CN1271109C - Method for preparing high-conductivity polypyrrole material - Google Patents
Method for preparing high-conductivity polypyrrole material Download PDFInfo
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- CN1271109C CN1271109C CN 200410028164 CN200410028164A CN1271109C CN 1271109 C CN1271109 C CN 1271109C CN 200410028164 CN200410028164 CN 200410028164 CN 200410028164 A CN200410028164 A CN 200410028164A CN 1271109 C CN1271109 C CN 1271109C
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- acid
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- aluminium flake
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- secondary water
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- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 title claims abstract description 14
- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 150000003233 pyrroles Chemical class 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 3
- 238000009415 formwork Methods 0.000 claims description 3
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 3
- 239000006210 lotion Substances 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 229940083608 sodium hydroxide Drugs 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000010408 sweeping Methods 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 238000002484 cyclic voltammetry Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229920001940 conductive polymer Polymers 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010291 electrical method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention discloses a method for preparing a high-conductivity polypyrrole material with a highly ordered nano array by using an electrochemical polymerization method. The preparation method is simple, the process is simplified, the time of the whole process is short, and the synthesis condition can be carried out under a normal state, so the cost is low; and as the secondary oxidation method is adopted to prepare the nano aluminum oxide material, the generated polypyrrole has uniform diameter and ordered arrangement, the polypyrrole material synthesized by the cyclic voltammetry has excellent conductivity, the length can be controlled by the cycle frequency, and the production requirement can be easily met.
Description
Technical field
The present invention relates to a kind of method for preparing the high conductivity polypyrrole material, particularly a kind of method of high conductivity polypyrrole material of the nano-array that utilizes electrochemical polymerization to prepare to have high-sequential.
Background technology
Conductive polymers is because satisfactory stability and electroconductibility have good prospects for application at secondary cell, solid electric capacity, photoelectric display device with as aspects such as conducting mediums, and the synthetic and preparation of conduction polymers nanotube and molecular wire is the key that restriction realizes nano-device and molecular device.When conductive polymers is in the nanometer state, under the effect of supramolecule effect, pyrroles's chain can be to be parallel to fibre axis to being preferred orientation in the nanofiber, and this preferred orientation makes the specific conductivity of conductive polymer nanometer fiber be the inverse ratio growth in following time of 100nm and diameter.So synthetic nano-wire array with orderly orientation unanimity has practical value.Pyrroles's line that electrode surface direct growth method generates among the preparation method is arranged in a jumble at present, can't be used for practical application; AC electrical method prepares overtension, and the peroxidation of pyrroles's reality can't realize pyrroles's conducting function; Chemical template method synthetic pyrroles is intermittent.Therefore have only electrochemistry template synthetic pyrroles that actual application prospect is just arranged.
Summary of the invention
The objective of the invention is to shortcoming, a kind of method for preparing the high conductivity polypyrrole material is provided at the prior art existence.The present invention is a polymerization face with the electrode, need not sputtering technology, saves expensive technology, adopts the template of secondary oxidation method preparation, synthesizes the nano-array material of high-sequential therein, makes it that Application Areas widely be arranged in future.
The present invention prepares the method for high conductivity polypyrrole material, is made up of following steps successively:
(1) synthesis of nano alumina formwork
(a) aluminium flake was polished 5～10 minutes down at 0～5 ℃ with 70% perchloric acid and dehydrated alcohol mixed solution earlier, voltage is 15～22V; The volume ratio 1: 4 of perchloric acid and dehydrated alcohol in the mixed solution;
(b) aluminium flake cleans back oxidation first 1～2 hour under polyprotonic acid and corresponding voltage thereof with secondary water, does counter electrode with stainless steel plate; Under 60 ℃, mix washing lotion then and clean aluminium flake half an hour, remove oxide film with the chromic acid of 6% phosphoric acid and 1.8%;
(c) after aluminium flake cleans with secondary water, use the voltage identical to carry out anodic oxidation 6 hours with above-mentioned (b) step; Peel off aluminum matrix with the tin protochloride saturated aqueous solution then, used 5% phosphoric acid through hole again 30 minutes, obtain nano-alumina template, clean and be kept in the secondary water;
(2) glass-carbon electrode is polished to minute surface through abrasive paper for metallograph and aluminum oxide, with 20% nitric acid and 10% sodium-hydroxide treatment, after using the redistilled water thorough washing then, be assemblied in nano-alumina template on the glass-carbon electrode closely, immerse 0.2mol/L pyrroles's solution of pH=3, in 0～0.75V voltage range, with velocity sweeping 200 cycles of 100mv/s, take out, use 5%HPO
3Soak 20min, moltenly dry after going after the template to wash with secondary water washing.
Described aluminium flake purity is 99.999%.
Polyprotonic acid in above-mentioned (b) step can be 0.5～1.5mol/L sulfuric acid, and corresponding voltage is 18～22V; Polyprotonic acid also can be 0.1～0.5mol/L oxalic acid, and corresponding voltage is 30～50V; Polyprotonic acid also can be 0.3～1.0mol/L phosphoric acid, and corresponding voltage is 100～130V.
Compared with the prior art, the present invention has following beneficial effect:
1, method is simple, work simplification, and the whole flow process time is short, and synthesis condition just can carry out under normal conditions, and is therefore with low cost;
2, owing to adopt the secondary oxidation legal system to be equipped with nano alumina material, the polypyrrole diameter of generation is unified, arranges in order, and is outstanding with cyclic voltammetry synthetic polypyrrole material conductivity, and length can be controlled by the circulation cycle, is easy to reach the production needs.
Description of drawings
Fig. 1 is conductive polymer nanometer array electrode surface observed figure under scanning electron microscope;
Fig. 2 is conductive polymer nanometer array electrode surface observed figure under scanning electron microscope.
Embodiment
The preparation of embodiment 1 high conductivity polypyrrole material of the present invention
(1) synthesis of nano alumina formwork
(a) aluminium flake was polished 8 minutes down at 2 ℃ with 70% perchloric acid and dehydrated alcohol mixed solution earlier, voltage is 20V; The volume ratio 1: 4 of perchloric acid and dehydrated alcohol in the mixed solution;
(b) aluminium flake cleans back oxidation first 1.5 hours under 1mol/L sulfuric acid, voltage 20v with secondary water, does counter electrode with stainless steel plate; Under 60 ℃, mix washing lotion then and clean aluminium flake half an hour, remove oxide film with the chromic acid of 6% phosphoric acid and 1.8%;
(c) after aluminium flake cleans with secondary water, use the voltage identical to carry out anodic oxidation 6 hours with above-mentioned (b) step; Peel off aluminum matrix with the tin protochloride saturated aqueous solution then, used 5% phosphoric acid through hole again 30 minutes, obtain nano-alumina template, clean and be kept in the secondary water;
(2) glass-carbon electrode is polished to minute surface through abrasive paper for metallograph and aluminum oxide, with nitric acid and sodium-hydroxide treatment, after using the redistilled water thorough washing then, be assemblied in nano-alumina template on the glass-carbon electrode closely, immerse 0.2mol/L pyrroles's solution of pH=3, in the 0.5V voltage range, with velocity sweeping 200 cycles of 100mv/s, take out, use 5%HPO
3Soak, moltenly dry after going after the template to wash with secondary water washing.
Claims (4)
1, a kind of method for preparing the electroconductibility polypyrrole material, form by following steps successively:
(1) synthesis of nano alumina formwork
(a) aluminium flake was polished 5～10 minutes down at 0～5 ℃ with 70% perchloric acid and dehydrated alcohol mixed solution earlier, voltage is 15～22V; The volume ratio 1: 4 of perchloric acid and dehydrated alcohol in the mixed solution;
(b) aluminium flake cleans back oxidation first 1～2 hour under polyprotonic acid and corresponding voltage thereof with secondary water, does counter electrode with stainless steel plate; Under 60 ℃, mix washing lotion then and clean aluminium flake half an hour, remove oxide film with the chromic acid of 6% phosphoric acid and 1.8%;
(c) after aluminium flake cleans with secondary water, use the voltage identical to carry out anodic oxidation 6 hours with above-mentioned (b) step; Peel off aluminum matrix with the muriate saturated aqueous solution then, used 5% phosphoric acid through hole again 30 minutes, obtain nano-alumina template, clean and be kept in the secondary water;
(2) glass-carbon electrode is polished to minute surface through abrasive paper for metallograph and aluminum oxide, with nitric acid and sodium-hydroxide treatment, after using the redistilled water thorough washing then, be assemblied in nano-alumina template on the glass-carbon electrode closely, immerse 0.2mol/L pyrroles's solution of pH=3, in 0～0.75V voltage range, with velocity sweeping 200 cycles of 100mv/s, take out, use 5%HPO
3Soak, moltenly dry after going after the template to wash with secondary water washing.
2, preparation method according to claim 1 is characterized in that the polyprotonic acid in (b) step is 0.5～1.5mol/L sulfuric acid, and corresponding voltage is 18～22V.
3, preparation method according to claim 1 is characterized in that the polyprotonic acid in (b) step is 0.1～0.5mol/L oxalic acid, and corresponding voltage is 30～50V.
4, preparation method according to claim 1 is characterized in that the polyprotonic acid in (b) step is 0.3～1.0mol/L phosphoric acid, and corresponding voltage is 100～130V.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410028164 CN1271109C (en) | 2004-07-21 | 2004-07-21 | Method for preparing high-conductivity polypyrrole material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410028164 CN1271109C (en) | 2004-07-21 | 2004-07-21 | Method for preparing high-conductivity polypyrrole material |
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| Publication Number | Publication Date |
|---|---|
| CN1597733A CN1597733A (en) | 2005-03-23 |
| CN1271109C true CN1271109C (en) | 2006-08-23 |
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| CN 200410028164 Expired - Fee Related CN1271109C (en) | 2004-07-21 | 2004-07-21 | Method for preparing high-conductivity polypyrrole material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102071433A (en) * | 2010-11-25 | 2011-05-25 | 武汉大学 | Interfacial polymerization method for conductive polymers |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029141B (en) * | 2007-02-08 | 2010-08-25 | 华东理工大学 | Production of de-novo hydrophobic poly-pyrrolidone film |
| CN101635201B (en) * | 2008-07-22 | 2011-02-09 | 国家纳米科学中心 | Polypyrrole nano structure electrode and preparation method and application thereof |
| CN101979438B (en) * | 2010-11-25 | 2012-08-08 | 武汉大学 | Preparation method of conductive polypyrrole |
| CN103451698B (en) * | 2013-09-03 | 2016-01-20 | 北京化工大学 | A kind of preparation method of conductive polymer film of high orientation, obtained film and application thereof |
| CN104164680B (en) * | 2013-11-04 | 2017-07-18 | 江苏大学 | A kind of preparation method of the Conductive Polypyrrole Film without substrate support |
| CN108642543B (en) * | 2018-05-30 | 2020-06-05 | 江苏和兴汽车科技有限公司 | Preparation process of high-temperature-resistant anodic oxide layer of aluminum alloy |
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- 2004-07-21 CN CN 200410028164 patent/CN1271109C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102071433A (en) * | 2010-11-25 | 2011-05-25 | 武汉大学 | Interfacial polymerization method for conductive polymers |
| CN102071433B (en) * | 2010-11-25 | 2013-04-24 | 武汉大学 | Interface polymerization method for conductive polymers |
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