2) porous polymer film of dipping aniline monomer impregnated in the acid solution, and reaction (reaction time can be 0.5-1 hour) contains 0.1-2M hydrochloric acid and 0.01-0.2M ammonium persulfate in the described acid solution in ice bath;
3) through reacted composite membrane washed with de-ionized water, place the ammonia spirit of 1-10wt% then, carry out dedoping and handle;
4) the composite membrane washed with de-ionized water behind the dedoping is neutral up to the aqueous solution;
5) be impregnated in the 0.1-2M aqueous hydrochloric acid solution 0.5-20 hour then, composite membrane shows green or bottle green;
6) vacuumize promptly gets described compound film electrode material.
Described porous polymer film can make for dry method, by the stretching pore-forming.
Described porous polymer film also can be for wet method makes, by extraction of low molecular weight material pore-forming.
Above-mentioned compound film electrode material can be used as electrode material, anti-static material or anticorrosive.
Above-mentioned compound film electrode material is particularly suitable for as lithium ion secondary battery positive electrode or electrode of super capacitor.
Its specific capacity is between 60-90Ah/Kg when utilizing above-mentioned compound film electrode material as lithium ion secondary battery positive electrode, and charging/discharging voltage reaches 4.0V, and cycle life is higher than 80 times.Its specific capacity is at 280-335F/g when using as the electrode of ultracapacitor.
Description of drawings
Fig. 1 is PANI/PP (electrically conductive polyaniline/polypropylene) the composite membrane surface electromicroscopic photograph of embodiment 1.
Fig. 2 is the PANI/PP composite membrane cross section electromicroscopic photograph of embodiment 1.
Fig. 3 is the battery capacity test of the PANI/PP composite membrane of embodiment 1 as positive pole.
Fig. 4 is the battery charging and discharging change in voltage curve of the PANI/PP composite membrane of embodiment 1 as positive pole.
Embodiment
1 polypropylene porous septum thickness is at 22 microns, and the aperture is between the 100-200 nanometer, and porosity 50～70% impregnated in through in the aniline monomer of decompression distillation, floods after 11 hours, dries the aniline monomer on surface.
2 polypropylene porous films that will flood aniline impregnated in the hydrochloric acid solution of ammonium persulfate and (form: ammonium persulfate: 0.1M; Hydrochloric acid: 1M), 40 fens clock times of reaction in 0 degree centigrade cryosel is bathed.
Take out 3 barrier films reaction back, soaked 10 minutes in deionized water, washes the polyaniline that adheres on surface and the oxidant in the barrier film.Barrier film is immersed in the acetone afterwards, cleans snperoxiaized polyaniline, and solution is bluish violet, at last composite diaphragm is impregnated in the deionized water till colourless to solution, washes the acetone in the barrier film, vacuumize.
4 barrier films impregnated in the ammonia spirit (2.5%wt) 1 hour, and barrier film cleans to neutral with deionization then, and the barrier film after going to mix is contra-doping in hydrochloric acid solution (1M), floods 2 hours, obtains final composite membrane of polymer after the vacuumize.
5. the various performances that record composite membrane of polymer are as follows: weight method records loading 24.7%; Four electrode method records body phase conductivity 0.81/S.cm; Conducting atomic force microscopy records surface conductivity 26.31S/cm, and battery test system records that specific capacity is 62 in the lithium battery, and specific discharge capacity is 273F/g in the ultracapacitor; The material extending machine records that hot strength is 112.86Mpa under the room temperature, and elongation at break is 54.43%, and modulus of elasticity is 913.42Mpa.
6. the electromicroscopic photograph of the surface topography of composite membrane of polymer and interface topography such as Fig. 1 are shown in Figure 2, the visible surface micropore, and about 30 nanometers in aperture, thickness is 25 microns.Its specific capacity was not less than 60Ah/Kg after the anodal specific capacity test of the conductive polymer composite film of Fig. 3 was presented at repeatedly cycle charge-discharge, and Fig. 4 shows that the conductive polymer composite film positive pole still keeps stable through its discharge voltage behind the cycle charge-discharge repeatedly.
1 quantitative thickness is at 22 microns, and the aperture is between the 100-200 nanometer, and the polypropylene porous septum of porosity 50～70% impregnated in the aniline monomer of decompression distillation, floods after 12 hours, dries the aniline monomer on surface.
2 polypropylene porous films that will flood aniline impregnated in the hydrochloric acid solution of ammonium persulfate and (form: ammonium persulfate: 0.15M; Hydrochloric acid: 1.2M), 60 fens clock times of reaction in 0 degree centigrade cryosel is bathed.
Take out 3 barrier films reaction back, soaked 15 minutes in deionized water, washes the polyaniline that adheres on surface and the oxidant in the barrier film.Barrier film is immersed in the acetone afterwards, cleans snperoxiaized polyaniline, and solution is bluish violet, at last composite diaphragm is impregnated in the deionized water till colourless to solution, washes the acetone in the barrier film, vacuumize.
4 barrier films impregnated in the ammonia spirit (2.5%wt) 1 hour, and barrier film cleans to neutral with deionization then, and the barrier film after going to mix is contra-doping in hydrochloric acid solution (1M), floods 2 hours, obtains final composite membrane of polymer after the vacuumize.
5. the thickness that records composite membrane of polymer is at 26 microns, the aperture is between the 10-100 nanometer, porosity 10～30%, conductivity are loading 28.1%, body phase conductivity 1.1S/cm, surface conductivity (four electrode method) 32.85S/cm, the battery specific capacity is 71Ah/Kg, and specific discharge capacity is 285F/g, and hot strength is 120.86Mpa under the room temperature, elongation at break is 55.75%, and modulus of elasticity is 930.21Mpa.
1 quantitative thickness is between 25 microns, and the aperture is between the 100-200 nanometer, and the polypropylene porous septum of porosity 50～70% impregnated in the aniline monomer of decompression distillation, floods after 14 hours, dries the aniline monomer on surface.
2 polypropylene porous films that will flood aniline impregnated in the hydrochloric acid solution of ammonium persulfate and (form: ammonium persulfate: 0.1M; Hydrochloric acid: 1M), 40 fens clock times of reaction in 0 degree centigrade cryosel is bathed.
Take out 3 barrier films reaction back, soaked 10 minutes in deionized water, washes the polyaniline that adheres on surface and the oxidant in the barrier film.Barrier film is immersed in the acetone afterwards, cleans snperoxiaized polyaniline, and solution is bluish violet, at last composite diaphragm is impregnated in the deionized water till colourless to solution, washes the acetone in the barrier film, vacuumize.
4 barrier films impregnated in the ammonia spirit (2.5%wt) 0.5 hour, and barrier film cleans to neutral with deionization then, and the barrier film after going to mix is contra-doping in hydrochloric acid solution (1.5M), floods 3 hours, obtains final composite membrane of polymer after the vacuumize.
5. the thickness that records composite membrane of polymer is at 27 microns, the aperture is between the 10-100 nanometer, porosity 10～30%, conductivity is a loading 30.3%, body phase conductivity 1.6S/cm, surface conductivity (four electrode method) 39.25S/cm, specific capacity is 78Ah/kg, specific discharge capacity is that hot strength is 127.44Mpa under the 297F/g room temperature, and elongation at break is 57.85%, and modulus of elasticity is 941.12Mpa.
1 quantitative thickness is between 25 microns, and the aperture is between the 100-200 nanometer, and the polypropylene porous septum of porosity 50～70% impregnated in the aniline monomer of decompression distillation, floods after 16 hours, dries the aniline monomer on surface.
2 polypropylene porous films that will flood aniline impregnated in the hydrochloric acid solution of ammonium persulfate and (form: ammonium persulfate: 0.2M; Hydrochloric acid: 1.5M), 40 fens clock times of reaction in 0 degree centigrade cryosel is bathed.
Take out 3 barrier films reaction back, soaked 10 minutes in deionized water, washes the polyaniline that adheres on surface and the oxidant in the barrier film.Barrier film is immersed in the acetone afterwards, cleans snperoxiaized polyaniline, and solution is bluish violet, at last composite diaphragm is impregnated in the deionized water till colourless to solution, washes the acetone in the barrier film, vacuumize.
4 barrier films impregnated in the ammonia spirit (2.5%wt) 0.5 hour, and barrier film cleans to neutral with deionization then, and the barrier film after going to mix is contra-doping in hydrochloric acid solution (0.8M), floods 2.5 hours, obtains final composite membrane of polymer after the vacuumize.
5. the thickness that records composite membrane of polymer is at 29 microns, the aperture is between the 10-100 nanometer, porosity 10～30%, conductivity is a loading 36.4%, body phase conductivity 2.2S/cm, surface conductivity 41.4S/cm specific capacity is 82Ah/kg, specific discharge capacity is that hot strength is 130.02Mpa under the 310F/g room temperature, elongation at break is 60.32%, and modulus of elasticity is 941.17Mpa.
Claims (10)
1. conductive type polyaniline composite film electrode material, it is characterized in that it goes up the composite membrane that constitutes in the hole that is incorporated into porous polymer film by polyaniline and surface, the thickness of described porous polymer film is between the 10-30 micron, the aperture between the 100-200 nanometer, porosity 50～70%.
2. compound film electrode material according to claim 1 is characterized in that, the porosity of described composite membrane is less than 20%, and the thickness of the polyaniline of combination is the 3-10 micron on the every side surface of described porous polymer film.
3. compound film electrode material according to claim 1 is characterized in that, the material of described porous polymer film is a polyolefin.
4. compound film electrode material according to claim 3 is characterized in that, described polyolefin is selected from a kind of in polypropylene, polyethylene and the Kynoar.
5. each described compound film electrode preparation methods of claim 1～4 is characterized in that, comprises the step of utilizing porous polymer film dipping aniline monomer and the step of utilizing doped hydrochloride to handle.
6. preparation method according to claim 5 is characterized in that concrete operations may further comprise the steps:
1) the preparation porous polymer film flooded aniline monomer 0.5-20 hour with it, took out after-purification remained on surface monomer;
2) porous polymer film of dipping aniline monomer impregnated in the acid solution, reacts in ice bath, contains 0.1-2M hydrochloric acid and 0.01-0.2M ammonium persulfate in the described acid solution;
3) through reacted composite membrane washed with de-ionized water, place the ammonia spirit of 1-10wt% then, carry out dedoping and handle;
4) the composite membrane washed with de-ionized water behind the dedoping is neutral up to the aqueous solution;
5) be impregnated in the 0.1-2M aqueous hydrochloric acid solution 0.5-20 hour then, composite membrane shows green or bottle green;
6) vacuumize promptly gets described compound film electrode material.
7. preparation method according to claim 5 is characterized in that, described porous polymer film is that dry method makes, by the stretching pore-forming.
8. preparation method according to claim 5 is characterized in that, described porous polymer film is that wet method makes, by extraction of low molecular weight material pore-forming.
9. each described compound film electrode material of claim 1～4 is as the purposes of electrode material, anti-static material or anticorrosive.
10. each described compound film electrode material of claim 1～4 is as the purposes of lithium ion secondary battery positive electrode or electrode of super capacitor.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432902A (en) * | 2011-09-05 | 2012-05-02 | 厦门华戎能源科技有限公司 | Preparation method of polyvinyl composite conducting film |
| CN102568841A (en) * | 2012-01-06 | 2012-07-11 | 黑龙江大学 | Preparation method for polyaniline membrane electrode |
| CN103956272A (en) * | 2014-03-18 | 2014-07-30 | 香港中文大学深圳研究院 | Composite plane electrode based on super capacitor diaphragm, and preparation method thereof |
| CN104091907A (en) * | 2014-06-12 | 2014-10-08 | 苏州经贸职业技术学院 | Fuel cell membrane material and preparation method thereof |
| CN104377374A (en) * | 2014-09-11 | 2015-02-25 | 中山大学 | Battery without additional electrolyte |
| CN106935414A (en) * | 2017-04-24 | 2017-07-07 | 福州大学 | A kind of cross linked porous polyaniline electrode material and preparation method thereof |
| CN109244319A (en) * | 2018-09-14 | 2019-01-18 | 北京工业大学 | A method of improving polyolefins lithium ion battery separator wetability |
| CN110444780A (en) * | 2019-08-12 | 2019-11-12 | 苏州汉为能源科技有限公司 | Cu-Mn-C class catalyst/composite membrane of polymer electrode assembly and preparation method thereof and application |
| CN110767926A (en) * | 2019-08-13 | 2020-02-07 | 武汉长海电力推进和化学电源有限公司 | Preparation method of fuel cell |
| CN114994997A (en) * | 2021-03-01 | 2022-09-02 | 中国科学院上海硅酸盐研究所 | Electrochromic device with mesoporous structure and preparation method thereof |
| CN115020705A (en) * | 2022-04-25 | 2022-09-06 | 合肥国轩科宏新能源科技有限公司 | Polyurethane elastic fiber positive electrode material and preparation method and application thereof |
| CN115364685A (en) * | 2022-10-25 | 2022-11-22 | 天津工业大学 | Preparation method of polyaniline composite conductive organic film |
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| CN102432902A (en) * | 2011-09-05 | 2012-05-02 | 厦门华戎能源科技有限公司 | Preparation method of polyvinyl composite conducting film |
| CN102432902B (en) * | 2011-09-05 | 2013-07-03 | 厦门华戎能源科技有限公司 | Preparation method of polyvinyl composite conducting film |
| CN102568841A (en) * | 2012-01-06 | 2012-07-11 | 黑龙江大学 | Preparation method for polyaniline membrane electrode |
| CN102568841B (en) * | 2012-01-06 | 2014-04-23 | 黑龙江大学 | Preparation method for polyaniline membrane electrode |
| CN103956272A (en) * | 2014-03-18 | 2014-07-30 | 香港中文大学深圳研究院 | Composite plane electrode based on super capacitor diaphragm, and preparation method thereof |
| CN103956272B (en) * | 2014-03-18 | 2017-08-25 | 香港中文大学深圳研究院 | Composite plane electrode based on diaphragm of supercapacitor and preparation method thereof |
| CN104091907A (en) * | 2014-06-12 | 2014-10-08 | 苏州经贸职业技术学院 | Fuel cell membrane material and preparation method thereof |
| CN104377374A (en) * | 2014-09-11 | 2015-02-25 | 中山大学 | Battery without additional electrolyte |
| CN104377374B (en) * | 2014-09-11 | 2017-07-07 | 中山大学 | One kind is without additional electrolytic cell |
| CN106935414A (en) * | 2017-04-24 | 2017-07-07 | 福州大学 | A kind of cross linked porous polyaniline electrode material and preparation method thereof |
| CN109244319A (en) * | 2018-09-14 | 2019-01-18 | 北京工业大学 | A method of improving polyolefins lithium ion battery separator wetability |
| CN110444780A (en) * | 2019-08-12 | 2019-11-12 | 苏州汉为能源科技有限公司 | Cu-Mn-C class catalyst/composite membrane of polymer electrode assembly and preparation method thereof and application |
| CN110444780B (en) * | 2019-08-12 | 2020-09-08 | 天津工业大学 | Cu-Mn-C catalyst/polymer composite membrane electrode assembly and manufacturing method and application thereof |
| CN110767926A (en) * | 2019-08-13 | 2020-02-07 | 武汉长海电力推进和化学电源有限公司 | Preparation method of fuel cell |
| CN110767926B (en) * | 2019-08-13 | 2020-08-07 | 武汉长海电力推进和化学电源有限公司 | Preparation method of fuel cell |
| CN114994997A (en) * | 2021-03-01 | 2022-09-02 | 中国科学院上海硅酸盐研究所 | Electrochromic device with mesoporous structure and preparation method thereof |
| CN114994997B (en) * | 2021-03-01 | 2023-10-13 | 中国科学院上海硅酸盐研究所 | Electrochromic device with mesoporous structure and preparation method thereof |
| CN115020705A (en) * | 2022-04-25 | 2022-09-06 | 合肥国轩科宏新能源科技有限公司 | Polyurethane elastic fiber positive electrode material and preparation method and application thereof |
| CN115020705B (en) * | 2022-04-25 | 2024-05-14 | 合肥国轩科宏新能源科技有限公司 | Polyurethane elastic fiber positive electrode material and preparation method and application thereof |
| CN115364685A (en) * | 2022-10-25 | 2022-11-22 | 天津工业大学 | Preparation method of polyaniline composite conductive organic film |
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Application publication date: 20110608 |