CN102381697A - Method for preparing spherical carbon material - Google Patents
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- CN102381697A CN102381697A CN2011102018190A CN201110201819A CN102381697A CN 102381697 A CN102381697 A CN 102381697A CN 2011102018190 A CN2011102018190 A CN 2011102018190A CN 201110201819 A CN201110201819 A CN 201110201819A CN 102381697 A CN102381697 A CN 102381697A
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Abstract
The invention relates to a method for preparing spherical porous carbon, wherein the spherical porous carbon is obtained through the following steps of taking commercialized spherical polyvinylidene fluoride (PVDF) resin as a raw material, carrying out defluorination stabilization at a low temperature below 150 DEG C, carrying out carbonization at high temperature, and activating. The commercial production of the spherical PVDF resin is realized, the particle diameter of the spherical PVDF resin is controllable, and the method for preparing the spherical porous carbon has the advantages that the method is simple, the degree of sphericity of a carbon sphere is good, the particle diameter is uniform, the size of the particle diameter is easy to regulate and control, and the like. The particle diameter of the spherical porous carbon is adjustable between 5 nm and 50 microns, the specific surface area is 50-3000 m<2>/g, and thus, the spherical porous carbon can be used for an electrode material of a super capacitor, an electrode material of a lithium ion battery, an electrode material of a capacitance-method desalination equipment, blood purification, a catalyst carrier, water treatment, gas purification, solvent recovery and the like.
Description
Technical field
The present invention relates to raw material of wood-charcoal preparation method for material and application thereof, particularly a kind of preparation method of spherical porous charcoal and application.
Technical background
Gac characteristics such as can regulate within the specific limits owing to have flourishing hole, high-specific surface area, high pore volume, aperture size; Be widely used in fields such as purification of water quality, gas delivery, solvent recuperation, decolouring as a kind of sorbing material, also can be used for the electrode materials of support of the catalyst and lithium ion battery, ultracapacitor etc.According to the difference of pattern, gac can be divided into powdered carbon, activated carbon granule, columnar activated carbon, NACF shape, ball shape active carbon, cellular activated carbon etc.The spherical carbon material has good spherical design, and tap density is big, has unique application advantage in some occasions.
The discovery of spherical carbon material is in the sixties in 20th century, and people find that in the forming process of research coke the pitch compounds intermediate phase can take place changes in heat treatment process, generate mesophase ball.1973, Honda and Yamada separated mesophase ball from the pitch parent, and were referred to as carbonaceous mesophase spherules to the micron-size spherical material of separating.But the productive rate of MCMB low (being generally 5%～10%), leaching process is lengthy and tedious, and the size of microballoon is also wayward.Owing to have a good application prospect in a lot of fields, in recent years, the preparation of spherical carbon material causes people's attention, and some new spherical carbon material preparation methods continue to bring out, can prepare size from nano level to micron-sized spherical carbon material.At present, the compound method of spherical carbon material mainly contains chemical Vapor deposition process, solvent-thermal method and template.The key of spherical carbon material prepn is the balling-up process, and the size of control sphericity, regulation and control ball is the difficult point place.Though can prepare various types of charcoal balls with chemical Vapor deposition process, solvent-thermal method and template, control the size of charcoal ball exactly, prepare the also prematurity of technology of single dispersion, purity height and charcoal ball of uniform size.Though template is easier to obtain diameter charcoal ball relatively uniformly, the preparation process is comparatively loaded down with trivial details, and used reagent toxicity is bigger, so better charcoal ball preparation method is still waiting to find.
Pvdf (PVDF) resin is a kind of common industrial copolymer; The pvdf that adopts letex polymerization to produce has the perfect spherical outward appearance; And particle diameter is controlled, is mainly used in the sticker of coatings industry and battery industry, and domestic and international many companies are all at this product of scale operation.It is raw material that the applicant adopts pvdf, has prepared specific surface area 1000m at 500～1000 ℃ of direct high temperature carbonizations
2The porous carbon material of/g has been applied for national inventing patent (application number: 2010101403088).But because pvdf at 154～184 ℃ fusion takes place promptly, lose the primary spherical design, so what in above-mentioned patent, obtain is unbodied powdery carbon material.
Summary of the invention
The object of the present invention is to provide a kind of short-cut method for preparing the spherical porous charcoal of good sphericity, uniform particle diameter, controllable size.Be different from methods such as existing chemical Vapor deposition process, solvent-thermal method and template; Thinking of the present invention is: to have the high molecular polymer of good spherical design---the spherical polyvinylidene fluoride resin of commercialization is a raw material; At first (＜150 ℃) carry out part defluorinate stabilization treatment to it under the temperature of its fusing point being lower than; Obtain charcoal ball raw material, and then in high temperature carbonization, activation, thereby prepare spherical porous charcoal.The thermostability of the charcoal ball raw material after the part defluorinate is handled improves greatly, in high temperature carbonization, reactivation process, no longer includes melting phenomenon and takes place, so the gained porous charcoal still keeps the original good spherical design of polyvinylidene fluoride resin.
Concrete steps of the present invention are following:
1, the low temperature defluorinate stabilization treatment of spherical polyvinylidene fluoride resin
With the spherical polyvinylidene fluoride resin of commercialization is raw material, and its particle diameter adopts following two kinds of methods to carry out low temperature defluorinate stabilization treatment at 5nm～50 μ m:
(1) the direct defluorinate method of highly basic: spherical PVDF resin is added strong alkali aqueous solution; Perhaps spherical PVDF is directly mixed with the highly basic solid fines; Then at 60～150 ℃ of heating 0.5～60h; Extremely neutral with deionized water wash again, drying obtains color and is brown low temperature defluorinate stabilization product to brown.Used highly basic is one or more among KOH, NaOH, the LiOH, and the mass ratio of highly basic and spherical PVDF is 0.5～10: 1.
(2) swelling removal method: spherical PVDF resin is joined N; In the mixing solutions of dinethylformamide (DMF) and organic alcohol, magnetic agitation 0.1～10h makes the PVDF swelling, adds highly basic again; Then at 60～150 ℃ of heating 0.5～60h; Extremely neutral with deionized water wash again, drying obtains color and is brown low temperature defluorinate stabilization product to brown.Used organic alcohol is one or more in methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, the octanol, and used highly basic is 1,8-diaza-bicyclo [5,4,0]-7-undecylene (C
9H
16N
2, be called for short DBU), among the KOH, NaOH, LiOH one or more, N, the volume ratio of dinethylformamide and organic alcohol is 0.1～10: 1, the mass ratio of highly basic and spherical PVDF is 0.5～10: 1.
2, charing is handled
The ball charcoal raw material that above-mentioned low temperature defluorinate stabilization treatment is obtained carry out charing under the protection of rare gas element (nitrogen or argon gas) handles and obtains carbonized material, 300～1000 ℃ of carbonization temperatures, charing constant temperature time 0.1～10h.
3, activation treatment
Carbonized material is carried out activation treatment pore-creating, and activation treatment can adopt physical activation method or chemical activation method.
(1) physical activation method is with H
2O, CO
2, O
2, airborne one or more are acvator, and carbonizing production is fed activated gas at 400～1000 ℃, constant temperature activation 0.1～20h obtains spherical porous charcoal.
(2) chemical activation method is with H
3PO
4, ZnCl
2, KOH, NaOH, K
2CO
3, Na
2CO
3In one or more be acvator; Adopt the method for solid phase mixing or solution soaking to carry out uniform mixing carbonizing production and acvator; Under the protection of rare gas element (nitrogen or argon gas), carry out high-temperature activation then, activation temperature is 300～1000 ℃, constant temperature soak time 0.1～10h.The mass ratio of acvator and carbonizing production is 0.1～10: 1.
4, aftertreatment
The chemical activation product also need wash, drying treatment.Product to be activated takes out after being cooled to room temperature, and to neutral, 100～150 ℃ of dryings obtain spherical porous charcoal with pickling, washing.Used acid can be one or more in hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, the oxalic acid.
The preparation method that the present invention proposes has following characteristics:
1, method is simple.Spherical polyvinylidene fluoride resin with large-scale commercial applications production is a raw material, after low temperature part defluorinate stabilization treatment, presses charing, the activation production process of conventional powdered gac again, can prepare spherical porous charcoal.
2, good sphericity, uniform particle diameter.It is harsh to the preparation condition requirement usually to adopt chemical Vapor deposition process and solvent-thermal method to prepare spherical carbon, and the charcoal ball is of low quality, has amorphous carbon and mixes wherein, and sphericity is not good, and particle size distribution range is wide.Adopt the polyvinylidene fluoride resin of emulsion polymerization production to have very homogeneous of perfect spherical outward appearance, particle diameter, this technology is quite ripe.Adopt spherical polyvinylidene fluoride resin to prepare the spherical carbon material according to the present invention; Melting deformation does not at high temperature take place in it owing to passed through low temperature part defluorinate stabilization treatment; Charing, reactivation process do not destroy spherical design basically yet, so the gained porous charcoal has been inherited the characteristics of raw material polyvinylidene fluoride resin good sphericity, uniform particle diameter.
3, adjustable grain.Adopt this patent, the particle diameter regulate and control method of charcoal ball is simple, and only needing selection and the close spherical polyvinylidene fluoride resin in target charcoal spherolite footpath is that raw material can be realized.Because the particle diameter modification scope of spherical polyvinylidene fluoride resin is very big, so the particle diameter of charcoal ball can regulation and control arbitrarily in 5nm～50 mu m ranges.
The spherical porous charcoal that this method is produced can be used for the electrode materials, blood purification, support of the catalyst, water treatment, gas sweetening, solvent recuperation of electrode materials, the capacitance method demineralization plant of ultracapacitor, lithium ion battery etc.
Description of drawings
Fig. 1 be adopt in the embodiment of the invention 1 solid phase method with KOH to PVDF low temperature defluorinate stabilization after, the sem photograph of the spherical carbon material that high temperature carbonization obtains
Fig. 2 A and B are respectively PVDF toners used in the embodiment of the invention 2, and adopt KOH solution to PVDF liquid phase low temperature defluorinate stabilization, high temperature carbonization, CO
2The sem photograph of the spherical carbon material that activation obtains
Fig. 3 is after adopting DBU swelling defluorinate method with chemical liquid phase defluorinate under the PVDF low temperature in the embodiment of the invention 3, the sem photograph of the spherical carbon material that high temperature carbonization, KOH activation obtain
Fig. 4 adopts swelling defluorinate method with PVDF at low temperatures after the chemical liquid phase defluorinate in the embodiment of the invention 4, the sem photograph of the spherical carbon material that high temperature carbonization, NaOH activation prepare
Fig. 5 is after adopting KOH solution to PVDF liquid phase low temperature defluorinate stabilization in the embodiment of the invention 5, the sem photograph of the spherical carbon that high temperature carbonization, impregnation of phosphoric acid activation obtain
Fig. 6 is to be the surface sweeping Electronic Speculum figure of the spherical carbon material that obtains of raw material with the PVDF powder of 1 μ m in the embodiment of the invention 6
Embodiment
Through embodiment the present invention is further described below.
Embodiment 1
Take by weighing the commercially available PVDF white powder of 5g (particle diameter 500nm) and 35g sheet KOH solid, mix, wear into uniform fine powder, take out after placing 120 ℃ of baking ovens heating 10h, wash successively to neutrality,, be brown the product drying with Hydrogen chloride and deionized water.Product is positioned in the tube furnace, under the protection of the high purity nitrogen of 200mL/min, rises to 150 ℃, rise to 700 ℃ with 5 ℃/min again, constant temperature 2h with 10 ℃/min.After treating that furnace temperature is cooled to room temperature, take out, get black powder.ESEM (Fig. 1) is viewed as the spherical carbon material, the about 500nm of particle diameter, specific surface area 550m
2/ g.
Embodiment 2
25g KOH is dissolved in the 70mL deionized water, adds 5g PVDF white powder (particle diameter 170nm), magnetic agitation 90min is placed in 120 ℃ of baking ovens and heats 20h, takes out the back and washs successively to neutrality with Hydrogen chloride and deionized water, and product is dry, is Vandyke brown.This product is placed tube type resistance furnace central authorities, under the protection of high-purity argon gas, be warming up to 600 ℃ of constant temperature charing 2h, be warming up to 850 ℃ with 10 ℃/min again, feed 100mL/min CO with 5 ℃/min
2Gas 5h treats to take out after furnace temperature is cooled to room temperature, obtains the black product, and scanning electron microscopic observation is spherical in shape, the about 170nm of particle diameter, specific surface area 1130m
2/ g.The stereoscan photograph of PVDF white powder and gained spherical carbon is seen Fig. 2 (A) and (B) respectively.
Embodiment 3
Measure the 60mL absolute ethyl alcohol in beaker, measure 40mL N, dinethylformamide (DMF) adds in the absolute ethyl alcohol.Measure about 18mL DBU and add in the above-mentioned solution, fully stir, take by weighing 5g PVDF white powder (particle diameter 170nm) and progressively join in the above-mentioned mixing solutions, stir and make it dissolving until solution becomes clarification homogeneous.In 70 ℃ of baking ovens, place 18h.Take out, colourless with methanol wash to filtrating, in 110 ℃ of dryings, get brown powder.Be placed on tube furnace central authorities, under the protection of the high purity nitrogen of 200mL/min, rise to 700 ℃ with 5 ℃/min, constant temperature charing 2h obtains the black carbonizing production.Carbonized material is mixed by mass ratio with KOH at 1: 3, place tube furnace central authorities, under the protection of the high purity nitrogen of 250mL/min; Rise to 780 ℃ with 5 ℃/min, constant temperature activation 5h treats to take out after furnace temperature is cooled to room temperature; Use dilute phosphoric acid, deionized water wash to neutral successively, get spherical porous charcoal.ESEM (Fig. 3) is observed the about 150～180nm in charcoal spherolite footpath, and it is 2800m that nitrogen absorption records its specific surface area
2/ g.With the electrode materials of this spherical carbon material, at 6mol.L as ultracapacitor
-1Record it with the 50mA/g constant current charge-discharge in the KOH electrolytic solution and reach 380F/g, at organic electrolyte 1mol.L than electric capacity
-1Et
4NBF
4Record it with the 50mA/g constant current charge-discharge in the/PC electrolytic solution and reach 160F/g than electric capacity.
Embodiment 4
The resulting brown powder of embodiment 3 usefulness DBU defluorinates is placed tube furnace central authorities, under the protection of 200mL/min high-purity argon gas, rise to 500 ℃ with 10 ℃/min, constant temperature charing 2h obtains the black carbonizing production.Carbonized material and NaOH are pressed 1: 2 uniform mixing of mass ratio, place tube furnace central authorities, under the protection of 250mL/min high-purity argon gas; Rise to 650 ℃ with 10 ℃/min; Constant temperature activation 1h treats to take out after furnace temperature is cooled to room temperature, uses Hydrogen chloride, deionized water wash to neutral successively; Get spherical porous charcoal as shown in Figure 4, its specific surface area 2200m
2/ g.
Embodiment 5
Get embodiment 2 Vandyke brown product of gained after the KOH defluorinate and place tube furnace central authorities, under the protection of 200mL/min high pure nitrogen, rise to 500 ℃ with 10 ℃/min, constant temperature charing 2h obtains the black carbonizing production.With phosphoric acid is acvator, and the mass ratio of phosphoric acid and carbonized material is 2: 1, and carbonized material is soaked 5h in phosphoric acid solution; After 130 ℃ of dryings, change tube type resistance furnace central authorities over to, under the protection of 200mL/min high-purity argon gas, be warming up to 650 ℃ of constant temperature activation 6h, treat to take out after furnace temperature is cooled to room temperature with 10 ℃/min; Obtain the black product; The scanning electron microscopic observation (see figure 5) is spherical in shape, particle diameter 140～160nm, specific surface area 980m
2/ g.
Embodiment 6
With particle diameter is that the PVDF powder of 1 μ m is a raw material, prepares particle diameter～0.9～1.0 μ m, specific surface area 1600m according to the method for embodiment 3
2The spherical carbon of/g, ESEM is seen Fig. 6.
Claims (4)
1. spherical porous charcoal preparation methods; It is characterized in that this method is that spherical pvdf (PVDF) resin of 5nm～50 μ m is a raw material with the particle diameter; After the stabilization of low temperature defluorinate below 150 ℃; In 300～1000 ℃ of constant temperature charing 0.1～10h, activation, washing, drying obtain spherical porous raw material of wood-charcoal material; Low temperature defluorinate stabilization can adopt following two kinds of methods:
(1) the direct defluorinate method of highly basic: directly mix with the highly basic solid fines with spherical PVDF resin adding strong alkali aqueous solution or with spherical PVDF; Then at 60～150 ℃ of heating 0.5～60h; Extremely neutral with deionized water wash again, drying obtains color and is brown low temperature defluorinate stabilization product to brown; Used highly basic is one or more among KOH, NaOH, the LiOH, and the mass ratio of highly basic and spherical PVDF is 0.5～10: 1;
(2) swelling removal method: spherical PVDF resin is joined N, and in the mixing solutions of dinethylformamide (DMF) and organic alcohol, magnetic agitation 0.1～10h makes the PVDF swelling; Add highly basic again, then at 60～150 ℃ of heating 0.5～60h, extremely neutral with deionized water wash again; Drying obtains color and is brown low temperature defluorinate stabilization product to brown, and used organic alcohol is one or more in methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, the octanol; Highly basic is 1; Among 8-diaza-bicyclo [5,4,0]-7-undecylene (DBU), KOH, NaOH, the LiOH one or more; N, the volume ratio of dinethylformamide and organic alcohol is 0.1～10: 1, the mass ratio of highly basic and spherical PVDF is 0.5～10: 1.
2. a kind of spherical porous charcoal preparation methods according to claim 1 is characterized in that carbonization process carries out under the protection of inert nitrogen gas or argon gas.
3. a kind of spherical porous charcoal preparation methods according to claim 1 is characterized in that reactivation process can adopt physically activated or chemical activation:
(1) physically activated: with H
2O, CO
2, O
2, airborne one or more are acvator, and carbonizing production is fed activated gas at 400～1000 ℃, constant temperature activation 0.1～20h obtains spherical porous charcoal;
(2) chemical activation: with H
3PO
4, ZnCl
2, KOH, NaOH, K
2CO
3, Na
2CO
3In one or more be acvator; Adopt the method for solid phase mixing or solution impregnation to carry out uniform mixing carbonizing production and acvator; Under the protection of inert nitrogen gas or argon gas, be warming up to 300～1000 ℃ of constant temperature activation 0.1～10h then; To be cooled to the room temperature with pickling, washing to neutral, 100～150 ℃ of dryings obtain spherical porous charcoal, the mass ratio of acvator and carbonizing production is 0.1～10: 1; Acid is one or more in hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, the oxalic acid.
4. a kind of spherical porous charcoal preparation methods according to claim 1, the particle diameter that it is characterized in that this spherical porous charcoal are 5nm～50 μ m, specific surface area 500～3000m
2/ g.
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| CN106477574A (en) * | 2016-10-21 | 2017-03-08 | 青岛富强新材料科技有限公司 | A kind of preparation method of environment-friendly multi-stage pore structure lithium ion battery negative pole carbon material |
| CN109280209A (en) * | 2017-07-19 | 2019-01-29 | 中国科学院化学研究所 | A kind of polyalcohol stephanoporate microballoons and carbon ball prepared therefrom, blacker-than-black material and application |
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| CN108455596A (en) * | 2018-04-18 | 2018-08-28 | 合肥工业大学 | One step charring prepares the method and its application of high-specific surface area richness nitrogen multi-stage porous Carbon Materials |
| CN111217353A (en) * | 2018-11-27 | 2020-06-02 | 中国科学院大连化学物理研究所 | Preparation method of polyvinyl chloride-based carbon powder |
| CN112978706A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院大连化学物理研究所 | Method for preparing high-strength carbon pellets by taking polyvinylidene chloride as raw material |
| CN111530423A (en) * | 2020-05-15 | 2020-08-14 | 南昌大学 | Integrally-formed granular carbon adsorbent and preparation method and application thereof |
| CN114906833A (en) * | 2022-05-07 | 2022-08-16 | 武汉楚能新能源有限公司 | Negative electrode carbon material of sodium ion battery, preparation method of negative electrode carbon material and battery |
| CN114906833B (en) * | 2022-05-07 | 2023-03-10 | 武汉楚能新能源有限公司 | Negative electrode carbon material of sodium ion battery, preparation method of negative electrode carbon material and battery |
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