CN112279645B - Preparation method of carbon electrode material - Google Patents
Preparation method of carbon electrode material Download PDFInfo
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- CN112279645B CN112279645B CN202011235059.0A CN202011235059A CN112279645B CN 112279645 B CN112279645 B CN 112279645B CN 202011235059 A CN202011235059 A CN 202011235059A CN 112279645 B CN112279645 B CN 112279645B
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- carbon
- oxide film
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- aluminum
- temperature
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000007772 electrode material Substances 0.000 title description 3
- 239000010405 anode material Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims description 62
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 46
- 238000005406 washing Methods 0.000 claims description 42
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 32
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- 239000000243 solution Substances 0.000 claims description 28
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- 239000010407 anodic oxide Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 26
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Abstract
The invention provides a preparation method of a rod-shaped carbon anode material, wherein the carbon rod has almost consistent size, size and shape, and the obtained carbon fiber anode material has high mechanical strength, good corrosion resistance, good uniformity and long service life, and has the breaking strength of 950+/-10 kg/cm 2 Average deviation of breaking strength 5.52, fluctuation coefficient of breaking strength 5.7×10 ‑3 The high-temperature use condition is free from swelling and breakage.
Description
Technical Field
The invention relates to the technical field of a preparation method of an inert anode material for nonferrous metal electrorefining.
Background
The electrode plays a very important role in the electrolysis industry, and the insoluble anode material used for nonferrous metal extraction at present mainly comprises a lead alloy (mainly Pb-Ag alloy) electrode and a titanium-based coating electrode, however, the former has high density and low strength and is easy to dissolve, and the lead alloy is adopted as the anode material, so that the lead content in an electrolysis product is increased; while the titanium-based noble metal (iridium, ruthenium and tantalum) oxide coated electrode in the latter is successfully applied to chlor-alkali industry, the electrode is not suitable for being used in oxygen-separating sulfuric acid electrolyte, and the problem that the internal resistance of titanium is too large is unavoidable.
To overcome the deficiencies of lead electrodes, researchers have mainly performed around two aspects: on one hand, the silver content in Pb-Ag alloy is reduced, and meanwhile, other alloying elements (Sr, sn, bi, sb and the like) and rare earth elements (Ce, tb, yb and the like) are added for multi-element alloying so as to improve the alloy strength and corrosion resistance and reduce the cell voltage; on the other hand, a layer of electrocatalytic active agent and reinforcing agent such as IrO2, ruO2, pbO2, mnO2 and the like are electrodeposited or coated on the surface of the lead electrode by means of electrochemical deposition, coating and the like, so that the conductivity and the stability of the electrode are improved, and the adhesive force of the surface coating is enhanced. However, various treatments are carried out on the lead alloy anode, or other elements are added into the alloy, or the alloy anode is activated and reinforced, so that the problem of dissolution of the lead matrix in the electrochemical corrosion process is always solved.
The carbon material, such as carbon fiber, has a series of excellent mechanical properties of high specific modulus, high specific strength, corrosion resistance, fatigue resistance, abrasion resistance, light specific gravity and the like, and meanwhile, the carbon material has the advantages of good conductivity, strong corrosion resistance, high strength, easy processing, long service life, low preparation cost, high electrode catalytic activity and suitability for non-ferrous metal electrorefining inert anodes.
At present, the carbon material is mainly concentrated on the aspects of porous carbon materials with high specific surface area and smaller internal resistance, modification research on carbon-based materials and the like. The usual carbon materials are: activated carbon, carbon black, carbon nanofibers, vitreous carbon, carbon nanotubes, carbon aerogels, network structured activated carbon, carbonized products of certain organics, and the like.
As disclosed in CN105386087 a, a preparation method of carbon fiber anode material for electrolysis comprises the steps of: 1 to 3:2, uniformly mixing to form a prefabricated ingredient; placing the prefabricated ingredients into a ball mill for ball milling and then screening to obtain ball grinding materials; placing the ball-milled material into forming equipment for cold press forming to obtain a formed material; placing the molding material in nitrogen or inert atmosphere or vacuum high-temperature atmosphere for anaerobic sintering molding, and cooling to obtain the carbon fiber anode material, wherein the carbon fiber anode has good conductivity, mechanical strength, corrosion resistance and chemical stability; simultaneously, the impurity content in the deposited metal is effectively reduced, and the purity of the cathode product is greatly improved.
However, the same problems exist in the electrode made of activated carbon, carbon black, carbon nanofibers, glass carbon, carbon nanotubes, carbon aerogel, activated carbon with network structure and carbonized products of certain organic matters, namely, the mechanical strength of the electrode, such as uneven breaking strength, is too low at a certain position, and the mechanical property of the whole electrode material is reduced, which is mainly caused by the uneven size of the raw materials of the activated carbon, carbon black and carbon nanofibers.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a preparation method of a rod-shaped carbon anode material, wherein the carbon rod-shaped carbon raw material has almost the same size, size and shape, and the obtained carbon fiber anode material has high mechanical strength, good corrosion resistance, good uniformity and long service life, and has the breaking strength of 950+/-10 kg/cm 2 Average deviation of breaking strength 5.52, fluctuation coefficient of breaking strength 5.7×10 -3 High heightThe temperature using condition is free from swelling and breakage.
A preparation method of a rod-shaped carbon anode material comprises the following steps:
(1) Uniformly mixing rod-shaped carbon and a binder according to the mass ratio of (7-8) to 1, wherein the binder is resin or asphalt;
(2) And (3) compression molding: in a cold press at a pressure of 800-850kg/cm 2 Prepressing and shaping to density of 1.2-1.3g/cm 3 ；
(3) Vacuum carbonization: vacuum degree 250-300torr, programmed heating parameter: at 5 o The C/h rate is raised to 450 o C, preserving heat for 1h, 2 o The C/h rate is raised to 550 o C, preserving heat for 2h, then adding 1 o The C/h rate is raised to 920 o C, preserving heat for 5 hours to obtain a carbon presintering embryo;
(4) High-temperature graphitization: put into a nitrogen high temperature graphitization furnace, 15 percent o The C/h rate is raised to 2400 o C, preserving heat for 8 hours; the density of the obtained rod-shaped carbon anode material is 1.85-1.89g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The breaking strength of the anode is 950+/-10 kg/cm 2 Average deviation of breaking strength 5.52, fluctuation coefficient of breaking strength 5.7×10 -3 ,
Wherein the rod-shaped carbon is prepared by the following steps:
(1) Forming a porous oxide film on the surface of an aluminum material by using the aluminum material as a base material through an electrochemical method;
(2) Repeatedly filling the carbon source into the oxide film pore canal for many times by taking the porous oxide film as a hard template and taking the asphalt resin polymer as a carbon source;
(3) Mechanically polishing the material obtained in step (2);
(4) Etching the material obtained in the step (3) by strong acid to remove the hard template;
(5) Washing and drying to obtain the rod-shaped carbon.
Further, the substrate is pretreated: degreasing-washing-pickling-washing-alkaline etching-washing-polishing-washing, wherein the degreasing solution: 45 g/L sodium bicarbonate, 45 g/L sodium carbonate, and a temperature of 40% o C, performing operation; pickling solution: hydrofluoric acid 0.02g1 g/L of sulfuric acid, 4 g/L of surfactant, room temperature, alkaline etching solution: 45/g/L sodium hydroxide, 1/g/L sodium gluconate, temperature 40 o C, the time is 2-3min; light-emitting liquid: 350g/L nitric acid solution for 2-3 min.
Further, the process of the step (1) is as follows: taking pretreated aluminum material as an anode, taking an inert lead material as a cathode, taking 10-20wt.% sulfuric acid aqueous solution as electrolyte, and the current density is 1-2A/dm 2 For 30-100min at 20-30 o And C, obtaining the anodic oxide film aluminum material.
Further, the obtained anodized film aluminum material was subjected to a treatment of 35 o And C, reaming with 5-7wt.% phosphoric acid for 40-50min, and vacuum drying.
Further, the preparation method of the asphalt resin polymer in the step (2) comprises the following steps: filling benzaldehyde, anthracene and concentrated sulfuric acid into a three-necked bottle, evacuating with nitrogen, and cooling at 135 o C, obtaining a black asphalt resin product under the continuous stirring condition, repeatedly washing, filtering and drying by using propanol to obtain a pale yellow powder solid, dissolving the pale yellow powder in tetrahydrofuran, stirring for 30min, then adding the reamed oxide film aluminum material obtained in the step (1), continuously stirring, carrying out auxiliary vacuumizing, filling for 12-24h, then carrying out rotary evaporation to obtain the pale yellow oxide film aluminum material, and further carrying out nitrogen atmosphere with 800 percent o Carbonizing for 4h under C.
Further, the vacuum degree of the vacuumized air is 10-20Pa.
Further, the multiple repeated fills are 1-2 times.
Further, the mechanical polishing is polishing by a polishing wheel and is used for removing the non-pore carbon materials on the anodic oxide film porous layer.
Further, the strong acid is 15wt.% H 2 SO 4 And 10wt.% HNO 3 The volume ratio is VH 2 SO 4 :VHNO 3 =1:1, under stirring at 100 o C reflux treatment 3 h.
Further, the washing is to wash the product with deionized water for a plurality of times to be neutral, then filter the product, and dry the product to 60 o C lower blastAnd drying 12 h.
Regarding the preparation method:
(a) After the carbon of the electrode raw material is determined, a certain amount of binder substances are added according to the physical and chemical properties of the molding main material, so that the powder adhesiveness and cohesiveness of the molding main material are improved, and a satisfactory molding effect is achieved. After the main molding materials are determined, different molding binders are selected to have great influence on the physical properties of the product. In order to improve the product performance and the molding process performance, a proper amount of molding binder should be added according to the physical properties of the molding main material.
The invention selects resin or asphalt as binder, in the process of electrode forming, the product is not expected to be polluted by the binder, the resin or asphalt can be decomposed in the roasting process, the obtained decomposed product and the rod-shaped carbon are bonded together to play a certain skeleton role, so that the dispersed rod-shaped carbon is combined into a firm integral electrode, and then the firm integral electrode is subjected to vacuum and high-temperature graphitization treatment, and finally the high-density and high-strength carbon anode material is obtained.
(b) Compression molding in a cold press at a pressure of 800-850kg/cm 2 Prepressing and shaping to density of 1.2-1.3g/cm 3 ；
For preliminary increasing the density of the carbon material as shown in fig. 8.
(c) Vacuum carbonization: by testing the carbon material on a TGA/DTA curve, the carbon material can be found to be 400 o About C has a small thermal weight loss, and the thermally decomposed small molecules begin to volatilize at 400-450 o C has no obvious thermal weight loss when the temperature is increased to 550 DEG C O C undergoes intense thermal decomposition and dehydrogenation reactions and generates a large amount of gas, the volume shrinkage during this process is about 9.78%, the weight loss is 11.32%, and the density at this time is 1.62 g/cm 3 This process requires at 450 o C and 550 o And C, fully reacting at two temperature points, thereby being beneficial to the growth of high-density carbon materials, specifically, the vacuum degree is 250-300torr, and the temperature programming parameters are as follows: at 5 o The C/h rate is raised to 450 o C, preserving heat for 1h, 2 o The C/h rate is raised to 550 o C, preserving heat for 2h, then adding 1 o C/h rate of rise to920 o And C, preserving heat for 5 hours to obtain the carbon presintering embryo body.
(d) High-temperature graphitization: : put into a nitrogen high temperature graphitization furnace, 15 percent o The C/h rate is raised to 2400 o C, preserving heat for 8 hours; further reducing volatile matters in the rod-shaped carbon, improving the heat conductivity of the anode, reducing carbonization and cracking caused by thermal stress generated by low heat conductivity and high shrinkage, wherein the shrinkage of the carbon anode is about 3.2%, the weight loss is 1.9%, and the density is 1.85-1.89g/cm 3
(1) The aluminum material used in the application should be pretreated before anodic oxidation, no matter what surface treatment process is used, good effect is to be obtained, and the clean surface is the primary condition, the application hopes to obtain the anodic oxidation film with uniform nano pore channels and uniform thickness, so that the pretreatment is the basis for obtaining the uniform oxidation film in all directions, and the substrate is pretreated: degreasing, water washing, acid washing, water washing, alkali etching, water washing, light emitting and water washing.
Wherein the degreasing solution: 45 g/L sodium bicarbonate, 45 g/L sodium carbonate, and a temperature of 40% o And C, removing greasy dirt on the surface of the workpiece before surface treatment, ensuring the bonding strength of the conversion film and the matrix metal, ensuring the smooth progress of chemical reaction of the conversion film, and obtaining the conversion film layer with qualified quality.
Pickling solution: 0.02g/L of hydrofluoric acid, 4 g/L of sulfuric acid, 1 g/L of surfactant, room temperature, acid washing to remove dirt and oxide on the surface, and no hydrogen embrittlement, wherein the acid degreasing mechanism of the aluminum alloy is as follows: and (3) dissolving out the oxide on the aluminum surface to loosen the greasy dirt, and separating the greasy dirt from the metal surface by utilizing the action of water flow.
Alkaline etching solution: 45/g/L sodium hydroxide, 1/g/L sodium gluconate, temperature 40 o C, the time is 2-3min, the aluminum alloy workpiece cannot be subjected to conversion film treatment after degreasing process, the surface of the aluminum alloy workpiece generally has the defects of natural oxide film, processing stripes and the like, and the aluminum alloy workpiece needs to be subjected to corrosion treatment to remove the natural oxide film and activate the surface. Alkaline corrosion is the most commonly used corrosion process, the main component is NaOH solution, the cost is low, the maintenance and the management are easy, and the alkaline corrosion is used for removing acid washing and cannot be removedAnd removing the oxide film.
Light-emitting liquid: 350g/L nitric acid solution for 2-3 min. The surface of the workpiece subjected to acid-base corrosion is usually darkened because of the existence of copper oxide on the surface of the aluminum alloy with higher copper content, so that black ash is formed. In order to make the surface of the workpiece bright, the polishing treatment is usually carried out in a nitric acid solution.
(2) Regarding anodic oxidation: 10-20wt.% sulfuric acid aqueous solution is adopted as electrolyte, and the current density is 1-2A/dm 2 For 30-100min at 20-30 o C, the thickness of the obtained anodic oxide film aluminum material is 10-20 micrometers, the pore diameter is concentrated below 500nm, and the pore diameter is smaller, as shown in figure 5, the pore diameter is unfavorable for the subsequent carbon filling precursor, so that the obtained anodic oxide film aluminum material is 35 percent o And C, reaming is carried out by using 5-7wt.% of phosphoric acid for 40-50min, and vacuum drying is carried out to finish reaming of the anodic oxide film pore canal, so that filling of a carbon precursor is facilitated, the thickness is not obviously reduced or the reduction is not obvious in the reaming process, the pore diameter is enlarged to 0.5-0.7 mu m, as shown in figure 6, the anodic oxide film pore canal hard template for reaming for 20min is obtained, as shown in figure 7, and the anodic oxide film hard template for reaming for 45min is obtained.
(3) Regarding the preparation of the precursor: the principle of selecting the carbon precursor is that the molecular size is suitable for entering the pore canal of the anodic oxide film template, the compatibility (wettability and hydrophilicity) with the pore wall is good, and the carbonization yield is higher after separating or further polymerizing substances in the pore is good. Currently, carbon precursors are mainly sucrose, xylose, glucose, furfuryl alcohol resins, phenolic resins, mesophase pitch, anthracene, phenanthrene, divinylbenzene, and some organic solvents such as ethanol, methanol, toluene, and the like. There are also a number of methods for introducing different precursors into the channels of a hard template, the most common being mainly solution impregnation, the type of carbon precursor having a large influence on the structure of the final resulting carbon material. Furfuryl alcohol is used as a carbon precursor, so that mesoporous carbon with good order is easily prepared; when the mesophase pitch is used as a carbon precursor, the microporosity of the material can be obviously reduced, and the carbon yield is high; in addition, the type of carbon precursor has a very important influence on the graphitization degree of the finally obtained carbon material, and precursors with loose molecular structures (such as phenolic resin) with high oxygen content can obtain hard carbon materials with a large number of micropores and higher oxygen content after carbonization, and the hard carbon materials are difficult to graphitize. The mesoporous carbon material with higher graphitization degree can be obtained after carbonization of the precursor (such as anthracene) with condensed ring structure and without oxygen, and the carbon filler of the invention hopes the microporosity of the carbon material and has high carbon yield, so that the pitch resin polymer is used for filling.
The preparation method comprises the following steps: filling benzaldehyde, anthracene and concentrated sulfuric acid into a three-necked bottle, evacuating with nitrogen, and cooling at 135 o C, obtaining a black asphalt resin product under the continuous stirring condition, repeatedly washing, filtering and drying by using propanol to obtain a pale yellow powder solid, dissolving the pale yellow powder in tetrahydrofuran, stirring for 30min, then adding the reamed oxide film aluminum material obtained in the step (1), continuously stirring, carrying out auxiliary vacuumizing, filling for 12-24h, then carrying out rotary evaporation to obtain the pale yellow oxide film aluminum material, and further carrying out nitrogen atmosphere with 800 percent o Carbonizing for 4h under C.
In the process, the temperature and the water are needed to be paid attention to in the filling process (a), so that the water-based hole sealing phenomenon of the anodic oxide film is avoided, and the filling of the carbon precursor liquid is obviously reduced due to the hole sealing; (b) Stirring and vacuumizing are necessary means, and because of the viscosity of the asphalt polymer, the filling process is slightly difficult, so that stirring is necessary at all times, vacuumizing is performed, and the carbon precursor is assisted to enter a pore channel, and then evaporation, drying and carbonization processes are performed; (c) The filling times are determined according to the needs, and the filling is not performed as much as possible.
In addition, the quality of the anodic oxidation porous film hard template, the carbon precursor filling amount and the carbonization process all affect the mesostructure of the nano carbon rod to a great extent. Of particular importance is the selection of the carbon precursor. The carbon precursor molecules can interact with the template molecules to form ordered mesostructures. Secondly, the precursor molecules must also be capable of cross-linking themselves to form a thermoset polymer network, which can be used to resist deformation caused by shrinkage of the framework during high temperature carbonization and template removal in template removal engineering. In addition, different carbon precursors undergo different carbonization processes, so that the mesostructure of the carbon rod can be influenced, and the microstructure such as graphitization degree and the like can be also influenced. Therefore, the carbon precursor molecules are required to have the characteristics of proper size, good thermal stability, abundant warp groups, high carbon residue of the polymer, and the like.
(4) Regarding polishing: mechanical polishing is a key step for controlling morphology of the invention, as shown in fig. 1, when excessive carbon precursor is filled, carbon materials are attached to the surface of the anodic oxide film, polishing by a polishing wheel is needed at the moment and used for removing the carbon materials in non-pore channels on the porous layer of the anodic oxide film, one end of the finally obtained carbon rod is a semicircular arc section of the position of the barrier layer of the anodic oxide film, and one end is a mechanically polished flat line end, as shown in fig. 2, wherein one end is arc-shaped and the other end is flat line end.
(5) Regarding corrosion, in the case of anodized aluminum, the base materials are aluminum oxide and aluminum, and because of the amphoteric nature of aluminum, it is possible to use an acidic solution or an alkaline solution for corrosion, but the present application abandons alkaline corrosion because the present invention requires the introduction of a large amount of hydrophilic radicals such as hydroxyl groups, oxy groups, etc. on the surface of a carbon material in addition to the removal of the aluminum template, and only alkaline corrosion is insufficient, and thus a strong acid of 15wt.% H is used 2 SO 4 And 10wt.% HNO 3 The volume ratio is VH 2 SO 4 :VHNO 3 =1:1, under stirring at 100 o And C, carrying out reflux treatment 3 h, namely, introducing hydroxyl through strong acid corrosion and reflux treatment, so that the water solubility of the carbon material is improved, and under an ethanol and water solution system, as shown in an SEM (scanning electron microscope) of a drawing 2, the carbon rod is uniformly dispersed and has low polymerization, and the application field of the carbon rod is remarkably widened due to the existence of the dispersion state.
As shown in fig. 3 and 4, the regular carbon rod material obtained after direct corrosion without polishing is shown in top view and side view.
The scheme of the invention has the following beneficial effects:
(1) The carbon rod prepared by the template method has almost consistent size, size and shape, and the finally obtained carbon material has good uniformity.
(2) The obtained carbon fiber anode material has high mechanical strength, good corrosion resistance, good uniformity and long service life,
(3) The breaking strength of the anode material was 950.+ -.10 kg/cm 2 Average deviation of breaking strength 5.52, fluctuation coefficient of breaking strength 5.7×10 -3 The high-temperature use condition is free from swelling and breakage.
Drawings
FIG. 1 is a schematic diagram of a carbon nanomaterial fabrication method according to the present invention.
Fig. 2 is a TEM image of the inventive nanocarbon stick under water-ethanol conditions.
Fig. 3 is a SEM plan view of the nanorod-shaped carbon material without polishing according to the present invention.
Fig. 4 is a side view of a polished nanorod-shaped carbon material of the present invention.
Fig. 5 is an SEM image of the pore channels of the un-reamed anodic oxide film of the invention.
FIG. 6 is an SEM image of an anodized film hole drilled for 20 minutes according to the present invention.
Fig. 7 is an SEM image of anodic oxide film pore canal reamed for 45min according to the present invention.
Fig. 8 is an SEM image of the anode material obtained by press molding according to the present invention.
Description of the embodiments
Examples
The preparation method of the rod-shaped carbon anode material is characterized by comprising the following steps of:
(a) Uniformly mixing rod-shaped carbon and a binder according to the mass ratio of 7:1, wherein the binder is resin or asphalt;
(b) And (3) compression molding: at a pressure of 800kg/cm in a cold press 2 Prepressing and forming;
(c) Vacuum carbonization: vacuum degree 250torr, programmed temperature parameters: at 5 o The C/h rate is raised to 450 o C, preserving heat for 1h, 2 o The C/h rate is raised to 550 o C, preserving heat for 2h, then adding 1 o The C/h rate is raised to 920 o C, preserving heat for 5 hours to obtain carbon presinteringA blank;
(d) High-temperature graphitization: put into a nitrogen high temperature graphitization furnace, 15 percent o The C/h rate is raised to 2400 o C, preserving heat for 8 hours;
wherein the rod-shaped carbon is prepared by the following steps: (1) Pretreatment, namely degreasing, water washing, acid washing, water washing, alkali etching, water washing, light emitting and water washing, wherein the degreasing solution is as follows: 45 g/L sodium bicarbonate, 45 g/L sodium carbonate, and a temperature of 40% o C, performing operation; pickling solution: 0.02g/L of hydrofluoric acid, 4 g/L of sulfuric acid, 1 g/L of surfactant, room temperature, alkaline etching solution: 45/g/L sodium hydroxide, 1/g/L sodium gluconate, temperature 40 o C, the time is 2min; light-emitting liquid: 350g/L nitric acid solution for 2min.
(2) Forming a porous oxide film on the surface of an aluminum material by using the aluminum material as a base material through an electrochemical method; takes aluminum or aluminum alloy as a base material, takes an inert lead material as a cathode, takes 10wt.% sulfuric acid aqueous solution as electrolyte, and has a current density of 1A/dm 2 For 30min at 20 o C, obtaining anodic oxide film aluminum material, and subjecting the obtained anodic oxide film aluminum material to 35 o Reaming was performed with 5wt.% phosphoric acid for 40min and vacuum drying.
(3) The porous oxide film is used as a hard template, the asphalt resin polymer is used as a carbon source, and the carbon source is repeatedly filled in the oxide film pore canal for a plurality of times, wherein the preparation method of the asphalt resin polymer comprises the following steps: filling benzaldehyde, anthracene and concentrated sulfuric acid into a three-necked bottle, evacuating with nitrogen, and cooling at 135 o C, obtaining a black asphalt resin product under the continuous stirring condition, repeatedly washing, filtering and drying by using propanol to obtain a pale yellow powder solid, dissolving the pale yellow powder in tetrahydrofuran, stirring for 30min, then adding the reamed oxide film aluminum material obtained in the step (1), continuously stirring, carrying out auxiliary vacuumizing, filling for 12h, then carrying out rotary evaporation to obtain the pale yellow oxide film aluminum material, and further carrying out rotary evaporation with nitrogen atmosphere of 800 percent o C, carbonizing for 4 hours, wherein the vacuum degree of vacuumizing is 10-20Pa, and filling twice.
(4) Mechanical polishing step materials: the mechanical polishing is polishing by a polishing wheel and is used for removing the non-pore carbon materials on the anodic oxide film porous layer.
(5) And (3) removing the hard template by strong acid corrosion: the strong acid is 15wt.% H 2 SO 4 And 10wt.% HNO 3 The volume ratio is VH 2 SO 4 :VHNO 3 =1:1, under stirring at 100 o C reflux treatment 3 h.
(6) Washing, drying, washing with deionized water for several times to neutral, filtering, and drying to 60 o And C, air drying 12 h.
Example 2
The preparation method of the rod-shaped carbon anode material is characterized by comprising the following steps of:
(a) Uniformly mixing rod-shaped carbon and a binder according to the mass ratio of 7.5:1, wherein the binder is resin or asphalt;
(b) And (3) compression molding: in a cold press at a pressure of 800-850kg/cm 2 Prepressing and forming;
(c) Vacuum carbonization: vacuum 300torr, programmed temperature parameters: at 5 o The C/h rate is raised to 450 o C, preserving heat for 1h, 2 o The C/h rate is raised to 550 o C, preserving heat for 2h, then adding 1 o The C/h rate is raised to 920 o C, preserving heat for 5 hours to obtain a carbon presintering embryo;
(d) High-temperature graphitization: put into a nitrogen high temperature graphitization furnace, 15 percent o The C/h rate is raised to 2400 o C, preserving heat for 8 hours; the breaking strength of the anode is 950+/-10 kg/cm 2 Average deviation of breaking strength 5.52, fluctuation coefficient of breaking strength 5.7×10 -3 ,
Wherein the rod-shaped carbon is prepared by the following steps:
(1) Pretreatment, namely degreasing, water washing, acid washing, water washing, alkali etching, water washing, light emitting and water washing, wherein the degreasing solution is as follows: 45 g/L sodium bicarbonate, 45 g/L sodium carbonate, and a temperature of 40% o C, performing operation; pickling solution: 0.02g/L of hydrofluoric acid, 4 g/L of sulfuric acid, 1 g/L of surfactant, room temperature, alkaline etching solution: 45/g/L sodium hydroxide, 1/g/L sodium gluconate, temperature 40 o C, the time is 2.5min; light-emitting liquid: 350g/L nitric acid solution for 2.5min.
(2) By electrochemical treatment with aluminum material as base materialForming a porous oxide film on the surface of the aluminum material by a chemical method; takes aluminum or aluminum alloy as a base material, takes an inert lead material as a cathode, takes 15wt.% sulfuric acid aqueous solution as electrolyte, and has a current density of 1.5A/dm 2 For 60min at 25 o C, obtaining anodic oxide film aluminum material, and subjecting the obtained anodic oxide film aluminum material to 35 o Reaming was performed with 6wt.% phosphoric acid for 45min and vacuum drying.
(3) The porous oxide film is used as a hard template, the asphalt resin polymer is used as a carbon source, and the carbon source is repeatedly filled in the oxide film pore canal for a plurality of times, wherein the preparation method of the asphalt resin polymer comprises the following steps: filling benzaldehyde, anthracene and concentrated sulfuric acid into a three-necked bottle, evacuating with nitrogen, and cooling at 135 o C, obtaining a black asphalt resin product under the continuous stirring condition, repeatedly washing, filtering and drying by using propanol to obtain a pale yellow powder solid, dissolving the pale yellow powder in tetrahydrofuran, stirring for 30min, then adding the reamed oxide film aluminum material obtained in the step (1), continuously stirring, carrying out auxiliary vacuumizing, filling for 18h, then carrying out rotary evaporation to obtain the pale yellow oxide film aluminum material, and further carrying out nitrogen atmosphere with 800 percent o C, carbonizing for 4 hours, wherein the vacuum degree of vacuumizing is 10-20Pa, and filling twice.
(4) Mechanical polishing step materials: the mechanical polishing is polishing by a polishing wheel and is used for removing the non-pore carbon materials on the anodic oxide film porous layer.
(5) And (3) removing the hard template by strong acid corrosion: the strong acid is 15wt.% H 2 SO 4 And 10wt.% HNO 3 The volume ratio is VH 2 SO 4 :VHNO 3 =1:1, under stirring at 100 o C reflux treatment 3 h.
(6) Washing, drying, washing with deionized water for several times to neutral, filtering, and drying to 60 o And C, air drying 12 h.
Examples
The preparation method of the rod-shaped carbon anode material is characterized by comprising the following steps of:
(a) Uniformly mixing rod-shaped carbon and a binder according to the mass ratio of 8:1, wherein the binder is resin or asphalt;
(b) And (3) compression molding: in a cold press at a pressure of 850kg/cm 2 Prepressing and forming;
(c) Vacuum carbonization: vacuum 300torr, programmed temperature parameters: at 5 o The C/h rate is raised to 450 o C, preserving heat for 1h, 2 o The C/h rate is raised to 550 o C, preserving heat for 2h, then adding 1 o The C/h rate is raised to 920 o C, preserving heat for 5 hours to obtain a carbon presintering embryo;
(d) High-temperature graphitization: put into a nitrogen high temperature graphitization furnace, 15 percent o The C/h rate is raised to 2400 o C, preserving heat for 8 hours;
wherein the rod-shaped carbon is prepared by the following steps:
(1) Pretreatment, namely degreasing, water washing, acid washing, water washing, alkali etching, water washing, light emitting and water washing, wherein the degreasing solution is as follows: 45 g/L sodium bicarbonate, 45 g/L sodium carbonate, and a temperature of 40% o C, performing operation; pickling solution: 0.02g/L of hydrofluoric acid, 4 g/L of sulfuric acid, 1 g/L of surfactant, room temperature, alkaline etching solution: 45/g/L sodium hydroxide, 1/g/L sodium gluconate, temperature 40 o C, the time is 3min; light-emitting liquid: 350g/L nitric acid solution for 3min.
(2) Forming a porous oxide film on the surface of an aluminum material by using the aluminum material as a base material through an electrochemical method; takes aluminum or aluminum alloy as a base material, takes an inert lead material as a cathode, takes a sulfuric acid aqueous solution with 20wt.% as an electrolyte, and has a current density of 2A/dm 2 For 100min at 30 o C, obtaining anodic oxide film aluminum material, and subjecting the obtained anodic oxide film aluminum material to 35 o Reaming was performed with 7wt.% phosphoric acid for 50min and vacuum drying.
(3) The porous oxide film is used as a hard template, the asphalt resin polymer is used as a carbon source, and the carbon source is repeatedly filled in the oxide film pore canal for a plurality of times, wherein the preparation method of the asphalt resin polymer comprises the following steps: filling benzaldehyde, anthracene and concentrated sulfuric acid into a three-necked bottle, evacuating with nitrogen, and cooling at 135 o C, obtaining a black asphalt resin product under the condition of continuous stirring, repeatedly washing with propanol, filtering and drying to obtain a pale yellow powder solid, dissolving the pale yellow powder in tetrahydrofuran, and stirring for 30min, adding the reamed oxide film aluminum obtained in the step (1), continuously stirring, carrying out auxiliary vacuumizing, filling for 24h, and carrying out rotary evaporation to obtain a yellowish oxide film aluminum, wherein the yellowish oxide film aluminum is further subjected to nitrogen atmosphere, and the temperature is 800 o C, carbonizing for 4 hours, wherein the vacuum degree of vacuumizing is 10-20Pa, and filling twice.
(4) Mechanical polishing step materials: the mechanical polishing is polishing by a polishing wheel and is used for removing the non-pore carbon materials on the anodic oxide film porous layer.
(5) And (3) removing the hard template by strong acid corrosion: the strong acid is 15wt.% H 2 SO 4 And 10wt.% HNO 3 The volume ratio is VH 2 SO 4 :VHNO 3 =1:1, under stirring at 100 o C reflux treatment 3 h.
(6) Washing, drying, washing with deionized water for several times to neutral, filtering, and drying to 60 o And C, air drying 12 h.
Using the procedure of example 2, 20 samples were prepared, and their breaking strengths were measured using an ST-5E strength tester and found to be 957 kg/cm, respectively 2 ；953 kg/cm 2 ；955 kg/cm 2 ；959 kg/cm 2 ；956 kg/cm 2 ；956 kg/cm 2 ；954 kg/cm 2 ；955 kg/cm 2 ；956 kg/cm 2 ；949 kg/cm 2 ；952 kg/cm 2 ；950 kg/cm 2 ；961 kg/cm 2 ；943 kg/cm 2 ；957 kg/cm 2 ；947 kg/cm 2 ；949 kg/cm 2 ；960 kg/cm 2 ；942 kg/cm 2 ；945 kg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The density of the anode material obtained by calculation is 1.85-1.89g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The breaking strength of the anode is 950+/-10 kg/cm 2 Average deviation of breaking strength 5.52, fluctuation coefficient of breaking strength 5.7×10 -3 The stability and breaking strength of the anode are far superior to those of similar products.
Although the present invention has been described by way of example with reference to the preferred embodiments, the present invention is not limited to the specific embodiments, and may be modified appropriately within the scope of the present invention.
Claims (1)
1. The preparation method of the carbon pole material is characterized in that the preparation process of the carbon pole material comprises the following steps:
(a) Uniformly mixing rod-shaped carbon and a binder according to the mass ratio of (7-8) to 1, wherein the binder is resin or asphalt;
(b) And (3) compression molding: in a cold press at a pressure of 800-850kg/cm 2 Prepressing and shaping to density of 1.2-1.3g/cm 3 ；
(c) Vacuum carbonization: vacuum degree 250-300torr, programmed heating parameter: heating to 450 ℃ at a speed of 5 ℃/h, preserving heat for 1h, heating to 550 ℃ at a speed of 2 ℃/h, preserving heat for 2h, heating to 920 ℃ at a speed of 1 ℃/h, and preserving heat for 5h to obtain a carbon presintering embryo body;
(d) High-temperature graphitization: placing the mixture into a nitrogen high-temperature graphitization furnace, heating to 2400 ℃ at a speed of 15 ℃/h, and preserving heat for 8h; the density of the obtained rod-shaped carbon anode material is 1.85-1.89g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The breaking strength of the anode is 950+/-10 kg/cm 2 Average deviation of breaking strength of 5.52, fluctuation coefficient of breaking strength of 5.7X10 -3 ；
Wherein the rod-shaped carbon is prepared by the following steps:
(1) Taking aluminum as a base material, and pretreating the base material: degreasing-washing-pickling-washing-alkaline etching-washing-polishing-washing, wherein the degreasing solution: 45 g/L of sodium bicarbonate, 45 g/L of sodium carbonate and the temperature is 40 ℃; pickling solution: 0.02g/L of hydrofluoric acid, 4 g/L of sulfuric acid, 1 g/L of surfactant, room temperature, alkaline etching solution: 45 g/L sodium hydroxide, 1 g/L sodium gluconate, and temperature of 40 ℃ for 2-3min; light-emitting liquid: 350g/L nitric acid solution for 2-3min; then forming a porous oxide film on the surface of the aluminum material by an electrochemical method: taking aluminum as an anode, taking an inert lead material as a cathode, taking 10-20wt.% sulfuric acid aqueous solution as electrolyte, and the current density is 1-2A/dm 2 The time is 30-100min, the temperature is 20-30 ℃, and the anodic oxide film aluminum material is obtained; reaming the obtained anodic oxide film aluminum material with 5-7wt.% phosphoric acid at 35deg.C for 40-50min, and vacuumDrying;
(2) Taking the porous oxide film obtained by the treatment in the step (1) as a hard template, taking the asphalt resin polymer as a carbon source, and repeatedly filling the carbon source into the oxide film pore canal for a plurality of times, wherein the repeated filling is 1-2 times;
the preparation method of the asphalt resin polymer in the step (2) comprises the following steps: filling benzaldehyde, anthracene and concentrated sulfuric acid into a three-mouth bottle, evacuating by using nitrogen, obtaining a black asphalt resin product under the condition of continuous stirring at 135 ℃, repeatedly washing by using propanol, filtering and drying to obtain a pale yellow powder solid, dissolving the pale yellow powder into tetrahydrofuran, stirring for 30min, adding the expanded oxide film aluminum obtained in the step (1), continuing stirring, and carrying out auxiliary vacuumizing, wherein the vacuumizing vacuum degree is 10-20Pa, filling for 12-24h, and then carrying out rotary evaporation to obtain the pale yellow oxide film aluminum, and carbonizing for 4h at 800 ℃ under the nitrogen atmosphere;
(3) Mechanically polishing the material obtained in the step (2) by a polishing wheel for removing the non-porous carbon material on the anodic oxide film porous layer;
(4) Etching the material obtained in the step (3) by strong acid to remove the hard template: a strong acid of 15wt.% H 2 SO 4 And 10wt.% HNO 3 Volume ratio H 2 SO 4 :HNO 3 =1:1, reflux treatment at 100 ℃ under stirring 3 h;
(5) Washing and drying, wherein the washing is carried out by washing with deionized water for a plurality of times until the washing is neutral, filtering, and drying is carried out by blast drying at 60 ℃ for 12 h.
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