CN101780379B - High-concentration carbon nano tube water dispersoid and preparation method thereof - Google Patents
High-concentration carbon nano tube water dispersoid and preparation method thereof Download PDFInfo
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- CN101780379B CN101780379B CN2009101858748A CN200910185874A CN101780379B CN 101780379 B CN101780379 B CN 101780379B CN 2009101858748 A CN2009101858748 A CN 2009101858748A CN 200910185874 A CN200910185874 A CN 200910185874A CN 101780379 B CN101780379 B CN 101780379B
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Abstract
The invention relates to a high-concentration carbon nano tube water dispersoid. The dispersal concentration of carbon nano tubes in de-ionized water containing 0.5-1.5 wt% of dispersant is 20-60mg/ml. The preparation method comprises the following steps: soaking the carbon nano tubes in concentrated inorganic acid at room temperature for at least 10 hours, sonic oscillating for at least 2 hours, neutralizing with sodium hydroxide solution until the pH value is less than or equal to 6, separating, washing to neutrality, and drying to obtain the pretreated carbon nano tubes. The high-concentration carbon nano tube water dispersoid can be obtained by dispersing the pretreated carbon nano tubes in the de-ionized water containing the dispersant and supersonic oscillating for at least half an hour, and can be stably stored for at least one year.
Description
One, technical field
The present invention relates to the dispersion and the process for dispersing thereof of nano material, exactly is a kind of high-concentration carbon nano tube water dispersoid and preparation method thereof.
Two, technical background
CNT is a kind of very important nano material, and it has unique character, is 100 times of steel on mechanical property, and density has only 1/6 of steel, than the high one magnitude of conventional graphite fibre; On electric conductivity, identical with the lamellar structure of graphite, have good electric property, can form conductive network; Utilize its nano effect, can absorb electromagnetic wave, reach the radiation proof effect, also have its good heat conduction and hydrogen storage property in addition; Utilize its above performance, the carbon current nanotube all has application at aspects such as ultracapacitor, conductive plastics, electromagnetic interference shield and stealth material, hydrogen storage material, lithium ion battery, launching site pipe, catalyst carriers.
The subject matter of restriction carbon nano tube device and carbon nano tube compound material application at present is the scattering problem of CNT; CNT solubility in all kinds of solvents is very low; There is stronger huge in addition surface area and the very high draw ratio of Van der Waals force between the CNT; Make it be very easy to reunite and twine, can not embody its premium properties as nano material.And present employed process for dispersing is methods such as reflow treatment, sonic oscillation or adding surfactant in acid solution; But the dispersion concentration of these method CNTs is low, the highest about 10mg/ml generally speaking, at most can only the stable existence two weeks about; Like application number is the concentration that 200810102321 patent can only be accomplished 0.5mg/ml; After two weeks, can reunite, can't satisfy the utilization in reality at all, for example carbon nano tube water dispersoid is used in the lithium ion battery; Under the certain condition of the viscosity of slurry and solid content; For improving battery performance, require CNT to add and must reach certain content, just can only improve the concentration of carbon nano tube water dispersoid; The conductance of carbon nano tube water dispersoid is directly proportional with its concentration under certain concentration in addition, adds in the material or requires the good conductive effect as coating, also can only be through improving the method for carbon nano tube water dispersoid concentration, or the like.Therefore how CNT is dispersed in the water, obtains the high concentration dispersion liquid and then be applied to commercial production being still a great challenge.
Three, summary of the invention
The carbon nano tube water dispersoid that the purpose of this invention is to provide a kind of high concentration, technical problem to be solved are the stability of carbon nano tube water dispersoid.
The alleged high-concentration carbon nano tube water dispersoid of the present invention comprises CNT and water, it is characterized in that dispersed carbon nano tube concentration is 20～60mg/ml in the deionized water that contains 0.5～1.5wt% (mass percentage concentration, down together) dispersant.
Described dispersant is selected from one or more mixed dispersants in the compounds such as polyalcohol, amino acid or amide-type.Polyalcohol is selected from ethylene glycol, glycerine or polyethylene glycol etc.; Amino acid is selected from glycine, serine or threonine etc., and amides compound is selected from asparagine or polyacrylamide etc.
The preparation method of described high-concentration carbon nano tube water dispersoid comprises preliminary treatment and separation, washing, the drying of CNT and disperses; Difference with the prior art is: described preliminary treatment be CNT at 65～70wt% nitric acid or/and soaked under the room temperature at least 10 hours in 95～98wt% sulfuric acid; ℃ following supersonic oscillations at least 2 hours in temperature≤60 then, at last room temperature with stir under slowly add sodium hydroxide solution to reacting liquid pH value≤6; It is dry to separate, wash extremely neutral back, obtains the preliminary treatment CNT; Described dispersion is the preliminary treatment CNT to be stirred to add down contain in the deionized water of 0.5～1.5wt% dispersant, add the back in temperature≤50 ℃ following supersonic oscillations half an hour at least, obtain high-concentration carbon nano tube water dispersoid.
Described dispersant is selected from one or more mixed dispersants in polyalcohol, amino acid or the amides compound.Polyalcohol is selected from ethylene glycol, glycerine or polyethylene glycol etc.; Amino acid is selected from glycine, serine or threonine etc.; Amides compound is selected from asparagine or polyacrylamide.
Preferred its saturated solution of described sodium hydroxide solution.
The useful result of the present invention is:
The present invention is not only that simple concentrated acid soaks, in saturated aqueous slkali and after, can make on the CNT band more oxy radical; Again under ultrasonic condition,, can form carbon nano tube water dispersoid stable, homodisperse, high concentration through the combination reaction or the steric effect of dispersant; In the year of preparation back; Agglomeration do not occur, this method manufacturing process is easy, can realize the CNT industrial applications.
Four, the specific embodiment
Embodiment 1:
(1) take by weighing the 10g CNT and be immersed in the 150ml concentration 69wt% red fuming nitric acid (RFNA), soak time is 12h, after the immersion at room temperature with its sonic oscillation 2h.
(2),, slowly add the NaOH saturated solution in room temperature with under stirring with the CNT red fuming nitric acid (RFNA) mixture behind the sonic oscillation in the step (1); 50～70 rev/mins of mixing speeds, water-cooled is but removed the heat of neutralization, to pH value about 5; Centrifugation is washed till neutrality with deionized water, oven dry.
(3) take by weighing the nanotube that 6g is dried in the step (2); Stir to add down and contain in the 100ml deionized water of 1wt% dispersant; Dispersant is the mixed dispersant of polyethylene glycol and threonine; Polyethylene glycol: threonine mass ratio=1: 1, at room temperature sonic oscillation is 30 minutes, obtains the carbon nano-tube aqueous solutions that concentration is 60mg/ml.
Embodiment 2:
(1) take by weighing the 10g CNT and be immersed in the 150ml 98wt% concentrated sulfuric acid, soak time is 15h, after the immersion at room temperature with its sonic oscillation 3h.
(2) with the CNT concentrated sulfuric acid mixture behind the sonic oscillation in the step (1), under room temperature and stirring condition, slowly add 1 NaOH saturated solution; Mixing speed is controlled at 50～70 rev/mins; Water-cooled is but removed the heat of neutralization, to pH value 5.5, and centrifugation; Be washed till neutrality with deionized water, oven dry.
(3) take by weighing the CNT that 3.5g is dried in the step (2), adding contains in the 100ml deionized water of 0.6wt% dispersant under stirring, and dispersant is a glycerine, at room temperature ultrasonic 40 minutes, obtains the carbon nano-tube aqueous solutions that concentration is 35mg/ml.
Embodiment 3:
(1) take by weighing the 10g CNT and be immersed in the red fuming nitric acid (RFNA) mixed acid of the concentrated sulfuric acid and 50ml concentration of 100m198wt%, soak 12h, after the immersion at room temperature with its sonic oscillation 3h.
(2), under room temperature and stirring condition, slowly add NaOH saturated solution, 50～70 rev/mins of mixing speeds with the CNT nitration mixture mixture behind the sonic oscillation in the step (1); Water-cooled is but removed the heat of neutralization, to pH value 6; Centrifugation is washed till neutrality with deionized water, oven dry.
(3) take by weighing the CNT that 5g is dried in the step (2); Stir to add down and contain in the 100ml deionized water of 1.2wt% dispersant; Dispersant is selected the mixed dispersant of polyethylene glycol and polyacrylamide here for use; Polyethylene glycol: polyacrylamide mass ratio=1: 1 at room temperature ultrasonic 30 minutes, obtains the carbon nano-tube aqueous solutions that concentration is 50mg/ml.
Embodiment 4:
(1) take by weighing the 10g CNT and be immersed in the red fuming nitric acid (RFNA) mixed acid of the concentrated sulfuric acid and 90ml concentration of 60ml concentration 98wt%, soak 12h, after the immersion at room temperature with its sonic oscillation 3h.
(2) with the CNT nitration mixture mixture behind the sonic oscillation in the step (1), under room temperature and stirring condition, slowly add the NaOH saturated solution, 50 rev/mins of mixing speeds; Water-cooled is but removed the heat of neutralization, to the pH5.5 value; Centrifugation is washed till neutrality with deionized water, oven dry.
(3) take by weighing the CNT that 4.5g is dried in the step (2), adding contains in the 100ml deionized water of 0.8wt% dispersant under stirring, and the dispersant polyacrylamide at room temperature played sound 60 minutes, obtained the carbon nano-tube aqueous solutions that concentration is 45mg/ml.
Claims (2)
1. a high-concentration carbon nano tube water dispersoid comprises CNT and water, it is characterized in that: in the deionized water that contains 0.5～1.5wt% dispersant, the concentration of dispersed carbon nano tube is 20～60mg/ml; Described dispersant is selected from one or more the mixture in polyalcohol, amino acid or the amides compound; The preparation method of high-concentration carbon nano tube water dispersoid; Comprise preliminary treatment and separation, washing, drying and the dispersion of CNT; Described preliminary treatment is that CNT soaked 10 hours under the room temperature in concentration 65～70wt% nitric acid or 95～98wt% sulfuric acid at least; ℃ following supersonic oscillations at least 2 hours in temperature≤60 then, at last room temperature with stir under slowly add sodium hydroxide solution to reacting liquid pH value 5-6; Described dispersion is pretreated CNT to be stirred to add down contain in the deionized water of 0.5～1.5wt% dispersant, and in temperature≤50 ℃ following sonic oscillation half an hour at least.
2. high-concentration carbon nano tube water dispersoid according to claim 1 is characterized in that: sodium hydroxide solution is its saturated solution.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102167912A (en) * | 2011-02-22 | 2011-08-31 | 徐州师范大学 | Method for improving dispersity of carbon nano tube in water and water-soluble polymer |
| KR102147002B1 (en) | 2011-06-24 | 2020-08-24 | 브레우어 사이언스 인코포레이션 | Highly soluble carbon nanotubes with enhanced conductivity |
| CN104334494B (en) * | 2012-04-26 | 2019-04-16 | 布鲁尔科技公司 | The polyfunctionality alcohol dispersion of carbon nanotube |
| CN104923095A (en) * | 2015-06-11 | 2015-09-23 | 长沙理工大学 | Physical dispersing method for carbon nano-tube |
| CN109638288A (en) * | 2018-12-06 | 2019-04-16 | 深圳市国创珈伟石墨烯科技有限公司 | A kind of method of stable carbon nano-tube electrocondution slurry viscosity |
| CN110697688A (en) * | 2019-11-15 | 2020-01-17 | 河北北方学院 | Preparation method of carbon nano tube water dispersion |
| CN114307791B (en) * | 2021-12-31 | 2023-02-24 | 无锡东恒新能源科技有限公司 | Dispersing system of carbon nano tube |
| CN115368788A (en) * | 2022-07-01 | 2022-11-22 | 江苏江南烯元石墨烯科技有限公司 | Preparation method of water-based carbon nanotube heat-dissipation coating for high-speed rail gear box |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1513589A (en) * | 2003-05-30 | 2004-07-21 | 中国科学院金属研究所 | Nano-carbon material dispersion liquid and its preparation method |
| CN101037198A (en) * | 2007-02-09 | 2007-09-19 | 浙江大学 | Carbon nano tube with high water-solubility and preparation method thereof |
| CN101177262A (en) * | 2007-11-08 | 2008-05-14 | 浙江大学 | Method for preparing water-soluble and high-biocompatibility carbon nano tube |
| CN101177258A (en) * | 2006-11-10 | 2008-05-14 | 同济大学 | Water-soluble carbon nano tube and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1513589A (en) * | 2003-05-30 | 2004-07-21 | 中国科学院金属研究所 | Nano-carbon material dispersion liquid and its preparation method |
| CN101177258A (en) * | 2006-11-10 | 2008-05-14 | 同济大学 | Water-soluble carbon nano tube and preparation method thereof |
| CN101037198A (en) * | 2007-02-09 | 2007-09-19 | 浙江大学 | Carbon nano tube with high water-solubility and preparation method thereof |
| CN101177262A (en) * | 2007-11-08 | 2008-05-14 | 浙江大学 | Method for preparing water-soluble and high-biocompatibility carbon nano tube |
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