CN104759241B - A kind of carbon hollow microsphere preparation method with unsymmetric structure - Google Patents
A kind of carbon hollow microsphere preparation method with unsymmetric structure Download PDFInfo
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Abstract
The present invention relates to a kind of carbon hollow microsphere preparation method with unsymmetric structure, prepare including precursor pulp, prepared by presoma, three steps of carburizing sintering, collect the hollow microsphere presoma drop of drippage using phase separation principle, the solidification so that drippage drop outer surface moment is separated, it is prevented effectively from drop deformation and merges, obtain carbon hollow microsphere presoma.Presoma afterwards carries out drying at room temperature and carburizing sintering is processed, and finally gives carbon hollow microsphere.Compared with prior art, carbon hollow microsphere good sphericity, sphere size and the controlled porosity of present invention preparation, need not consume mass energy and acid-base reagent, process is simple is easily achieved mass industrialized production.
Description
Technical field
The present invention relates to a kind of method preparing carbon hollow microsphere, especially relate in a kind of carbon with unsymmetric structure
Empty method for preparing microsphere.
Background technology
Carbon hollow ball material has big specific surface area, big pore volume, chemical inertness and excellent mechanical stability, these
Special performance determines its wide application prospect in fields such as catalysis, adsorbent, electrode material, capacitor, energy storage materials.
At present, the method preparing carbon hollow ball is mainly：Template, vapour deposition process, arc discharge method etc..Template is to adopt
A kind of widely method preparing hollow carbon balls.Template can be divided into hard template method and soft template according to its material character again
Method.Template is the most widely a kind of method preparing carbon hollow ball adopting.Template can divide according to its material character again
For hard template method and soft template method.The hollow carbon sphere of hard template method preparation has size uniformity, the controlled advantage of core-shell structure.
Jang etc. [J.Jang, B.Lim, Advanced Materials, 2002,14 (19):1390-1393] it was modified using surface
SiO2 as template, divinylbenzene is carbon source, is prepared for the hollow carbon balls of size about 22nm.But, hard template method needs
Synthesize uniform mould material first, also need to afterwards remove template, not only complex operation, and in the operation of each step all
Have product loss, the yield of the target product therefore finally obtaining is very low, removes in operating process in template and easily causes
Shell wall damages, and the rigidity of the shell wall of the product therefore obtaining is very poor, or even some templates are very difficult to remove, such as Chinese patent
CN102054974 (preparation methoies of stannic oxide/carbon composite hollow balls).Chinese invention patent CN104150465A is (in preparation
The method of empty carbon ball) with oxygen-bearing organic matter, ammonium salt, water as raw material, hollow carbon balls are prepared by hydro-thermal method.Its ultimate principle is profit
The bubble being produced with ammonium salt decomposition in water-heat process in bubble surface carbonization, then passes through and takes out as soft template, oxygen-bearing organic matter
Filter, wash, be dried, obtain finished product.This inventive method has that the response time is short, technological process simple, product hollow carbon balls are water-soluble
Property good and the advantages of hollow volume accounting is big, shortcoming is that hydro-thermal reaction need to be carried out in sealed pressure vessel, leads to the method product
Measure low, high cost.Wang etc. [Z.L.Wang, J.S.Yin, Chemical physics letters, 1998,289 (1):189-
192] adopt CVD method at first, by the use of MnO2 as catalyst, synthesized in 900 1050 DEG C of pyrolysis by CH4 a diameter of
The carbon hollow ball of 800nm and hollow calabash shaped carbon structure.Because CVD synthesis carbon hollow ball is typically urged with metal-oxide
Agent, but less to the study on mechanism of catalyst, thus how to generate with a large amount of by-products, and carbon hollow ball purity is not
High.The purity of the carbon hollow ball of arc discharge method preparation is high, a kind of such as Chinese invention patent CN1454839A (arc discharge method
Method the method for preparation hollow carbon balls), but high-voltage arc reative cell increases substantially the cost of carbon hollow ball.
Content of the invention
The purpose of the present invention be exactly provide to overcome the defect that above-mentioned prior art exists a kind of technological process simple,
Without template, sphere size and hollow rate are controlled, yield is high, the peristaltic pump of low cost assists coaxial microfluidic system to prepare in carbon
Empty micro-sphere method.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of carbon hollow microsphere preparation method with unsymmetric structure, using following steps：
(1) precursor pulp configuration：Add polymer in a solvent, after being sufficiently stirred for being uniformly dissolved, the slurry obtaining is entered
Row degasification, obtains preparing the slurry of carbon hollow microsphere presoma；
(2) presoma preparation：Slurry is forced into outside coaxial microfluidic system shower nozzle through compressed gas in material liquid tank
Layer pipe forms continuous state fluid；Non-solvent passes through compressed air and peristaltic pump controls quantity delivered, by coaxial microfluidic system
Shower nozzle inner tube forms discontinuity drop makes slurry form inner surface instantaneous solidification at spray outlet, and then slurry gravity overcomes
Slurry surface tension falls in the collecting tank filling non-solvent, carries out solvent and non-solvent exchanges, and causing is separated is solidified
Carbon hollow microsphere presoma；
(3) sinter：Carbon hollow microsphere presoma is dried 24 hours under air ambient, puts into vacuum drying oven or indifferent gas
Sinter in atmosphere stove, control vacuum to be 10-1Pa～10-3Pa, 800～1500 DEG C of sintering temperature, sintering time is 2～4 hours,
Obtain carbon hollow microsphere.
Preferably, the mass ratio of the polymer described in step (1) and solvent is 10～40：90～60.
It is further preferred that polymer is any one in cellulose acetate, polysulfones, polyether sulfone or Kynoar, molten
Agent is any one in N-Methyl pyrrolidone, acetone, acetylacetone,2,4-pentanedione or dimethyl acetylamide.
The discharge pressure that slurry enters the compressed gas of coaxial microfluidic system shower nozzle outer tube is promoted to exist in step (2)
0.05～0.5MPa.
Preferably, in step (2), realize slurry and form inner surface instantaneous solidification at spray outlet in 0～35 DEG C of temperature
Room temperature environment under the conditions of carry out, temperature is higher, and surface instantaneous solidification rate is faster, control non-solvent quantity delivered compressed air
Air pressure be 0.05～0.5MPa.The rotating speed controlling the peristaltic pump of non-solvent quantity delivered is 0.1～20 rev/min, controls non-molten
Agent is smooth, and in droplet-like, drippage flows out.
It is further preferred that non-solvent is selected from one or more in deionized water, ethanol or propylene glycol.
Preferably, in collecting tank, non-solvent is room temperature, and non-solvent is slowly circulated by mechanical pump.
Preferably, the sintering temperature in step (3) is 800～1200 DEG C.
Compared with prior art, the present invention utilizes peristaltic pump to assist coaxial microfluidic system, according to non-molten liquid phase separation
Principle, prepares carbon hollow microsphere presoma under normal temperature condition, and presoma obtains unsymmetric structure porous after low temperature calcination
Carbon hollow microsphere, the method in the present invention is not related to high-temperature fusion, because the polymer precursor adopting in invention is containing benzene
The macromolecular material of ring, belongs to heat proof material, can lose hydrogen molecule with temperature rising and other is little under the conditions of no oxygen
Molecular radical, last carbonization is graphite or amorphous carbon material.The method does not need using high-temperature fusion process, without pulverizing
Grind and classification molten sintering, technological process is simple, energy consumption is low, sphere size and hollow rate are controlled.
In addition, causing inversion of phases principle to prepare carbon hollow microsphere presoma using non-solvent in the present invention, in precursor pulp
Solvent under non-solvent environment (one or more in deionized water, ethanol or propylene glycol) mutual diffusional precipitation can occur, from
And lead to the polymer in precursor pulp to define Concentraton gradient, run into polymer in the precursor pulp of non-solvent because molten
Xie Du reduces and solidifies, and the mutual the evolving path of solvent and non-solvent ultimately forms hole, and this non-solvent causes polymerization
Thing occurs the transition process of the phase from liquid phase to solid-state to make hollow microsphere in the present invention have unsymmetric structure.Unsymmetrical knot
The microsphere of structure has more rich pore-size distribution, and, from nano-pore to hundreds of micron openings, thus specific surface area is high for pore-size distribution, absorption
Ability is strong, and liquid storage capacity is big, and remains under the conditions of high temperature cabonization retain more than 40% high porosity.
Brief description
Fig. 1 assists the structural representation of microfluidic system for peristaltic pump；
Fig. 2 obtains the SEM photograph of carbon hollow microsphere precursor pulp for embodiment 1
The Raman spectrogram of the carbon hollow microsphere that Fig. 3 prepares for embodiment 1；
The SEM photograph of the carbon hollow microsphere that Fig. 4 prepares for embodiment 1；
The SEM photograph of the carbon hollow microsphere that Fig. 5 prepares for embodiment 1；
The Raman spectrogram of the carbon hollow microsphere that Fig. 6 prepares for embodiment 2；
The SEM photograph of the carbon hollow microsphere that Fig. 7 prepares for embodiment 2；
The Raman spectrogram of the carbon hollow microsphere that Fig. 8 prepares for embodiment 3；
In figure, 1- slurry tank；2- compressed nitrogen gas cylinder；3- non-solvent tank；4- peristaltic pump；5- Coaxial nozzle；6- inner tube；7-
Outer tube；8- non-solvent groove；9- mechanical pump；10- air relief valve；11- precision pressure gauge；12- screws valve；13- spinner flowmeter.
Specific embodiment
A kind of carbon hollow microsphere preparation method with unsymmetric structure, using following steps：
Step 1：The preparation of carbon hollow microsphere precursor pulp
Carbon hollow microsphere precursor pulp is formulated by solute and solvent, is initially charged polymer in solvent, is sufficiently stirred for
Slurry after being uniformly dissolved carries out degasification, finally obtains the slurry being suitable for preparing carbon hollow microsphere presoma.The polymer adding
For any one in cellulose acetate, polysulfones, polyether sulfone or Kynoar, solvent is N-Methyl pyrrolidone, acetone, second
Any one in acyl acetone or dimethyl acetylamide.The mass ratio of solute and solvent is 10～40：90～60.
Step 2：Prepared by carbon hollow microsphere presoma
Peristaltic pump shown in Fig. 1 for the carbon hollow microsphere presoma assists in coaxial microfluidic system to be prepared, and peristaltic pump assists
Microfluidic system structure is：Slurry tank 1；Compressed nitrogen gas cylinder 2；Non-solvent tank 3；Peristaltic pump 4；Coaxial nozzle 5 (includes inner tube 6；
Outer tube 7)；Non-solvent groove 8；Mechanical pump 9；Air relief valve 10；Precision pressure gauge 11；Screw valve 12；Spinner flowmeter 13, each knot
Software silica gel tube is had to connect between structure constituent element.A diameter of 0.15～the 0.8mm of Coaxial nozzle inner tube 6, Coaxial nozzle outer tube 7 is straight
Footpath is 0.7～2.0mm, and between Coaxial nozzle 5 and non-solvent groove 8, distance is 10～50mm.It is first turned on compressed nitrogen driving pressure
Force system：I.e. compressed nitrogen gas cylinder 2, air relief valve 10, precision pressure gauge 11, screw valve 12, spinner flowmeter 13 discharge pressure exists
Driving pressure in the range of 0.05～0.5MP, by adjust on non-solvent pipeline line screw valve and wriggling revolution speed (0.1～
20 revs/min) so that the smooth drippage outflow in droplet-like of the non-solvent in non-solvent tank 3.Then slurry step 1 prepared
Pour in slurry tank 1, open and valve 12 is screwed on slurry pipe route, adjust spinner flowmeter and reach in the range of 0.05～0.5MP
Driving pressure promotes slurry in slurry tank to enter Coaxial nozzle outer tube 7, finally observes that slurry is in that droplet-like is dripped.Non-
Flux bath 8 is used for solidifying ceramic hollow microspheres presoma, and slurry drips can be pulled out with screen cloth after 0.5～3 hour, room temperature
It is dried.Can adjust as needed and screw valve, spinner flowmeter and peristaltic pump realization control slurry drips speed, chi
Very little and form.
Step 3：Sintering
The carbon hollow microsphere presoma that step 2 is obtained is dried 24 hours under air ambient, puts into afterwards in vacuum drying oven
(vacuum is 10-1Pa～10-3Pa) or inert gas shielding atmosphere (nitrogen and argon) sintering, 800 DEG C of sintering temperature～
1300 DEG C, sintering time is 2-4 hour, that is, obtain ceramic hollow microspheres.
The innovation of the present invention is that to employ autonomous Design and manufacture peristaltic pump and assists coaxial microfluidic system, this
In system, the amount of feeding of slurry is by pressurized gas system (including compressed nitrogen gas cylinder 2, air relief valve 10, precision pressure gauge 11) and rotor
Effusion meter controls (screwing valve 12, spinner flowmeter 13)；The amount of feeding of non-solvent (includes compressed nitrogen gas cylinder by pressurized gas system
2nd, air relief valve 10, precision pressure gauge 11), spinner flowmeter (screwing valve 12, spinner flowmeter 13) and peristaltic pump 4 co- controlling.
Being introduced into of peristaltic pump can be realized controlling the non-solvent amount of feeding in Coaxial nozzle inner tube 6 in a microlitre magnitude, can overcome the defect that
Surface tension and the impact of gravity, realize micron order drop, and then reach slurry drop shape in control Coaxial nozzle outer tube 7
Shape, size and drippage speed.Collect the carbon hollow microsphere presoma drop of drippage using phase separation principle so that dripping
Fall the separated solidification of drop outer surface moment, is prevented effectively from drop deformation and merges, obtains carbon hollow microsphere presoma.Afterwards
Presoma carry out drying at room temperature and vacuum atmosphere or inert gas shielding atmosphere sintering and process, finally give carbon hollow micro-
Ball.Adopt this method carbon hollow microsphere good sphericity, sphere size and the controlled porosity of preparation, mass energy need not be consumed
And acid-base reagent, process is simple is easily achieved mass industrialized production.
The following is specific embodiment.
Embodiment 1
Step 1：Add 8g polyether sulfone in 90gNMP, after stirring and dissolving mix homogeneously, ageing degasification obtains slurry.
Step 2：Deionized water selected by non-solvent.From a diameter of 0.15mm of Coaxial nozzle inner tube 6, Coaxial nozzle outer layer
The Coaxial nozzle of a diameter of 0.5mm of pipe 7, sets between Coaxial nozzle 5 and non-solvent groove 8 distance as 10mm.It is first turned on compressing
Nitrogen driven pressure systems：I.e. compressed nitrogen gas cylinder 2, air relief valve 10, precision pressure gauge 11, to screw valve 12, spinner flowmeter 13 defeated
Driving pressure in 0.1MP for the pressurization pressure, by adjust non-solvent pipeline line on screw valve and (0.5 rev/min of wriggling revolution speed
Clock) so that the smooth drippage outflow in droplet-like of the non-solvent in non-solvent tank 3.Then the slurry that step 1 is prepared is poured into slurry
In tank 1, open and valve 12 is screwed on slurry pipe route, adjust spinner flowmeter and reach the driving pressure promotion slurry in the range of 0.2MP
In batch can, slurry enters Coaxial nozzle outer tube 7, finally observes that slurry is in that droplet-like is dripped.Non-solvent groove 8 is used for solid
Change carbon hollow microsphere presoma, slurry drips can pull (as shown in Figure 2), drying at room temperature out with screen cloth after 3 hours.
Step 3：The carbon hollow microsphere presoma that step 2 is obtained is dried 24 hours under air ambient, puts into true afterwards
Sinter in empty stove, vacuum is 10-3Pa, 800 DEG C of sintering temperature, and sintering time is 2 hours, that is, obtain in the high carbon of hollow rate
Empty microsphere (as shown in Figure 4).Raman atlas analysis are carried out to the carbon hollow microsphere obtaining and are shown to be amorphous phase carbon (as Fig. 3),
With SEM to carbon hollow microsphere analysis shows, spheroid is asymmetric hollow-core construction (as Fig. 5), and spheroid external diameter meansigma methodss areBody size distribution ranges are narrow, hollow rate 45～65%.
Embodiment 2
Step 1：Add 28g polyether sulfone in 60gNMP, after mixing mix homogeneously after stirring and dissolving, ageing degasification is starched
Material.
Step 2：Non-solvent selects deionized water to select a diameter of 0.5mm of Coaxial nozzle inner tube 6, Coaxial nozzle outer tube
The Coaxial nozzle of 7 a diameter of 1.2mm, sets between Coaxial nozzle 5 and non-solvent groove 8 distance as 50mm.It is first turned on compressed nitrogen
Gas driven pressure systems：I.e. compressed nitrogen gas cylinder 2, air relief valve 10, precision pressure gauge 11, screw valve 12, spinner flowmeter 13 conveys
Driving pressure in 0.1MP for the pressure, by adjust non-solvent pipeline line on screw valve and (0.5 rev/min of wriggling revolution speed
Clock) so that the smooth drippage outflow in droplet-like of the non-solvent in non-solvent tank 3.Then the slurry that step 1 is prepared is poured into slurry
In tank 1, open and valve 12 is screwed on slurry pipe route, adjust spinner flowmeter and reach the driving pressure promotion slurry in the range of 0.2MP
In batch can, slurry enters Coaxial nozzle outer tube 7, finally observes that slurry is in that droplet-like is dripped.Non-solvent groove 8 is used for solid
Change carbon hollow microsphere presoma, slurry drips can be pulled out with screen cloth after 3 hours, drying at room temperature.
Step 3：The carbon hollow microsphere presoma that step 2 is obtained is dried 24 hours under air ambient, puts into true afterwards
Sinter in empty stove, vacuum is 10-3Pa, 1500 DEG C of sintering temperature, and sintering time is 2 hours, that is, obtain degree of graphitization higher
Carbon hollow microsphere.
Raman spectrum analysis are carried out to the carbon hollow microsphere obtaining and is shown to be graphite crystalline phase (as Fig. 6), with SEM in carbon
Empty microsphere analysis shows, carbon ball is asymmetric hollow-core construction (as Fig. 7), and spheroid external diameter meansigma methodss are Hollow rate
40～50%.
Embodiment 3
Step 1：Add 30g polyether sulfone in 60gNMP, after stirring and dissolving, add 9.8g stable type zirconia ceramics powder
Body and the mixture of 0.2g ferric oxide powder, after continuing to be uniformly mixed, ageing degasification obtains slurry.
Step 2：Deionized water selected by non-solvent.From a diameter of 0.8mm of Coaxial nozzle inner tube 6, Coaxial nozzle outer layer
The Coaxial nozzle of a diameter of 3.0mm of pipe 7, sets between Coaxial nozzle 5 and non-solvent groove 8 distance as 50mm.It is first turned on compressing
Nitrogen driven pressure systems：I.e. compressed nitrogen gas cylinder 2, air relief valve 10, precision pressure gauge 11, to screw valve 12, spinner flowmeter 13 defeated
Driving pressure in 0.2MP for the pressurization pressure, by adjust non-solvent pipeline line on screw valve and (2.0 revs/min of wriggling revolution speed
Clock) so that the smooth drippage outflow in droplet-like of the non-solvent in non-solvent tank 3.Then the slurry that step 1 is prepared is poured into slurry
In tank 1, open and valve 12 is screwed on slurry pipe route, adjust spinner flowmeter and reach the driving pressure promotion slurry in the range of 0.3MP
In batch can, slurry enters Coaxial nozzle outer tube 7, finally observes that slurry is in that droplet-like is dripped.Non-solvent groove 8 is used for solid
Change carbon hollow microsphere presoma, slurry drips can be pulled out with screen cloth after 3 hours, drying at room temperature.
Step 3：The carbon hollow microsphere presoma that step 2 is obtained is dried 24 hours under air ambient, puts into true afterwards
Sinter in empty stove, vacuum is 10-3Pa, 1200 DEG C of sintering temperature, and sintering time is 2 hours, that is, obtain graphite wafer phase/nothing fixed
Shape phase carbon hollow microsphere.The carbon hollow microsphere obtaining is carried out with Raman atlas analysis it is shown to be graphite crystalline phase and amorphous carbon mixing
Synthetic phase (as Fig. 8), carbon ball is hollow-core construction, and spheroid external diameter meansigma methodss areThe average chi of crystal grain on hollow ball
Very little it isSphere size narrow distribution range, hollow rate 20～28%.
Embodiment 4
A kind of carbon hollow microsphere preparation method with unsymmetric structure, using following steps：
(1) precursor pulp configuration：Add polymer in a solvent, after being sufficiently stirred for being uniformly dissolved, the slurry obtaining is entered
Row degasification, obtains preparing the slurry of carbon hollow microsphere presoma, the mass ratio of polymer and solvent is 10：90, the polymerization of employing
Thing is cellulose acetate, and solvent is N-Methyl pyrrolidone；
(2) presoma preparation：Slurry is forced into outside coaxial microfluidic system shower nozzle through compressed gas in material liquid tank
Layer pipe forms continuous state fluid, and the discharge pressure of compressed gas is in 0.05MPa；Non-solvent deionized water pass through compressed air and
Peristaltic pump controls quantity delivered, and in 0.05MPa, the rotating speed of the peristaltic pump of control non-solvent quantity delivered is the discharge pressure of compressed gas
0.1 rev/min, forming discontinuity drop by coaxial microfluidic system shower nozzle inner tube makes in slurry formed at spray outlet
Surface instantaneous solidification, at 0 DEG C, then slurry gravity overcomes slurry surface tension to fall into fill non-solvent temperature control now
In collecting tank, carry out solvent and non-solvent exchanges, cause the carbon hollow microsphere presoma obtaining solidifying that is separated, non-in collecting tank
Solvent is room temperature, and non-solvent is slowly circulated by mechanical pump；
(3) sinter：Carbon hollow microsphere presoma is dried 24 hours under air ambient, puts into sintering in vacuum drying oven, control
Vacuum processed is 10-1Pa, 800 DEG C of sintering temperature, sintering time is 4 hours, that is, obtain carbon hollow microsphere.
Embodiment 5
A kind of carbon hollow microsphere preparation method with unsymmetric structure, using following steps：
(1) precursor pulp configuration：Add polymer in a solvent, after being sufficiently stirred for being uniformly dissolved, the slurry obtaining is entered
Row degasification, obtains preparing the slurry of carbon hollow microsphere presoma, the mass ratio of polymer and solvent is 30：70, the polymerization of employing
Thing is polysulfones, and solvent is acetone；
(2) presoma preparation：Slurry is forced into outside coaxial microfluidic system shower nozzle through compressed gas in material liquid tank
Layer pipe forms continuous state fluid, and the discharge pressure of compressed gas is in 0.1MPa；Non-solvent ethanol passes through compressed air and wriggling
Pump controls quantity delivered, the discharge pressure of compressed gas in 0.1MPa, the rotating speed that controls the peristaltic pump of non-solvent quantity delivered is 10 turns/
Minute, forming discontinuity drop by coaxial microfluidic system shower nozzle inner tube makes slurry form inner surface wink at spray outlet
Between solidify, at 10 DEG C, then slurry gravity overcomes slurry surface tension to fall into the collection filling non-solvent to temperature control now
In groove, carry out solvent and non-solvent exchanges, cause the carbon hollow microsphere presoma obtaining solidifying that is separated, non-solvent in collecting tank
For room temperature, non-solvent is slowly circulated by mechanical pump；
(3) sinter：Carbon hollow microsphere presoma is dried 24 hours under air ambient, puts into sintering in vacuum drying oven, control
Vacuum processed is 10-3Pa, 1200 DEG C of sintering temperature, sintering time is 3 hours, that is, obtain carbon hollow microsphere.
Embodiment 6
A kind of carbon hollow microsphere preparation method with unsymmetric structure, using following steps：
(1) precursor pulp configuration：Add polymer in a solvent, after being sufficiently stirred for being uniformly dissolved, the slurry obtaining is entered
Row degasification, obtains preparing the slurry of carbon hollow microsphere presoma, the mass ratio of polymer and solvent is 40：60, the polymerization of employing
Thing is Kynoar, and solvent is dimethyl acetylamide；
(2) presoma preparation：Slurry is forced into outside coaxial microfluidic system shower nozzle through compressed gas in material liquid tank
Layer pipe forms continuous state fluid, and the discharge pressure of compressed gas is in 0.5MPa；Non-solvent propylene glycol passes through compressed air and compacted
Dynamic pump controls quantity delivered, and in 0.5MPa, the rotating speed controlling the peristaltic pump of non-solvent quantity delivered is 20 to the discharge pressure of compressed gas
Rev/min, forming discontinuity drop by coaxial microfluidic system shower nozzle inner tube makes slurry form interior table at spray outlet
Face instantaneous solidification, at 35 DEG C, then slurry gravity overcomes slurry surface tension to fall into fill non-solvent temperature control now
In collecting tank, carry out solvent and non-solvent exchanges, cause the carbon hollow microsphere presoma obtaining solidifying that is separated, non-in collecting tank
Solvent is room temperature, and non-solvent is slowly circulated by mechanical pump；
(3) sinter：Carbon hollow microsphere presoma is dried 24 hours under air ambient, puts in inert atmosphere stove and burn
Knot, 1500 DEG C of sintering temperature, sintering time is 2 hours, that is, obtain carbon hollow microsphere.
Specific implementation method to the present invention and effect have carried out citing description above, but the invention is not limited in
The specific embodiment stated, above-mentioned specific embodiment is only schematically, rather than restricted, this area common
Technical staff, under the enlightenment of the present invention, in the case of without departing from present inventive concept and scope of the claimed protection, also may be used
Make a lot of forms, these belong within the protection of the present invention.
Claims (8)
1. a kind of carbon hollow microsphere preparation method with unsymmetric structure is it is characterised in that adopt following steps：
(1) precursor pulp configuration：Add polymer in a solvent, after being sufficiently stirred for being uniformly dissolved, the slurry obtaining is removed
Gas, obtains preparing the slurry of carbon hollow microsphere presoma；
(2) presoma preparation：Slurry is forced into coaxial microfluidic system shower nozzle outer tube through compressed gas in material liquid tank
Form continuous state fluid；Non-solvent passes through compressed air and peristaltic pump controls quantity delivered, by coaxial microfluidic system shower nozzle
Inner tube forms discontinuity drop makes slurry form inner surface instantaneous solidification at spray outlet, and then slurry gravity overcomes slurry
Surface tension falls in the collecting tank filling non-solvent, carries out solvent and non-solvent exchanges, cause the carbon obtaining solidifying that is separated
Hollow microsphere presoma；
(3) sinter：Carbon hollow microsphere presoma is dried 24 hours under air ambient, puts into vacuum drying oven or inert atmosphere stove
Middle sintering, 800～1500 DEG C of sintering temperature, sintering time is 2～4 hours, that is, obtain carbon hollow microsphere；
Described polymer is any one in cellulose acetate, polysulfones, polyether sulfone or Kynoar, and described solvent is
Any one in N-Methyl pyrrolidone, acetone, acetylacetone,2,4-pentanedione or dimethyl acetylamide, the non-solvent described in step (2)
In deionized water, ethanol or propylene glycol one or more.
2. a kind of carbon hollow microsphere preparation method with unsymmetric structure according to claim 1 is it is characterised in that walk
Suddenly the mass ratio of the polymer described in (1) and solvent is 10～40：90～60.
3. a kind of carbon hollow microsphere preparation method with unsymmetric structure according to claim 1 is it is characterised in that walk
Suddenly promote in (2) slurry enter the discharge pressure of compressed gas of coaxial microfluidic system shower nozzle outer tube 0.05～
0.5MPa.
4. a kind of carbon hollow microsphere preparation method with unsymmetric structure according to claim 1 is it is characterised in that walk
Suddenly when in (2), slurry forms inner surface instantaneous solidification at spray outlet, temperature control is at 0～35 DEG C.
5. a kind of carbon hollow microsphere preparation method with unsymmetric structure according to claim 1 is it is characterised in that walk
Suddenly the air pressure controlling the compressed air of non-solvent quantity delivered in (2) is 0.05～0.5MPa.
6. a kind of carbon hollow microsphere preparation method with unsymmetric structure according to claim 1 is it is characterised in that walk
Suddenly the rotating speed controlling the peristaltic pump of non-solvent quantity delivered in (2) is 0.1～20 rev/min, controls non-solvent smooth in droplet-like
Drippage flows out.
7. a kind of carbon hollow microsphere preparation method with unsymmetric structure according to claim 1 is it is characterised in that receive
, as room temperature, non-solvent is slowly circulated by mechanical pump to integrate non-solvent in groove.
8. a kind of carbon hollow microsphere preparation method with unsymmetric structure according to claim 1 is it is characterised in that walk
Suddenly the sintering temperature in (3) is 800～1200 DEG C.
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| CN107353429B (en) * | 2017-07-21 | 2020-03-24 | 中国工程物理研究院激光聚变研究中心 | Method for preparing polymer hollow microspheres by using three-dimensional random flow field |
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| CN102898134A (en) * | 2012-09-28 | 2013-01-30 | 清华大学 | Method for preparing zirconium dioxide ceramic microspheres with microfluid device |
| CN104150465A (en) * | 2014-08-11 | 2014-11-19 | 常州大学 | Method for preparing hollow carbon ball |
| CN104387061A (en) * | 2014-11-06 | 2015-03-04 | 上海交通大学 | Method for preparing ceramic hollow microspheres by using peristaltic pump assisted coaxial micro-fluidic system |
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| KR101087260B1 (en) * | 2009-06-23 | 2011-11-29 | 한국외국어대학교 연구산학협력단 | Hollow mesoporous silica capsule and method for preparing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102898134A (en) * | 2012-09-28 | 2013-01-30 | 清华大学 | Method for preparing zirconium dioxide ceramic microspheres with microfluid device |
| CN104150465A (en) * | 2014-08-11 | 2014-11-19 | 常州大学 | Method for preparing hollow carbon ball |
| CN104387061A (en) * | 2014-11-06 | 2015-03-04 | 上海交通大学 | Method for preparing ceramic hollow microspheres by using peristaltic pump assisted coaxial micro-fluidic system |
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