CN101800131A - Active carbon-based material and preparation method thereof - Google Patents
Active carbon-based material and preparation method thereof Download PDFInfo
- Publication number
- CN101800131A CN101800131A CN201010123555A CN201010123555A CN101800131A CN 101800131 A CN101800131 A CN 101800131A CN 201010123555 A CN201010123555 A CN 201010123555A CN 201010123555 A CN201010123555 A CN 201010123555A CN 101800131 A CN101800131 A CN 101800131A
- Authority
- CN
- China
- Prior art keywords
- based material
- preparation
- electrode
- carbon
- active carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides an active carbon-based material and a preparation method thereof. The carbon-based material comprises the following components based on parts by weight percent: 50-90% of carbon, 0.1-35% of oxygen, 0.1-35% of nitrogen, 0.0%-10% of sulphur, 0.0%-15% of phosphorus and 0.0-15% of boron. The preparation method comprises the following step of carbonizing doped or undoped polyaniline polymer at 500-1200 DEG C for 1-24h under the protection of inert gas. Heteroatom N, O, S, P, B, H and group thereof are induced to the carbon atom to change the chemical environment of the carbon atom and increase the space charge density of the carbon atom and the polarity of the material, so that the material has surface standard faraday capacitance and double electric layer capacitance, and has higher specific capacity, good electrical conductivity, and higher energy density and power density under the condition that the specific surface area is not increased. The preparation method of the active carbon-based material has the advantages of simple technology, easily-obtained raw materials, low cost, small pollution and being capable of being produced on a large scale.
Description
Technical field
The present invention relates to a kind of active carbon-based material and preparation method thereof, relate in particular to a kind of a kind of active carbon-based material that is used for ultracapacitor and lithium ion battery negative and preparation method thereof.
Background technology
Ultracapacitor (Supercapacitor) claims electric chemical super capacitor (Electrochemical Supercapacitor) again, is a kind of new energy storage device between battery and conventional electrostatic capacitor.Electrode material is the core part of ultracapacitor, and its structure and performance are directly determining the quality of a ultracapacitor performance.Electrode material mainly contains three classes: carbon-based material, conducting polymer materials and metal oxide materials.Material with carbon element because have porous, big specific area, chemical stability is good, with low cost and advantage such as long service life, as the double electric layers supercapacitor electrode material, can obtain better electrochemical performance, thus the capacitor that uses at present mostly with material with carbon element as work electrode.But existing ultracapacitor material with carbon element, mainly be specific area and the control hole structure that rely on to improve material with carbon element itself improves the capacitance of its electric double layer, thereby developed the porous carbon of high-specific surface area of carbon aerogels, various pore structures and the carbon nanomaterial of various forms; But, increase substantially material with carbon element specific area and hole voidage, can cause the appearance of degradation problem under contact performance decline, conductivity variation, the volume and capacity ratio between its particle and the particle; Though and the specific area of its formation is big but effective ratio area is less, thereby causes the energy density of ultracapacitor and power density to be in very low level, limits its application.Moreover the space that its specific area improves is very limited.
Summary of the invention
At above problem, the invention provides the ultracapacitor active carbon-based material and preparation method thereof that contains hetero-atom N, O, S, P, B, H and group thereof.On carbon atom, introduce hetero-atom N, O, S, P, B, H and group thereof, change carbon atom chemical environment, increase its space charge density and polarity, make material have surperficial accurate faraday's electric capacity and electric double layer capacitance, realize that active material has higher specific capacity, excellent conducting performance, high energy density and power density when not increasing specific area.
For solving the problems of the technologies described above, technical scheme provided by the invention is: a kind of active carbon-based material, the quality of each element composition percentage composition is in the carbon-based material: carbon 50%～90%, oxygen 0.1%～35%, nitrogen 0.1%～35%, sulphur 0.0%～10%, phosphorus 0.0%～15%, boron 0.0%～15%.
The technology of the active carbon-based material that the ultracapacitor that the present invention also provides a kind of simple preparation to contain hetero-atom N, O, S, P, B, H and group thereof is used.Absorbent charcoal material has that cheapness, source are wide, environmental friendliness, chemically stable, low-density, good heat conduction and electric conductivity, better machining property.The preparation method who is above-mentioned active carbon-based material is, under the protection of inert gas, will mix or plain polyaniline polymer, makes char-forming material at 500 ℃～1200 ℃ carbonization 1h～24h.
Further: in the preparation method of above-mentioned active carbon-based material, it comprises that also the material after the carbonization carries out the step of high-temperature activation or solution activation processing again, to improve its specific area, wettability and surface functional group.Described high-temperature activation is to carry out high-temperature activation after activator and char-forming material are mixed to handle, described activator is 0.1～5 with the quality of char-forming material than scope, temperature ranges is 100 ℃～1000 ℃, and constant temperature time is 0～20h, and heat treated gas atmosphere is N
2, Ar, CO
2, H
2In O steam or oxygen and the inert gas one or more and be 1%～90% mixed atmosphere with percent by volume.The activation of described solution chemistry is to be 0.1molL with char-forming material in concentration
-1～10molL
-1H
2SO
4, HNO
3, soak in one or more aqueous solution among the HCl, potassium permanganate, hydrogen peroxide, ammonium persulfate, soaking temperature is 10 ℃～100 ℃, soak time is 30min～96h.Clean to noresidue then for final products.
Perhaps, in the preparation method of above-mentioned active carbon-based material, it comprises that also the activation step that carries out simultaneously with carbonization is as follows: will mix earlier or plain polyaniline polymer to be put into concentration be 0.1molL
-1～10molL
-1Flood 1h～60h in the activator solution, through super-dry, the quality that obtains activator and polymer is 0.1～5 precursor mixture than scope; Be that 400 ℃～1000 ℃, constant temperature time are that 0～20h, heat treatment environment atmosphere are N with the precursor mixture of gained in temperature range then
2, Ar, CO
2, H
2In O steam or oxygen and the inert gas one or more are 1%～90% mixed atmosphere with percent by volume, carry out synchronous carbonization and activation processing.Make through cleaning again with drying process.
Further again: in the preparation method of the active carbon-based material that above-mentioned and carbonization activate simultaneously, described activator is KOH, NaOH, ZnCl
2, H
3PO
4, H
3BO
3, in sodium salt and the sylvite aqueous solution one or more.Described doping or plain polyaniline polymer be utilize aniline monomer, by chemical polymerization or electrochemical polymerization, the method synthesizing blender or the plain polyaniline polymer that adopt protonic acid doping or go to mix.
Described chemical polymerization is meant following process:
1. aniline monomer is dissolved in Bronsted acid, wiring solution-forming A; 2. oxidant is made into 0.5～2mol/L solution B with distilled water or deionized water, wherein the mol ratio of oxidant and organic monomer is 0.1～10 among the B; 3. solution A is transferred in the reactor and stirred, again solution B is added drop-wise in the reaction bulb, two kinds of solution polymerization reaction take places, the reaction time is 1h～30h, and the reaction room temperature is-5 ℃～50 ℃, and the mode that course of reaction is taked to stir, leave standstill or the two combines is carried out; 4. after reaction finishes, product washing being separated several times, after filtrate is neutrality, is 50 ℃～100 ℃, normal pressure or vacuumize 2h～12h obtain the mixing polyaniline of attitude in temperature.Described oxidant is persulfate, chloric acid or perchlorate, KMnO
4, HClO
4, CuCl
2, Ce (SO
4)
2, H
2O
2, trivalent soluble ferric iron salt, V
2O
5, MnO
2In the mixture of one or more aqueous solution.
Described electrochemical polymerization is meant following process: 1. aniline monomer and Bronsted acid are made into mixed electrolyte solutions, wherein the concentration of aniline is 0.01molL
-1～3.0molL
-1, Bronsted acid concentration be 0.1molL
-1～5molL
-1, aniline and Bronsted acid mol ratio be 0.05～5; 2. the electrode that adopted of aniline electrochemical polymerization comprises carbon electrode, lead and alloy electrode thereof, lead dioxide electrode, stainless steel electrode, nickel and alloy electrode thereof, titanium and alloy electrode thereof, conductive glass electrode or noble metal electrode; The shape of electrode comprises plate electrode, mesh electrode, stick electrode; 3. the constant potential polymerization is adopted in the electrochemical polymerization of aniline, and potential range is that 0.4V～3.0V, current density are 0.1Adm
-2～10Adm
-2Perhaps adopt electrokinetic potential scanning polymerization, potential range is that 0.4V～3.0V, electric potential scanning speed are 1mVs
-1～300mVs
-1, polymerization time is 10min～20h; Polymerization temperature is 5 ℃～50 ℃; The alr mode of electrolyte is gas stirring, mechanical agitation or does not stir; 4. after reaction finishes, product washing being separated several times, after filtrate is neutrality, is 50 ℃～100 ℃, normal pressure or vacuumize 2h～12h obtain the mixing polyaniline of attitude in temperature.Described Bronsted acid is H
2SO
4, HCl, HClO
4, HNO
3, H
3PO
4, H
3BO
3, CH
3In CHOOH, CHOOH, benzoic acid, p-methyl benzenesulfonic acid, citric acid, the oxalic acid one or more.Described method of going to mix is meant that claim 7 or 8 described polyaniline polymer carry out dedoping with ammonia spirit dipping 2h～36h of 1%～20%, the solid-to-liquid ratio of doped polyaniline and ammonia spirit is 0.01～10, repeatedly reach 7.0 with distilled water or deionized water wash separation behind the dedoping, or promptly obtain plain polyaniline 1～2 time with the ethanol cleaning again until pH.
The present invention has the following advantages compared to existing technology:
The invention provides active carbon-based material that the ultracapacitor that contains hetero-atom N, O, S, P, B, H and group thereof uses and preparation method thereof.On carbon atom, introduce hetero-atom N, O, S, P, B, H and group thereof, change carbon atom chemical environment, increase the polarity of its space charge density and molecule, make material have surperficial accurate faraday's electric capacity and electric double layer capacitance, realize that active material has higher specific capacity, excellent conducting performance, high energy density and power density when not increasing specific area.Absorbent charcoal material has that cheapness, source are wide, environmental friendliness, chemically stable, low-density, good heat conduction and electric conductivity, better machining property.Active carbon is to collect rice space, ultramicron and Surface Physical Chemistry characteristic in the new material of one.Have abundant hole institutional framework and surface chemical structure.So absorbent charcoal material is widely used as all many-sides such as adsorbent, catalyst carrier, filter membrane, electrode material.The preparation of novel carbon-based material and application study thereof are one of the forward position in current investigation of materials field and focus, in the preparation active carbon, its hole institutional framework and surface chemical structure are regulated and control, be not only perfect and development, and help further to expand the application of raw material of wood-charcoal material the absorbent charcoal material research system.The preparation method of doping active carbon-based material provided by the invention has advantages such as technology is simple, raw material is easy to get, cost is low, pollution is little, can be mass-produced, and is easy to industrialization.
Description of drawings
(current density is 1Ag to Fig. 1 for the constant current charge-discharge curve of the ultracapacitor be made up of the carbon-based material of embodiment 1 preparation
-1).
Fig. 2 is the AC impedance figure of the ultracapacitor be made up of the carbon-based material of embodiment 2 preparation.
Ultracapacitor the continuous charge and discharge circulation life figure under different current densities of Fig. 3 for forming by the carbon-based material of embodiment 3 preparations.
Fig. 4 is the cyclic voltammogram of ultracapacitor under different scanning rates of being made up of the carbon-based material of embodiment 4 preparations.
Fig. 5 is the scanning electron microscope diagram SEM of the carbon-based material of embodiment 5 preparations.
Embodiment
Purport of the present invention is to introduce hetero-atom N, O, S, P, B, H and group thereof on carbon atom, change carbon atom chemical environment, increase the polarity of its space charge density and molecule, make material have surperficial accurate faraday's electric capacity and electric double layer capacitance, realize that active material has higher specific capacity, excellent conducting performance, high energy density and power density when not increasing specific area.The preparation method of doping active carbon-based material provided by the invention has advantages such as technology is simple, raw material is easy to get, cost is low, pollution is little, can be mass-produced, and is easy to industrialization.Below in conjunction with embodiment content of the present invention is described in further detail, mentioned content is not a limitation of the invention among the embodiment, and the time in the method and the selection of temperature can be suited measures to local conditions and the result be there is no substantial effect.
(1) 1.86mL aniline (AN) is dissolved in 25mLH
2SO
4Middle wiring solution-forming A, 1.14g ammonium persulfate (APS) is dissolved in wiring solution-forming B in 50mL distilled water or the deionized water ([APS]/[AN]=1: 4); (2) solution A is changed in the reaction bulb, under stirring B is added drop-wise in the reaction bulb, after dripping off, room temperature reaction 4h; (3) collect product in the reaction bulb, water, ethanol or acetone is washed product repeatedly, is neutral until cleaning solution; (4) product after will washing obtains the polyaniline that sulfuric acid mixes in 60 ℃ of vacuumize 48h; (5) at inert gas N
2Protection is descended polyaniline at 800 ℃ of carbonization 2h; (6) char-forming material activation processing constant temperature 2h in 200 ℃ water vapour that will make above, cool to room temperature promptly obtains N, O, the atom doped activated carbon sill of S.Each component and the quality thereof of the active carbon-based material that obtains mixing through the test of elementary analysis and x-ray photoelectron power spectrum (XPS) than content are: carbon C content is 78.95%, oxygen O content is 12.21%, nitrogen N content is 7.118%, and sulphur S content is 0.257%, and hydrogen H content is 1.446%.The not activated sample code name that this embodiment makes is that C800, activated sample code name are CA800.
C800 and CA800 with preparation are that electrode active material C, acetylene black AB are that conductive agent, polyvinylidene fluoride PVDF are binding agent, and the mass ratio of C: AB: PVDF is to make the electrode of ultracapacitor at 80: 10: 10.At first, active material C is mixed with acetylene black, fully grinds, then ground powder is fully mixed with PVDF in being dissolved in N-N-methyl-2-2-pyrrolidone N-NMP, mix well pulping, be uniformly coated on then on the collector nickel foil, dry 10h under 90 ℃ promptly gets electrode slice.With 6molL
-1KOH solution is electrolyte, is assembled into two electrode system ultracapacitors of symmetry, and in 0～1V voltage range, the CHI660A electrochemical workstation that utilizes Shanghai occasion China instrument company to produce carries out charge-discharge test.Fig. 1 represents the charge-discharge test result of the ultracapacitor that the sample of embodiment 1 preparation is made.Time by the charging and discharging curve among Fig. 1 can find out that CA800 has much longer discharging and recharging the time under identical current density, and the specific capacity of this explanation CA800 sample is much bigger.
(1) 1.86mL aniline is dissolved in 25mLH
2SO
4Middle wiring solution-forming A, the 2.28g ammonium persulfate is dissolved in wiring solution-forming B in 50mL distilled water or the deionized water ([APS]/[AN]=1: 2); (2) solution A and solution B behind the rapid mixing stirring 1min, are at room temperature left standstill reaction 10h with it in reaction bulb; (3) collect product in the reaction bulb, water, ethanol or acetone is washed product repeatedly, is neutral until cleaning solution; (4) product after will washing is in 60 ℃ of vacuumize 48h, the polyaniline that obtains mixing; (5) at inert gas N
2Protection is descended polyaniline at 800 ℃ of carbonization 2h; (6) char-forming material that will make above is at 10 ℃～40 ℃ 1molL
-1Soak 24h in the salpeter solution and carry out activation processing, promptly obtain the material with carbon element that activates through washing, dry, ball milling again.The not activated sample code name that this embodiment makes is that C800, activated sample code name are CA800.
Electrode making in the present embodiment, the assembling of ultracapacitor, tester are with embodiment 1.Fig. 2 is that 5mV, temperature are to carry out under the condition of room temperature for this embodiment at test frequency scope 0.01Hz～100KHz, voltage amplitude.Find out by the AC impedance curve among Fig. 2, CA800 than C800 have littler impedance, straight line portion has bigger slope, the sample after this explanation activation has better charge transmission and better capacitance characteristic.
(1) 20mmol aniline and the HAc of 20mmol are ultrasonic mixes about 2min and gets A; (2) 25mmolAPS is dissolved among the HAc of 20mmol, the ultrasonic about 2min of abundant dissolving mixing that makes gets B.(3) mix about 2min with A and B are ultrasonic under room temperature, leave standstill reaction 8h in room temperature then.(3) collecting reaction product washes product with water, is neutral until cleaning solution; (4) product after will washing is in 60 ℃ of vacuumize 24h, the polyaniline that obtains mixing; (5) at inert gas N
2Protection is descended polyaniline at 800 ℃ of carbonization 4h; (6) after char-forming material that will make above and NaOH mixed, 700 ℃ of activation 2h (mass ratio of carbon and NaOH is 2: 1) under nitrogen protection promptly obtained the carbon-based material that activates through washing, drying, ball milling again.
Electrode making in the present embodiment, the assembling of ultracapacitor, tester are with embodiment 1.In the cycle life curve such as Fig. 3 of the ultracapacitor that the sample behind overactivation makes.Find out by the curve among Fig. 3, be respectively 1Ag in current density
-1, 3Ag
-1And 5Ag
-1Condition under continuous charge and discharge cycles 10000 times respectively, its specific capacity keeps 260Fg respectively
-1, 230Fg
-1, 180Fg
-1, decay hardly.Current density is by 1Ag
-1Be increased to 5Ag
-1, it still keeps 1Ag than electric capacity
-1Under the condition 69%.These data declarations, the capacitor of prepared material have current ratio characteristic and good circulation life characteristic preferably.
(1) 1.86mL aniline is dissolved in 25mLH
2SO
4Middle wiring solution-forming A, the 3.42g ammonium persulfate is dissolved in wiring solution-forming B in 50mL distilled water or the deionized water ([APS]/[AN]=1: 1); (2) solution A is changed in the reaction bulb, under stirring B is added drop-wise in the reaction bulb, after dripping off, room temperature reaction 8h; (3) collect product in the reaction bulb, water, ethanol or acetone is washed product repeatedly, is neutral until cleaning solution; (4) product after will washing is in 60 ℃ of vacuumize 10h, the polyaniline that obtains mixing; (5) with the polyaniline and the activator K that prepare
2CO
3Solution impregnation (polyaniline and K
2The mass ratio of CO3 is 2: 1), 105 ℃ of dryings promptly obtain K then
2CO
3The polyaniline precursor material of dipping; (6) with polyaniline precursor material at N
2Under the Buchholz protection, at 600 ℃ of following carbonization constant temperature 1h; After naturally cooling to room temperature, with it at first at 1molL
-1H
2SO
4Wash, in deionized water, clean to again till the pH value neutrality, the carbon-based material that the hetero-atom that promptly obtains activating mixes.
Electrode making in the present embodiment, the assembling of ultracapacitor, tester are with embodiment 1.Dress up the cyclic voltammetric test result of ultracapacitor such as the curve among Fig. 4 through the sample sets after synchronous carbonization and the activation.Being respectively in sweep speed among Fig. 4 is 2mVs
-1, 5mVs
-1, 10mVs
-1And 20mVs
-1Cyclic voltammetry curve under the condition.Can find out by the curve among Fig. 4, be the curve that is similar to rectangular symmetrical.This explanation, the capacitor of prepared material has desirable capacitance characteristic.Unipolarly adopt following formula to calculate than electric capacity:
C, I, m and v represent that respectively ultracapacitor is unipolar than electric capacity (Fg in the formula
-1), the electric current (A) that cyclic voltammetry curve intermediate potential point is corresponding, quality of activated carbon (g) and sweep speed (Vs
-1).Sweep speed is 5mVs
-1Condition under, calculating it unipolar is 210Fg than electric capacity
-1
(1) 1.86mL aniline is dissolved in 25mLH
2SO
4Middle wiring solution-forming A, the 3.42g ammonium persulfate is dissolved in wiring solution-forming B in 50mL distilled water or the deionized water ([APS]/[AN]=1: 1); (2) solution A is changed in the reaction bulb, under stirring B is added drop-wise in the reaction bulb, after dripping off, room temperature reaction 8h; (3) collect product in the reaction bulb, water, ethanol or acetone is washed product repeatedly, is neutral until cleaning solution; (4) product after will washing is in 50 ℃ of vacuumize 30h, the polyaniline that obtains mixing; (5) doped polyaniline is carried out dedoping with 5% ammonia spirit dipping 12h, the solid-to-liquid ratio of doped polyaniline and ammonia spirit is 0.01～10.Repeatedly reach 7.0 with distilled water or deionized water wash separation behind the dedoping, clean the intrinsic polyaniline that promptly obtains dedoping for 1～2 time with ethanol again until pH.(5) with the dedoping intrinsic polyaniline and the activator ZnCl that prepare
2Solution impregnation (intrinsic polyaniline and ZnCl
2Mass ratio be 1: 1), 105 ℃ of dryings promptly obtain ZnCl then
2The polyaniline precursor material of dipping; (6) with polyaniline precursor material under the Ar Buchholz protection, at 700 ℃ of carbonization constant temperature 1h; After naturally cooling to room temperature, with it at first at 1molL
-1H
2SO
4Wash, in deionized water, clean to again till the pH value neutrality, the carbon-based material that the hetero-atom that promptly obtains activating mixes.
Prepared material adopts LEO1525 type sem observation pattern as shown in Figure 5.As can be seen from Figure 5, prepared material is the particle of more homodisperse almost spherical, and granular size is below 1 μ m.
Claims (10)
1. active carbon-based material is characterized in that: the quality of each element is formed percentage composition and is in the carbon-based material: carbon 50%～90%, oxygen 0.1%～35%, nitrogen 0.1%～35%, sulphur 0.0%～10%, phosphorus 0.0%～15%, boron 0.0%～15%.
2. the preparation method of an active carbon-based material according to claim 1 is characterized in that: under the protection of inert gas, will mix or plain polyaniline polymer, and make char-forming material at 500 ℃～1200 ℃ carbonization 1h～24h.
3. the preparation method of active carbon-based material according to claim 2, it is characterized in that: it also comprises the high-temperature activation of char-forming material or the step of solution activation processing.
Described high-temperature activation is to carry out high-temperature activation after activator and char-forming material are mixed to handle, described activator is 0.1～5 with the quality of char-forming material than scope, temperature ranges is 100 ℃～1000 ℃, and constant temperature time is 0～20h, and heat treated gas atmosphere is N
2, Ar, CO
2, H
2In O steam or oxygen and the inert gas one or more and be 1%～90% mixed atmosphere with percent by volume.
The activation of described solution chemistry is to be 0.1molL with char-forming material in concentration
-1～10molL
-1H
2SO
4, HNO
3, soak in one or more aqueous solution in the hydrochloric acid, potassium permanganate, hydrogen peroxide, ammonium persulfate, soaking temperature is 10 ℃～100 ℃, soak time is 30min～96h.
4. the preparation method of active carbon-based material according to claim 2, it is characterized in that: it comprises that also the activation step that carries out simultaneously with carbonization is as follows:
To mix earlier or plain polyaniline polymer to be put into concentration be 0.1molL
-1～10molL
-1Flood 1h～120h in the activator solution, through super-dry, the quality that obtains activator and polymer is 0.1～5 carbon precursor mixture than scope; Be that 400 ℃～1000 ℃, constant temperature time are that 0～20h, heat treatment environment atmosphere are N with the precursor mixture of gained in temperature range then
2, Ar, CO
2, H
2In O steam or oxygen and the inert gas one or more are 1%～90% mixed atmosphere with percent by volume, carry out synchronous carbonization and activation processing, making through cleaning with drying process again.
5. according to the preparation method of claim 3 or 4 described active carbon-based materials, it is characterized in that: described high-temperature activation agent is KOH, NaOH, ZnCl
2, H
3PO
4, H
3BO
3, in sodium salt and the sylvite aqueous solution one or more.
6. the preparation method of active carbon-based material according to claim 2 is characterized in that: described doping or plain polyaniline polymer be utilize aniline monomer, by chemical polymerization or electrochemical polymerization, the method synthesizing blender or the plain polyaniline polymer that adopt protonic acid doping or go to mix.
7. the preparation method of active carbon-based material according to claim 6, it is characterized in that: described chemical polymerization is meant following process:
1. aniline monomer is dissolved in Bronsted acid, wiring solution-forming A;
2. oxidant is made into 0.5molL with distilled water or deionized water
-1～2molL
-1Solution B, wherein the mol ratio of oxidant and organic monomer is 0.1～5 among the B;
3. solution A is transferred in the reactor and stirred, again solution B is added drop-wise in the reaction bulb, two kinds of solution polymerization reaction take places, the reaction time is 1h～30h, and the reaction room temperature is-5 ℃～50 ℃, and the mode that course of reaction is taked to stir, leave standstill or the two combines is carried out;
4. after reaction finishes, product washing being separated several times, after filtrate is neutrality, is 50 ℃～100 ℃, normal pressure or vacuumize 2h～12h obtain the mixing polyaniline of attitude in temperature.
Described oxidant is persulfate, chloric acid or perchlorate, KMnO
4, HClO
4, CuCl
2, Ce (SO
4)
2, H
2O
2, trivalent soluble ferric iron salt, V
2O
5, MnO
2In the mixture of one or more aqueous solution.
8. the preparation method of active carbon-based material according to claim 6, it is characterized in that: described electrochemical polymerization is meant following process:
1. aniline monomer and Bronsted acid are made into mixed electrolyte solutions, wherein the concentration of aniline is 0.01molL
-1～3.0molL
-1, Bronsted acid concentration be 0.1molL
-1～5molL
-1, aniline and Bronsted acid mol ratio be 0.05～5;
2. the electrode that adopted of aniline electrochemical polymerization comprises carbon electrode, lead and alloy electrode thereof, lead dioxide electrode, stainless steel electrode, nickel and alloy electrode thereof, titanium and alloy electrode thereof, conductive glass electrode or noble metal electrode; The shape of electrode comprises plate electrode, mesh electrode, stick electrode;
3. the constant potential polymerization is adopted in the electrochemical polymerization of aniline, and potential range is that 0.4V～3.0V, current density are 0.1Adm
-2～10Adm
-2Perhaps adopt electrokinetic potential scanning polymerization, potential range is that 0.4V～3.0V, electric potential scanning speed are 1mVs
-1～300mVs
-1, polymerization time is 10min～20h; Polymerization temperature is 5 ℃～50 ℃; The alr mode of electrolyte is gas stirring, mechanical agitation or does not stir;
4. after reaction finishes, product washing being separated several times, after filtrate is neutrality, is 50 ℃～100 ℃, normal pressure or vacuumize 2h～12h obtain the mixing polyaniline of attitude in temperature.
9. select the preparation method of a described active carbon-based material according to claim 6-8, it is characterized in that: described Bronsted acid is H
2SO
4, HCl, HClO
4, HNO
3, H
3PO
4, H
3BO
3, CH
3In CHOOH, CHOOH, benzoic acid, p-methyl benzenesulfonic acid, citric acid, the oxalic acid one or more.
10. the preparation method of active carbon-based material according to claim 6, it is characterized in that: described method of going to mix is meant that claim 7 or 8 described polyaniline polymer carry out dedoping with ammonia spirit dipping 2h～36h of 1%～20%, the solid-to-liquid ratio of doped polyaniline and ammonia spirit is 0.01～10, repeatedly reach 7.0 with distilled water or deionized water wash separation behind the dedoping, or promptly obtain plain polyaniline 1～2 time with the ethanol cleaning again until pH.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101235557A CN101800131B (en) | 2010-03-11 | 2010-03-11 | Active carbon-based material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101235557A CN101800131B (en) | 2010-03-11 | 2010-03-11 | Active carbon-based material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101800131A true CN101800131A (en) | 2010-08-11 |
| CN101800131B CN101800131B (en) | 2012-09-05 |
Family
ID=42595758
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101235557A Expired - Fee Related CN101800131B (en) | 2010-03-11 | 2010-03-11 | Active carbon-based material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101800131B (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051047A (en) * | 2010-11-19 | 2011-05-11 | 南京邮电大学 | Method for preparing carbon nitride tube-polyaniline-gold composite material and application method thereof |
| CN102923689A (en) * | 2012-11-06 | 2013-02-13 | 中国科学院宁波材料技术与工程研究所 | Method for preparing grapheme/carbon composite material |
| CN104851601A (en) * | 2015-04-03 | 2015-08-19 | 安徽江威精密制造有限公司 | Terne metal-clad straw-based active carbon composite electrode material and preparation method thereof |
| CN104867692A (en) * | 2015-04-03 | 2015-08-26 | 安徽江威精密制造有限公司 | Copper-tin-alloy-coated straw based active carbon electrode material and preparation method thereof |
| CN105253871A (en) * | 2015-09-25 | 2016-01-20 | 深圳博磊达新能源科技有限公司 | Nitrogen-containing carbon material for supercapacitosr, preparation method thereof, and supercapacitor electrode material |
| CN106298265A (en) * | 2015-06-10 | 2017-01-04 | 辽宁立德电力工程设计有限公司 | Ultracapacitor composite and preparation method thereof |
| CN106784759A (en) * | 2017-04-01 | 2017-05-31 | 重庆大学 | A kind of silicon/activated carbon composite negative pole material and preparation method thereof |
| CN106784712A (en) * | 2016-12-28 | 2017-05-31 | 中国人民解放军国防科学技术大学 | Positive electrode and preparation method thereof, positive plate and lithium-sulfur cell |
| CN107732209A (en) * | 2017-10-18 | 2018-02-23 | 中南大学 | It is a kind of to mix the method that bacteria residue waste material prepares lithium ion carbon negative pole material |
| CN108780707A (en) * | 2016-03-18 | 2018-11-09 | 国立大学法人信州大学 | Lithium composite negative pole and mixed capacitor and their manufacturing method |
| CN108807889A (en) * | 2018-05-24 | 2018-11-13 | 天津工业大学 | A kind of preparation method and applications of porous Fe2O3 doping barium oxide electrode material |
| CN108950740A (en) * | 2018-06-26 | 2018-12-07 | 合肥萃励新材料科技有限公司 | A kind of synthetic method of FTO load carbon fiber |
| CN110112003A (en) * | 2019-04-01 | 2019-08-09 | 中国矿业大学 | A method of recycling industrial waste Oil Paint Slag prepares electrode material for super capacitor |
| CN111620428A (en) * | 2020-06-03 | 2020-09-04 | 北京林业大学 | Method for degrading organic pollutants by activating persulfate through polyaniline carbide |
| CN112915966A (en) * | 2021-01-28 | 2021-06-08 | 东北大学 | Preparation method and application of polyaniline-based activated carbon |
| CN114613611A (en) * | 2022-03-23 | 2022-06-10 | 黄山学院 | Preparation method and application of oxygen-enriched hollow tubular porous carbon |
| CN115295325A (en) * | 2022-08-05 | 2022-11-04 | 山东精工能源科技有限公司 | Preparation method of high-performance nitrogen-doped porous carbon electrode |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1419256A (en) * | 2001-11-14 | 2003-05-21 | 成都茵地乐电源科技有限公司 | Polarizable electrode carbon material for super capacitor and preparation method thereof |
| CN101388291A (en) * | 2008-10-31 | 2009-03-18 | 中国科学院上海硅酸盐研究所 | Boron containing porous carbon electrode material and preparation thereof |
| CN101587951A (en) * | 2008-05-23 | 2009-11-25 | 中国人民解放军63971部队 | Novel carbon-sulfur compound for lithium-sulfur battery |
-
2010
- 2010-03-11 CN CN2010101235557A patent/CN101800131B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1419256A (en) * | 2001-11-14 | 2003-05-21 | 成都茵地乐电源科技有限公司 | Polarizable electrode carbon material for super capacitor and preparation method thereof |
| CN101587951A (en) * | 2008-05-23 | 2009-11-25 | 中国人民解放军63971部队 | Novel carbon-sulfur compound for lithium-sulfur battery |
| CN101388291A (en) * | 2008-10-31 | 2009-03-18 | 中国科学院上海硅酸盐研究所 | Boron containing porous carbon electrode material and preparation thereof |
Non-Patent Citations (2)
| Title |
|---|
| 吴宇平 等: "《磷的掺杂对碳负极材料性能的影响》", 《应用化学》, 31 December 1998 (1998-12-31) * |
| 汪树军 等: "《导电高分子聚苯胺碳化材料的电化学性能》", 《北京科技大学学报》, 31 August 1996 (1996-08-31), pages 374 * |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051047B (en) * | 2010-11-19 | 2012-04-11 | 南京邮电大学 | Method for preparing carbon nitride tube-polyaniline-gold composite material and application method thereof |
| CN102051047A (en) * | 2010-11-19 | 2011-05-11 | 南京邮电大学 | Method for preparing carbon nitride tube-polyaniline-gold composite material and application method thereof |
| CN102923689A (en) * | 2012-11-06 | 2013-02-13 | 中国科学院宁波材料技术与工程研究所 | Method for preparing grapheme/carbon composite material |
| CN102923689B (en) * | 2012-11-06 | 2015-08-19 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of graphene/carbon composite material |
| CN104851601A (en) * | 2015-04-03 | 2015-08-19 | 安徽江威精密制造有限公司 | Terne metal-clad straw-based active carbon composite electrode material and preparation method thereof |
| CN104867692A (en) * | 2015-04-03 | 2015-08-26 | 安徽江威精密制造有限公司 | Copper-tin-alloy-coated straw based active carbon electrode material and preparation method thereof |
| CN106298265A (en) * | 2015-06-10 | 2017-01-04 | 辽宁立德电力工程设计有限公司 | Ultracapacitor composite and preparation method thereof |
| CN105253871A (en) * | 2015-09-25 | 2016-01-20 | 深圳博磊达新能源科技有限公司 | Nitrogen-containing carbon material for supercapacitosr, preparation method thereof, and supercapacitor electrode material |
| CN108780707A (en) * | 2016-03-18 | 2018-11-09 | 国立大学法人信州大学 | Lithium composite negative pole and mixed capacitor and their manufacturing method |
| CN108780707B (en) * | 2016-03-18 | 2021-06-01 | 国立大学法人信州大学 | Lithium composite negative electrode, hybrid capacitor, and methods for producing same |
| CN106784712A (en) * | 2016-12-28 | 2017-05-31 | 中国人民解放军国防科学技术大学 | Positive electrode and preparation method thereof, positive plate and lithium-sulfur cell |
| CN106784712B (en) * | 2016-12-28 | 2019-09-17 | 中国人民解放军国防科学技术大学 | Positive electrode and preparation method thereof, positive plate and lithium-sulfur cell |
| CN106784759A (en) * | 2017-04-01 | 2017-05-31 | 重庆大学 | A kind of silicon/activated carbon composite negative pole material and preparation method thereof |
| CN107732209A (en) * | 2017-10-18 | 2018-02-23 | 中南大学 | It is a kind of to mix the method that bacteria residue waste material prepares lithium ion carbon negative pole material |
| CN107732209B (en) * | 2017-10-18 | 2020-08-25 | 中南大学 | Method for preparing lithium ion carbon negative electrode material from mixed bacteria residue waste |
| CN108807889A (en) * | 2018-05-24 | 2018-11-13 | 天津工业大学 | A kind of preparation method and applications of porous Fe2O3 doping barium oxide electrode material |
| CN108950740A (en) * | 2018-06-26 | 2018-12-07 | 合肥萃励新材料科技有限公司 | A kind of synthetic method of FTO load carbon fiber |
| CN110112003A (en) * | 2019-04-01 | 2019-08-09 | 中国矿业大学 | A method of recycling industrial waste Oil Paint Slag prepares electrode material for super capacitor |
| CN110112003B (en) * | 2019-04-01 | 2020-12-25 | 中国矿业大学 | Method for preparing supercapacitor electrode material by recycling industrial waste paint residues |
| CN111620428A (en) * | 2020-06-03 | 2020-09-04 | 北京林业大学 | Method for degrading organic pollutants by activating persulfate through polyaniline carbide |
| CN111620428B (en) * | 2020-06-03 | 2022-02-08 | 北京林业大学 | Method for degrading organic pollutants by activating persulfate through polyaniline carbide |
| CN112915966A (en) * | 2021-01-28 | 2021-06-08 | 东北大学 | Preparation method and application of polyaniline-based activated carbon |
| CN114613611A (en) * | 2022-03-23 | 2022-06-10 | 黄山学院 | Preparation method and application of oxygen-enriched hollow tubular porous carbon |
| CN115295325A (en) * | 2022-08-05 | 2022-11-04 | 山东精工能源科技有限公司 | Preparation method of high-performance nitrogen-doped porous carbon electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101800131B (en) | 2012-09-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101800131B (en) | Active carbon-based material and preparation method thereof | |
| Manikandan et al. | Self-coupled nickel sulfide@ nickel vanadium sulfide nanostructure as a novel high capacity electrode material for supercapattery | |
| CN101696323B (en) | Method for preparing polyaniline/manganese dioxide composite material for super capacitor | |
| CN101599370B (en) | Method for fast preparing conductive carbon/manganese dioxide composite electrode material | |
| CN105253871B (en) | Ultracapacitor nitrogenous carbon material and preparation method thereof, electrode material for super capacitor | |
| Gu et al. | Local protonation of polyaniline induced by nitrogen-doped carbon skeleton towards ultra-stable Zn-organic batteries with a dual-ion insertion/extraction mechanism | |
| CN102751101B (en) | A kind of platinum/graphene nano matrix material and its preparation method and application | |
| CN102800432A (en) | Method for preparing oxidized graphene/conductive polypyrrole nano wire composite material | |
| Gong et al. | Facile synthesis of Ni 0.85 Se on Ni foam for high-performance asymmetric capacitors | |
| CN110335764B (en) | Pre-sodium treatment method for efficiently constructing sodium ion capacitor | |
| CN101546650B (en) | Electrode material of super capacitor and its preparation method | |
| CN106847547A (en) | Three-dimensional tubulose molybdenum bisuphide/polypyrrole composite electrode material for super capacitor and its preparation | |
| CN109678139A (en) | Fluorine nitrogen codope porous graphene hydrogel and preparation method thereof for electrode of super capacitor | |
| Yang et al. | A novel self-supported structure of Ce-UiO-66/TNF in a redox electrolyte with high supercapacitive performance | |
| CN106876154A (en) | The preparation method of polyaniline-sulfonated graphene combination electrode material | |
| Yang et al. | A bubble-templated approach to holey N/S-codoped carbon nanosheet aerogels with honeycomb-like structure for supercapacitors | |
| Zhao et al. | Fabrication of 3D micro-flower structure of ternary Ni-Co-Cu hydroxide based on Co-MOF for advanced asymmetric supercapacitors | |
| Luo et al. | Preparation of NiMoO4 nanoarrays electrodes with optimized morphology and internal crystal water for efficient supercapacitors and water splitting | |
| CN103359796A (en) | Preparation method of supercapacitor cobaltous oxide electrode material | |
| CN102820137A (en) | High-activity TiO2 nanometer pipe/ intermediate phase carbon microsphere composite material and preparation method and application thereof | |
| CN104134548A (en) | Porous composite material of manganese dioxide and carbon and preparation method thereof | |
| CN104124435B (en) | Multiple edge MoS2nanometer sheet/Graphene electrochemistry storage sodium combination electrode and preparation method | |
| Yi et al. | Local spin-state tuning enables high-efficiency nickel sulfide cathode for stable alkaline Zn batteries | |
| CN111029163B (en) | Spherical cobalt oxide/carbon/manganese oxide/carbon compound and preparation method and application thereof | |
| CN103839691A (en) | Nitrogen-doped graphene composite material, preparation method thereof, electrode plate and supercapacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120905 Termination date: 20160311 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |