CN110330016A - An a kind of step cooperative development method of anthracite-base porous carbon graphite microcrystal and hole - Google Patents

An a kind of step cooperative development method of anthracite-base porous carbon graphite microcrystal and hole Download PDF

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CN110330016A
CN110330016A CN201910736936.3A CN201910736936A CN110330016A CN 110330016 A CN110330016 A CN 110330016A CN 201910736936 A CN201910736936 A CN 201910736936A CN 110330016 A CN110330016 A CN 110330016A
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porous carbon
anthracite
hole
development method
graphite microcrystal
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孙飞
吴东阳
裴桐
王坤芳
高继慧
赵广播
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Harbin Institute of Technology
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Harbin Institute of Technology
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/30Active carbon
    • C01B32/312Preparation
    • C01B32/318Preparation characterised by the starting materials
    • C01B32/33Preparation characterised by the starting materials from distillation residues of coal or petroleum; from petroleum acid sludge
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/30Active carbon
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Abstract

An a kind of step cooperative development method of anthracite-base porous carbon graphite microcrystal and hole, belongs to porous carbon materials preparation technical field.The present invention realizes the porous carbon preparation for having both flourishing hole and microstructure using chemical activation processes for the contradiction of Pore development and high-quality microcrystalline structure in porous carbon preparation process.Specially it is sufficiently mixed by potassium base activator with coal dust for raw material with high-order coal (anthracite), prepares anthracite-base porous carbon materials by a step chemical activation and subsequent cleaning-drying process.By change temperature can coordinated regulation porous carbon hole combo and microstructure, and then obtain hole prosperity and the high porous carbon materials of graphite microcrystal content.Gained anthracite-base porous carbon specific surface area is up to 3214.5m2/ g, total pore volume is up to 1.83cm3/ g, and the graphite microcrystalline structure with high quality.The present invention (such as has broad application prospects in energy storage technology in terms of supercapacitor.

Description

An a kind of step cooperative development method of anthracite-base porous carbon graphite microcrystal and hole
Technical field
The invention belongs to porous carbon materials preparation technical fields, and in particular to a kind of anthracite-base porous carbon graphite microcrystal and One step cooperative development method of hole.
Background technique
Super capacitor realizes charge and discharge process to the Electrochemical adsorption of ion and desorption based on electrode material, this mistake Journey is not related to chemically reacting, and has many advantages, such as that charge/discharge speed is fast, has extended cycle life, is a kind of ideal energy-storage travelling wave tube.Electrode Material is the key component for influencing super capacitor system energy-storage property, and the electrode material for how preparing high activity and high stability is The important development direction of super capacitor at present.Porous carbon materials belong to nano material scope, are one kind by being mutually communicated or closing Hole constitute network structure material, have hole and structure controllability.It is special by the distribution of pores for regulating and controlling porous material Sign makes it have high-specific surface area and Kong Rong, can expand ion diffusion admittance;The microstructure of controlled material fills it simultaneously Distribution exhibition also can be improved the electric conductivity and steady chemical structure of material.Graphite microcrystal and Pore development based on porous carbon Structure-activity relationship between application performance, constructing the porous carbon with high-specific surface area, high quality graphite microcrystal is to prepare high property The important goal of energy electrode function material.
Low cost preparation method and predecessor (carbon-based material) selection be determine porous carbon materials form, property and The key of its application performance.Based on prior art means, generally pass through template, physical activation method and chemical activation method in the world Prepare porous carbon.Template removes mould using in the hole that porous carbon matrix precursor is deposited to template or by the way of surface after deposition Plate obtains and the consistent porous nanometer material of the morphology and size of template.But the method requires carbon-based material to have good stream Dynamic property, just can uniformly mix with template.The preprocessing process that solid precursors are then needed to carry out it with complex process, at This is higher, and lacks the regulating and controlling effect to microstructure during template prepares porous carbon, and the microstructure of carbon is usual It is difficult to attain full development.Physically activated process is mainly shown as weak oxide gas (such as carbon dioxide, vapor) to carbon The oxide etch of sill acts on, and process is by various influences such as gas absorption, oxide etch and product diffusion rates. Through physically activated obtained porous carbon materials based on micropore, pore-size distribution is relatively narrow.Chemical activation is to pass through chemical reagent With the chemical reaction of predecessor, the development of hole is realized.Compared to physically activated, chemical activation show as higher carbon yield and Specific surface area.General chemical activating agent (such as Bronsted acid) activating mechanism is chiefly to facilitate urging for coal sill hydrogen-oxygen functional group Change dehydration, poration process is comparatively mild, cannot achieve flourishing hole.
Biomass and coal can be used as predecessor system containing higher carbon density as natural solid carbon resource treasure-house Standby porous carbon materials.However the carbon material of different structure internal void, surface chemical property and in terms of also have Biggish difference.Carbon structure includes a large amount of oxygen-containing groups (hydroxyl, carboxyl, carbonyl, ehter bond etc.), longer fat in biomass Side chain, heterocycle are cross-linked with each other (partly) cellulose or lignin structure to be formed, and fragrant extent of polymerization is lower.Because of biomass sources Diversity, microstructure show such as spherical shape, threadiness, sheet, tubulose and rodlike a variety of irregular structures.By right Biomass carbon source is activated, and is removed the organic and volatile components being rich in carbon source, is obtained with certain pore size structure Carbon material.However a degree of pyrolysis and polycondensation reaction has occurred in inside configuration during preparing flourishing hole, produces Raw a large amount of unpaired electrons form the miscellaneous member rings such as five yuan, seven yuan, cause frame sheet that a degree of torsional deformation occurs, into And cause the structural stability of biomass-based porous carbon poor, it is unable to satisfy wanting for the high stability of electrode material for super capacitor It asks.
Summary of the invention
The purpose of the present invention is to solve in traditional porous carbon preparation method for material, flourishing pore structure with it is high-quality The graphite microcrystalline structure of amount is often difficult to satisfactory to both parties, to keep the application field of porous carbon limited problem, and it is more to provide a kind of anthracite-base One step cooperative development method of hole carbon graphite crystallite and hole, this kind of method is based on more smokeless of starting graphite content of crystallite Coal makes the one step cooperative development of crystallite and hole.
To achieve the above object, the technical solution adopted by the present invention is as follows:
An a kind of step cooperative development method of anthracite-base porous carbon graphite microcrystal and hole, the method is according to the following steps It carries out:
Step 1: raw material refinement: being successively crushed coal raw material, ground and sieved, obtains refinement coal dust;The refinement The partial size of coal dust is 60 mesh~100 mesh;
Step 2: chemical activating agent is mixed with raw material: the refinement coal dust and chemical activating agent that step 1 is obtained are sufficiently mixed It closes uniformly, obtains mixture;
Step 3: high-temperature activation: the mixture that step 2 is obtained is transferred in crucible, is placed in atmosphere furnace, temperature liter Up to 600 DEG C~1000 DEG C and 0.5h~10h is kept the temperature, atmosphere furnace is then naturally cooling to room temperature, the mixing after being activated Solid matter;
Step 4: the cleaning and drying of activation products: the hybrid solid substance that step 3 obtains successively is carried out at pickling Reason 2~5 times and washing process 2~5 times, until supernatant is in neutrality, the solid matter after cleaning is dried, porous carbon is obtained Material.
The present invention having the beneficial effect that compared with the existing technology
(1) present invention uses the maximum anthracite of degree of coalification for porous carbon matrix precursor, and carbon source is from a wealth of sources, is derived from certainly So, and low in cost, fixed carbon content is higher, and impurity content is few, does not need additional pretreatment (as being carbonized) process, effectively benefit With the natural structure of high-order coal sill, so that it may obtain the higher predecessor of content of crystallite, be the graphite microcrystalline structure of porous carbon Depth regulation provides platform, is suitable for volume production.
(2) compared to template for predecessor be in flowable state requirement, the present invention by the way of a step chemical activation, The complicated technique such as melting is not needed, does not need additionally to add catalyst yet, mixed, heat together and washed with predecessor by activator Wash process, using between activator and solid-state material diffusion and corrasion pore-creating can be realized, it is easy to operate, eliminate cumbersome Complicated process route;
(3) present invention uses potassium base activator (such as potassium hydroxide, potassium carbonate, saleratus, potassium ferrate), by one It walks chemical activation method and realizes crystallite and hole cooperative development.The intermediate product of the method activation process compared with other activation methods (such as potassium) can catalysis material graphitization process, while pore-creating, the graphite microcrystalline structure of porous carbon is also synchronized collaboration Development.3214.5m is up to by porous carbon specific surface area prepared by the method2/ g, total pore volume 1.83cm3/ g, and have good Graphite microcrystalline structure.In the application of the symmetrical supercapacitor of organic electrolysis plastidome, 1Ag-1When specific capacitance be up to 170.8F g-1, conductivity influenced by activation condition (such as temperature) up to 8 times or more of commercial activated carbons, is expected to reach more High index.
In conclusion the present invention is suitable for regulation porous carbon graphite microcrystal and one step cooperative development of hole.Based on anthracite Using potassium base activator, a step is activated at high temperature, and it is more that available graphite microcrystal quality is higher, pore structure is more flourishing Hole carbon material, this material (have broad application prospects in technical field of energy storage in terms of such as super capacitor.
Detailed description of the invention
Fig. 1 is the TEM figure for the 100nm coal base porous carbon materials that embodiment 1 is prepared;
Fig. 2 is the TEM figure for the 5nm coal base porous carbon materials that embodiment 1 is prepared;
Fig. 3 is the uv raman spectroscopy figure for the coal base porous carbon materials that embodiment 1 is prepared;
Fig. 4 is the Nitrogen adsorption isotherm figure for the coal base porous carbon materials that embodiment 1 is prepared;
Fig. 5 is the constant current charge-discharge curve graph that the coal base porous carbon materials that embodiment 1 is prepared are electrode;
Fig. 6 is the TEM figure for the 100nm coal base porous carbon materials that embodiment 2 is prepared;
Fig. 7 is the TEM figure for the 5nm coal base porous carbon materials that embodiment 2 is prepared;
Fig. 8 is the Nitrogen adsorption isotherm figure for the coal base porous carbon materials that embodiment 2 is prepared;
Fig. 9 is the TEM figure for the 100nm coal base porous carbon materials that embodiment 3 is prepared;
Figure 10 is the TEM figure for the 5nm coal base porous carbon materials that embodiment 3 is prepared;
Figure 11 is the uv raman spectroscopy figure for the coal base porous carbon materials that embodiment 3 is prepared;
Figure 12 is the Nitrogen adsorption isotherm figure for the coal base porous carbon materials that embodiment 3 is prepared;
Figure 13 is the constant current charge-discharge curve graph that the coal base porous carbon materials that embodiment 3 is prepared are electrode;
Figure 14 is that the sweep speed that the coal base porous carbon materials that embodiment 1 and embodiment 3 are prepared are electrode is 50mV s-1Cyclic voltamogram contrast curve chart;
Figure 15 is that the sweep speed that the coal base porous carbon materials that embodiment 1 and embodiment 3 are prepared are electrode is 500mV s-1Cyclic voltamogram contrast curve chart.
Specific embodiment
Further description of the technical solution of the present invention with reference to the accompanying drawings and examples, and however, it is not limited to this, All to be modified to technical solution of the present invention or equivalent replacement, range without departing from the spirit of the technical scheme of the invention should all Cover within the protection scope of the present invention.
The present invention is based on the analyses to activation method and porous carbon matrix precursor structure to pass through one using anthracite as carbon source Chemical activation method preparation is walked containing a large amount of porous carbon materials for stablizing graphite microcrystalline structure and hole prosperity, realizes graphite microcrystal With a step cooperative development of hole, specific manifestation are as follows: with anthracite for porous carbon matrix precursor, using potassium base chemical activating agent with before Driving object, heat together is handled at high temperature, when being handled using anthracite itself more regular graphite microcrystalline structure and high-temperature activation Activator poration process provides the chance of self assembly again for crystallite tile structure, can get the graphite microcrystal and hair of high quality The porous carbon materials of the one step cooperative development of hole reached.
For coal as the most important non-renewable energy in China, rich reserves are low in cost, are the large-scale production of porous carbon Necessary condition is provided.Compared with biomass, the microstructure of coal is comparatively dense, is that plant is poly- by dehydrogenation, deoxidation, aromatization Close the orderly macromolecular structure formed.Because being influenced by factors such as Coal-forming Plants, age, conditions, the coal of different degrees of coalification Its organic molecule of charcoal is constituted and crosslinking method also has larger difference.With the intensification of degree of coalification, fatty carbon chain length in coal Shorten, aromatic side chain structure gradually decreases, and fragrant fragment increases graphite flake layer diameter by intermolecular self assembly effect, stone Mo Huadu is promoted.Fixed carbon, the difference of volatile matter content and inherent ash and heteroatomic content in different rank, for coal Porous carbon is prepared for carbon material predecessor and more possibility are brought to the coordinated regulation of its crystallite and Pore development.In coal sp3Carbon is the main connection structure of graphite microcrystal, and is easier the structure reacted with activator.By carrying out chemistry to coal Activation makes activator etching carbon structure form dangling bond, sp3Carbon content is reduced.Continuity and pore structure with poration process Development, the three-dimensional mobile space of graphite microcrystal are no longer influenced by the limitation of bridged bond connection, mention for reconfiguring for microstructure fragment For opportunity, the further regulation to microstructure can be realized while pore-creating.
Anthracite is as high-order coal, and phosphorus content is up to 90% or more, and fatty carbon content is few, and aromatization is more abundant.Smokelessly Graphite microcrystal content is high in coal, and crystal structure arrangement is more regular, while crystallite scale is bigger, stable structure with higher Property.Using anthracite as porous carbon matrix precursor, the comparatively dense orderly high quality graphite microcrystalline structure contained based on itself, Through overactivation poration process, it can be achieved that a step depth cooperative development of hole and graphite microcrystal.
Specific embodiment 1: what present embodiment recorded is the one of a kind of anthracite-base porous carbon graphite microcrystal and hole Cooperative development method is walked, the method sequentially includes the following steps:
Step 1: raw material refinement: being successively crushed coal raw material, ground and sieved, obtains refinement coal dust;The refinement The partial size of coal dust is 60 mesh~100 mesh;
Step 2: chemical activating agent is mixed with raw material: the refinement coal dust and chemical activating agent that step 1 is obtained are sufficiently mixed It closes uniformly, obtains mixture;
Step 3: high-temperature activation: the mixture that step 2 is obtained is transferred in crucible, is placed in atmosphere furnace, temperature liter Up to 600 DEG C~1000 DEG C and 0.5h~10h is kept the temperature, atmosphere furnace is then naturally cooling to room temperature, the mixing after being activated Solid matter;
Step 4: the cleaning and drying of activation products: the hybrid solid substance that step 3 obtains successively is carried out at pickling Reason 2~5 times and washing process 2~5 times, until supernatant is in neutrality, the solid matter after cleaning is dried, porous carbon is obtained Material.
Specific embodiment 2: a kind of anthracite-base porous carbon graphite microcrystal and hole described in specific embodiment one One step cooperative development method, in step 1, the coal raw material is without any pretreated anthracite, Industrial Analysis (quality Score) it be moisture content is 0~10%, content of ashes is 0~20%, and volatile matter content is 0~10%, and fixed carbon content is 70%~99%;It is 90%~99% that elemental analysis (mass fraction), which is carbon element content, and protium content is 0%~10%, Oxygen element content is 0%~10%.The raw material is the mixture of a kind of coal or a variety of coals in any proportion in above range.
Specific embodiment 3: a kind of anthracite-base porous carbon graphite microcrystal and hole described in specific embodiment one One step cooperative development method, in step 2, the chemical activating agent is potassium base activator, and the potassium base activator is hydroxide One of potassium, potassium carbonate, saleratus and potassium ferrate or a variety of mixtures combined in any proportion.Potassium base activator (such as potassium hydroxide, potassium ferrate) is to realize pore-creating by the oxidation under its strong corrosive and high temperature.It activates simultaneously The intermediate product (such as potassium simple substance) of agent can be catalyzed the graphitization process of carbon material, and potassium simple substance is made by intercalation in activation process With graphite microcrystal interlayer is entered, hole increasing specific surface area is further generated.
Specific embodiment 4: a kind of anthracite-base porous carbon graphite microcrystal and hole described in specific embodiment one One step cooperative development method, in step 2, the mass ratio of the refinement coal dust and chemical activating agent is 1:0.1~10.
Specific embodiment 5: a kind of anthracite-base porous carbon graphite microcrystal and hole described in specific embodiment one One step cooperative development method, in step 2, the mixed mode is that ball milling mixing or liquid phase mix.
Specific embodiment 6: a kind of anthracite-base porous carbon graphite microcrystal and hole described in specific embodiment one One step cooperative development method, in step 3, the atmosphere of the atmosphere furnace is high pure nitrogen or high-purity argon gas, the volume of the atmosphere Flow is 50mL/min~500mL/min.
Specific embodiment 7: a kind of anthracite-base porous carbon graphite microcrystal and hole described in specific embodiment one One step cooperative development method, in step 3, the heating rate of the atmosphere furnace is 0.1 DEG C/min~20 DEG C/min.
Specific embodiment 8: a kind of anthracite-base porous carbon graphite microcrystal and hole described in specific embodiment one One step cooperative development method, in step 4, the pickling solution that whens pickling processes uses for dilute hydrochloric acid, dust technology or spirit of vinegar, The concentration of the pickling solution is 0.01mol/L~10mol/L.
Specific embodiment 9: a kind of anthracite-base porous carbon graphite microcrystal and hole described in specific embodiment one One step cooperative development method, in step 4, the cleaning way is to be filtered by vacuum or realize separation of solid and liquid by centrifuge, repeatedly Cleaning until the pH of supernatant close to 7.
Specific embodiment 10: a kind of anthracite-base porous carbon graphite microcrystal and hole described in specific embodiment one One step cooperative development method, in step 4, the drying mode is vacuum drying, heated-air drying or natural evaporation drying mode.
Specific embodiment 11: a kind of anthracite-base porous carbon graphite microcrystal and hole described in specific embodiment one A step cooperative development method, in step 4, the drying temperature is 60~160 DEG C, and drying time is 6~for 24 hours.
Embodiment 1:
An a kind of step cooperative development method of anthracite-base porous carbon graphite microcrystal and hole, sequentially includes the following steps:
One, raw material refines: taking 3g anthracite to be successively crushed, ground and sieved, obtains refinement coal dust.The refinement coal The partial size of powder is 60 mesh~100 mesh.
Two, activator is mixed with raw material: after activation of potassium hydroxide agent is dissolved in 150ml deionized water, refinement coal dust being added Enter into activator solution, the mixture of activator and raw material is obtained with liquid phase hybrid mode, is evaporated after stirring, dipping are uniform. The refinement coal dust and the mass ratio of activation of potassium hydroxide agent are 1:4, i.e. 3g coal dust corresponds to 12g potassium hydroxide;The side of being evaporated Formula is electric hot plate heating;The evaporated temperature is 85~100 DEG C, and being evaporated the time is 12h.
Three, high-temperature activation: the mixture after above-mentioned impregnation drying being transferred in crucible, is placed in atmosphere furnace, activation temperature Degree is 1000 DEG C and keeps the temperature 1h, atmosphere furnace is naturally cooling to room temperature after heat preservation, the hybrid solid substance after being activated. The crucible is nickel crucible, and the atmosphere furnace is horizontal pipe furnace;The atmosphere of the atmosphere furnace is high pure nitrogen, the atmosphere Volume flow is 200mL/min;The heating rate of the atmosphere furnace is 5 DEG C/min.
Four, the cleaning and drying of activation products: the activation products of step 3 are carried out pickling processes 3 times, and are washed to The neutral liquid that clear liquid is 7 in pH.Solid matter after cleaning is dried, coal Quito hole active carbon material is obtained. The pickling solution used when the pickling processes is dilute hydrochloric acid, concentration 2mol/L.The drying mode is heated-air drying, described dry The temperature of dry processing is 80 DEG C, time 12h.
For the crystallite and hole cooperative development effect for testing the material, TEM characterization, ultraviolet Raman point have been carried out respectively to it Analysis and N2 adsorption detection.Fig. 1 and Fig. 2 is the TEM figure for the anthracite-base porous carbon materials that embodiment 1 is prepared, can from Fig. 1 Find out that gauze-like structure is presented in anthracite after activation of potassium hydroxide at 1000 DEG C, occurs in Fig. 2 by being orientated similar graphite microcrystal The apparent graphite striped constituted, graphite microcrystal is more and order is fine.Fig. 3 is the anthracite-base that embodiment 1 is prepared The ultraviolet Raman map of porous carbon can be seen that sp in figure3The carbon structure (σ key) of hydridization is in~1100cm-1Excitation signal it is weaker, Illustrate sp3Carbon is less.In addition, representing the peak the D (~1350cm of graphite lattice defect sturcture-1) intensity is very low, and represent sp2Key The peak G (~1580cm-1) intensity is very high.It is computed the relative intensity (I at the peak D Yu the peak GD/IG=0.208) ratio is lower, shows this The porous carbon materials degree of graphitization of method preparation is higher, has good graphite microcrystal quality, consistent with Fig. 1 conclusion.Fig. 4 is real The nitrogen absorption under low temperature thermoisopleth for the anthracite-base porous active carbon material that example 1 obtains is applied, typical I is presented in this adsorption isothermal curve The curve form that type-IV type combines, and be that the section 0.5~0.6MPa hysteresis loop occurs in relative pressure, show exist in hole Micropore and middle macroporous structure.By calculating it is found that the specific surface area of porous active carbon material is 3214.5m2/ g, total pore volume are 1.83cm3/ g, Micropore volume accounting are 89.6%, and pore structure is flourishing.By being analyzed above it is found that this material has both high quality Crystallite and flourishing pore structure.
Further using this material as the electrode material of supercapacitor, the material is detected in the application of technical field of energy storage Performance.Specific assembling and detection method are as follows: by this porous carbon materials, conductive black, polytetrafluoroethylene (PTFE) (PTFE) according to quality Mixing more uniform than 8:1:1 rolls film forming, drying and is coated in carbon-coated aluminum foils, later using 2032 type button shells in gloves Assembled in case, positive and negative electrode uses identical electrode material, use glass fibre as diaphragm, TEABF4/AN for Electrolyte is assembled into the symmetrical super capacitor of organic system.In constant current charge-discharge test, organic symmetrical system voltage window is 0~2.5V, current density are set as 0.5A g-1、1A g-1、2A g-1、5A g-1、10A g-1;In Cyclic voltamogram test, Voltage window is same as described above, and setting sweep speed is respectively 50mV s-1With 500mV s-1.Fig. 5 is the perseverance of the supercapacitor Current charging and discharging curve, it can thus be appreciated that porous carbon materials of the anthracite after activation of potassium hydroxide at 1000 DEG C, show very well Capacitive property.It is computed, current density 1Ag-1Shi Zhiliang specific capacitance is 170.8F g-1, and almost without pressure drop.The material Material not only shows higher quality specific capacitance, is still able to achieve higher capacity at higher current densities, has good multiplying power Performance.The graphite microcrystal for the big pi bond of conjugation for including in carbon structure provides good condition, flourishing hole for the transmitting of electronics Also place and space are provided for the transport of electronics.The cooperative development of graphite microcrystal and hole inherently makes the super capacitor of material Performance is not fully exerted.The Cyclic voltamogram curve of the embodiment will be subsequent to be compared and analyzed with embodiment 3.
Embodiment 2:
An a kind of step cooperative development method of anthracite-base porous carbon graphite microcrystal and hole, sequentially includes the following steps:
One, raw material refines: taking 3g anthracite to be successively crushed, ground and sieved, obtains refinement coal dust.The refinement coal The partial size of powder is 60 mesh~100 mesh.
Two, activator is mixed with raw material: after activation of potassium hydroxide agent is dissolved in 150ml deionized water, refinement coal dust being added Enter into activator solution, the mixture of activator and raw material is obtained with liquid phase hybrid mode, is evaporated after stirring, dipping are uniform. The refinement coal dust and the mass ratio of activation of potassium hydroxide agent are 1:4, i.e. 3g coal dust corresponds to 12g potassium hydroxide;The side of being evaporated Formula is electric hot plate heating;The evaporated temperature is 85~100 DEG C, and being evaporated the time is 12h.
Three, high-temperature activation: the mixture after above-mentioned impregnation drying being transferred in crucible, is placed in atmosphere furnace, activation temperature Degree is 800 DEG C and keeps the temperature 1h, atmosphere furnace is naturally cooling to room temperature after heat preservation, the hybrid solid substance after being activated. The crucible is nickel crucible, and the atmosphere furnace is horizontal pipe furnace;The atmosphere of the atmosphere furnace is high pure nitrogen, the atmosphere Volume flow is 200mL/min;The heating rate of the atmosphere furnace is 5 DEG C/min.
Four, the cleaning and drying of activation products: the activation products of step 3 are carried out pickling processes 3 times, and are washed to The neutral liquid that clear liquid is 7 in pH.Solid matter after cleaning is dried, coal Quito hole active carbon material is obtained. The pickling solution used when the pickling processes is dilute hydrochloric acid, concentration 2mol/L.The drying mode is heated-air drying, described dry The temperature of dry processing is 80 DEG C, time 12h.
Fig. 6 and Fig. 7 is the TEM figure for the anthracite-base porous carbon materials that embodiment 2 is prepared, compared with Fig. 1 and Fig. 2, The form of anthracite-base porous carbon at 800 DEG C after activation of potassium hydroxide is thicker, and crystallite dimension slightly reduces;Fig. 8 is real The nitrogen absorption under low temperature thermoisopleth for the anthracite-base porous carbon materials that example 2 obtains is applied, similar I type-IV is presented in this adsorption isothermal curve Type combine curve form, be by the specific surface area that Fig. 8 curve can calculate the porous active carbon material that embodiment 2 obtains 3047.5m2/ g, total pore volume 1.67cm3/ g, Micropore volume accounting are 88.6%.The anthracite-base prepared by this embodiment method Graphite microcrystal and hole in porous carbon materials still have better quality.
Embodiment 3:
An a kind of step cooperative development method of anthracite-base porous carbon graphite microcrystal and hole, sequentially includes the following steps:
One, raw material refines: taking 3g anthracite to be successively crushed, ground and sieved, obtains refinement coal dust.The refinement coal The partial size of powder is 60 mesh~100 mesh.
Two, activator is mixed with raw material: after activation of potassium hydroxide agent is dissolved in 150ml deionized water, refinement coal dust being added Enter into activator solution, the mixture of activator and raw material is obtained with liquid phase hybrid mode, is evaporated after stirring, dipping are uniform. The refinement coal dust and the mass ratio of activation of potassium hydroxide agent are 1:4, i.e. 3g coal dust corresponds to 12g potassium hydroxide;The side of being evaporated Formula is electric hot plate heating;The evaporated temperature is 85~100 DEG C, and being evaporated the time is 12h.
Three, high-temperature activation: the mixture after above-mentioned impregnation drying being transferred in crucible, is placed in atmosphere furnace, activation temperature Degree is 600 DEG C and keeps the temperature 1h, atmosphere furnace is naturally cooling to room temperature after heat preservation, the hybrid solid substance after being activated. The crucible is nickel crucible, and the atmosphere furnace is horizontal pipe furnace;The atmosphere of the atmosphere furnace is high pure nitrogen, the atmosphere Volume flow is 200mL/min;The heating rate of the atmosphere furnace is 5 DEG C/min.
Four, the cleaning and drying of activation products: the activation products of step 3 are carried out pickling processes 3 times, and are washed to The neutral liquid that clear liquid is 7 in pH.Solid matter after cleaning is dried, coal Quito hole active carbon material is obtained. The pickling solution used when the pickling processes is dilute hydrochloric acid, concentration 2mol/L.The drying mode is heated-air drying, described dry The temperature of dry processing is 80 DEG C, and the time of drying process is 12h.
Fig. 9 and Figure 10 is the TEM figure for the anthracite-base porous carbon materials that embodiment 3 is prepared, it can be seen that at 600 DEG C Anthracite-base porous carbon illustrates the nothing under lower activation temperature there is also certain graphite microcrystalline structure after activation of potassium hydroxide Its graphite microcrystalline structure of bituminous coal base porous carbon can also be developed, but crystallite dimension is smaller;Figure 11 is that embodiment 3 is prepared Anthracite-base porous carbon ultraviolet Raman map, it can be seen that with anthracite through 1000 DEG C activate sample compared with, through 600 Porous carbon its D peak stretching of DEG C activation is wider, illustrates sp3The carbon structure (σ key) of hydridization is in~1100cm-1There are stronger excitations Signal.It is computed rear ID/IG=0.521 explanation activates at a lower temperature still can get the structure with certain crystallite ordered state, But compared with activating under high temperature, graphite microcrystal content is slightly reduced.Figure 12 is the anthracite-base porous carbon that embodiment 3 is prepared The nitrogen absorption under low temperature thermoisopleth of material, adsorption isothermal curve are presented typical I type feature, can calculate reality by Figure 12 curve The specific surface area for applying 3 carbon material of example is 1964.5m2/ g, total pore volume 1.08cm3/ g, Micropore volume accounting are 88.9%, these Statistics indicate that being acted on by potassium hydroxide the pore-creating of anthracite at a lower temperature, can still successfully obtain containing large number of orifices The porous carbon materials of gap.The porous carbon of the method preparation known to analyzing above can realize graphite microcrystal and one step of hole collaboration hair Exhibition.
The test of super capacitor performance, Integration Assembly And Checkout method and reality further are carried out to porous carbon prepared by embodiment 3 It is identical to apply example 1.Figure 13 is the constant current charge-discharge curve that the coal base porous carbon materials that embodiment 3 is prepared are electrode, from figure In can be seen that the porous carbon prepared at a temperature of this still be able to maintain more symmetrical charging and discharging curve, compared with Example 1 slightly Pressure drop.It follows that its electric conductivity of the porous carbon materials of the higher preparation of temperature is better.Figure 14 and Figure 15 is for embodiment 1 and in fact The Cyclic voltamogram correlation curve that the anthracite-base porous carbon materials that example 3 is prepared are electrode is applied, sweep speed is respectively 50mV s-1With 500mV s-1.It can thus be seen that the porous carbon materials prepared under two kinds of embodiments are bent as the C-V characteristic of electrode More regular rectangle is presented in line, shows the performance with supercapacitor.The volt-ampere of the porous carbon prepared at 600 DEG C recycles Curve shows certain redox peaks under low potential, this may be that in charge and discharge process faraday to have occurred anti-for material It answers, the porous carbon prepared at 1000 DEG C is in 50mV s-1With 500mV s-1Without apparent polarization phenomena, still it is able to maintain preferable Rectangular shape illustrates that the graphite microcrystal development of material is abundant, and high rate performance is good.
By analyzing above it is found that using anthracite as porous carbon matrix precursor, can not only be manufactured after activation of potassium hydroxide Sensible pore structure is enriched, high-specific surface area is realized, can also realize the abundant development of graphite microcrystal in carbon material, very big journey Degree improves the electric conductivity of carbon material.When being applied to super capacitor as electrode material, capacity with higher, while high rate performance It is excellent.This method successfully realizes the one step cooperative development of porous carbon crystallite and hole.

Claims (11)

1. an a kind of step cooperative development method of anthracite-base porous carbon graphite microcrystal and hole, it is characterised in that: the method It sequentially includes the following steps:
Step 1: raw material refinement: being successively crushed coal raw material, ground and sieved, obtains refinement coal dust;The refinement coal dust Partial size be 60 mesh~100 mesh;
Step 2: chemical activating agent is mixed with raw material: refinement coal dust and chemical activating agent that step 1 obtains are sufficiently mixed It is even, obtain mixture;
Step 3: high-temperature activation: the mixture that step 2 is obtained is transferred in crucible, is placed in atmosphere furnace, and temperature is increased to 600 DEG C~1000 DEG C and 0.5h~10h is kept the temperature, atmosphere furnace is then naturally cooling to room temperature, the hybrid solid after being activated Substance;
Step 4: the cleaning and drying of activation products: by the hybrid solid substance that step 3 obtains successively carry out pickling processes 2~ 5 times and washing process 2~5 times, until supernatant is in neutrality, the solid matter after cleaning is dried, porous carbon materials are obtained.
2. a step cooperative development method of a kind of anthracite-base porous carbon graphite microcrystal according to claim 1 and hole, It is characterized by: the coal raw material is without any pretreated anthracite in step 1.
3. a step cooperative development method of a kind of anthracite-base porous carbon graphite microcrystal according to claim 1 and hole, It is characterized by: the chemical activating agent is potassium base activator in step 2, the potassium base activator is potassium hydroxide, carbonic acid One of potassium, saleratus and potassium ferrate or a variety of mixtures combined in any proportion.
4. a step cooperative development method of a kind of anthracite-base porous carbon graphite microcrystal according to claim 1 and hole, It is characterized by: the mass ratio of the refinement coal dust and chemical activating agent is 1:0.1~10 in step 2.
5. a step cooperative development method of a kind of anthracite-base porous carbon graphite microcrystal according to claim 1 and hole, It is characterized by: the mixed mode is that ball milling mixing or liquid phase mix in step 2.
6. a step cooperative development method of a kind of anthracite-base porous carbon graphite microcrystal according to claim 1 and hole, It is characterized by: the atmosphere of the atmosphere furnace is high pure nitrogen or high-purity argon gas, and the volume flow of the atmosphere is in step 3 50mL/min~500mL/min.
7. a step cooperative development method of a kind of anthracite-base porous carbon graphite microcrystal according to claim 1 and hole, It is characterized by: the heating rate of the atmosphere furnace is 0.1 DEG C/min~20 DEG C/min in step 3.
8. a step cooperative development method of a kind of anthracite-base porous carbon graphite microcrystal according to claim 1 and hole, It is characterized by: in step 4, the pickling solution that whens pickling processes uses is dilute hydrochloric acid, dust technology or spirit of vinegar, the acid The concentration of washing lotion is 0.01mol/L~10mol/L.
9. a step cooperative development method of a kind of anthracite-base porous carbon graphite microcrystal according to claim 1 and hole, It is characterized by: the cleaning way is vacuum filtration or realizes separation of solid and liquid by centrifuge in step 4, it is cleaned multiple times straight To the pH of supernatant close to 7.
10. a step cooperative development method of a kind of anthracite-base porous carbon graphite microcrystal according to claim 1 and hole, It is characterized by: the drying mode is vacuum drying, heated-air drying or natural evaporation drying mode in step 4.
11. a step cooperative development method of a kind of anthracite-base porous carbon graphite microcrystal according to claim 1 and hole, It is characterized by: in step 4, the drying temperature is 60~160 DEG C, drying time is 6~for 24 hours.
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