CN104319402A - Preparation method for multi-layer carbon hollow sphere anode material - Google Patents
Preparation method for multi-layer carbon hollow sphere anode material Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method for a multi-layer carbon hollow sphere anode material. The material is of a multilayer hollow carbon sphere structure; a carbon shell is double-layered or four-layered; the diameter of the carbon sphere is at a nanometer or submicron level. According to the preparation method, the multi-layer carbon hollow sphere material can be obtained by taking tetraethoxysilane as a silicon source, preparing a single-layer or double-layer hollow silicone dioxide hard template by adopting a surfactant soft template method, then, performing pyrolysis on an organic carbon source to coat the silicone dioxide hollow sphere template, performing high-temperature carbonization under an inert atmosphere, and finally, etching the silicon dioxide template. The method disclosed by the invention is simple and easy to operate, high in controllability, low in pollution, low in cost, and has universality. The prepared product is of a hollow structure, and has the shell with the thickness of nanoscale; meanwhile, the internal space can be effectively utilized by a multilayer structure; compared with the conventional nanomaterial, the single-layer carbon hollow spheres show excellent electrochemical performance when the product is applied to the anode material of a lithium-ion battery.
Description
Technical field
The present invention relates to technical field of lithium ion, particularly relate to a kind of preparation method of multilayer carbon hollow ball negative material.
Background technology
The advantages such as specific energy is high, operating voltage is high owing to having for lithium rechargeable battery, have extended cycle life, self discharge is little, pollution-free, lightweight, fail safe is good will become the main lift-launch power supply of electric automobile, be that the chemical energy storage technology of representative also actively drops into research and development with lithium ion battery.Positive pole material of lithium cobalt acid (LiCoO
2), LiMn2O4 (LiMn
2o
4) and LiFePO4 (LiFePO
4) etc. the technological break-through of electrode material make lithium ion battery applications scope turn to electric automobile and technical field of energy storage from the electric terminal equipment such as mobile phone, notebook computer.Current lithium ion battery negative material adopts traditional graphite mostly, and it has the advantages such as cheap, source is wide, good conductivity, but is only 372mAh/g (LiC due to the theoretical capacity of graphite material
6), and lithium ion diffusion coefficient in graphite material on the low side (10
-11~ 10
-6cm
2s
-1), these factors cause the memory capacity of graphite material and high rate performance all poor, seriously limit its application as following high performance lithium ionic cell cathode material.
For attempting addressing this problem, hollow nano material with carbon element comes into one's own gradually, as: monoshell layer hollow nano carbon ball (K.Tang et al.Chemsuschem 5 (2012) 400-403), the hollow nano carbon ball (F.D.Han et al.Advanced Energy Materials 1 (2011) 798-801) of internal crosslinking, carbon nanotubes (L.G.Bulusheva et al.Carbon 49 (2011) 4013-4023) etc.Research finds that these materials all have good lithium storage content and good high rate performance, and the performance of these excellences is because hollow ultra-thin carbon shell can improve the specific area of material on the one hand, provides more lithium ion reaction site, to improve the capacitance of material; Ultra-thin carbon shell can make lithium ion transport distance shorten on the other hand, and high rate performance is got a promotion; And the hollow space of inside can well hold the change in volume of material in charge and discharge process.But the hollow carbon material of this single wall causes activity substance content lower due to the hollow structure that inside is large, and then makes the specific capacity of whole electrode and energy density still on the low side.
Therefore, those skilled in the art is devoted to develop that a kind of energy density is high, good cycle, the cell negative electrode material that lithium storage content is large.
Summary of the invention
Because the above-mentioned defect of prior art, technical problem to be solved by this invention is to provide a kind of nanometer scale, even particle size distribution, has the lithium ion battery cathode material and its preparation method of good electrical chemical property.
For achieving the above object, the invention provides a kind of multilayer carbon hollow ball negative material, described negative material is the nanometer or the submicron order hollow carbon balls structure that comprise multilayer carbon shell, wherein, carbon shell is the amorphous carbon layer that organic substance is formed after polycondensation, carbonization, multilayer is double-deck or four layers, and the inside of carbon ball is hollow-core construction.
Present invention also offers a kind of preparation method of multilayer carbon hollow ball negative material, comprise the steps:
Steps A: organo-silicon compound are hydrolyzed in the aqueous solution of surfactant, obtain individual layer hollow ball-shape silica template, organo-silicon compound are added in the aqueous surfactant solution being mixed with individual layer hollow ball-shape silica spheres, obtain double-layer hollow spherical silicon dioxide template through hydrolysis;
Step B: the list that steps A is obtained/double-layer hollow spherical silicon dioxide surfaces externally and internally adheres to organic RESEARCH OF PYROCARBON raw material, and organic RESEARCH OF PYROCARBON raw material is through hydro-thermal reaction aftercondensated;
Step C: organic RESEARCH OF PYROCARBON raw material of polycondensation is coated on hollow ball-shape silicon dioxide surfaces externally and internally under inert atmosphere protection after carbonization, obtained hollow shape nano composite material has carbon-silica-carbon " sandwich " shell structurre.
Step D: etched by the silica template hydrofluoric acid solution in hollow shape nano composite material, obtains bilayer/tetra-layer carbon hollow ball;
Preferably, in above-mentioned preparation method, organo-silicon compound are 3-aminopropyl triethoxysilane and tetraethoxysilane, and surfactant is neopelex and dodecyl sulfobetaine.
More preferably, a kind of preparation method of multilayer carbon hollow ball negative material, comprises the steps:
Step one: under room temperature, adds in deionized water using neopelex and dodecyl sulfobetaine as surfactant, magnetic agitation 0.5 ~ 2 hour, forms surfactant solution;
Step 2: surfactant solution is heated to 40 ~ 50 DEG C, then 3-aminopropyl triethoxysilane and tetraethoxysilane are instilled respectively, stir 0.5 ~ 2 hour, be formed with the mixed solution of organic silicon compound and surfactant;
Step 3: the solution of organo-silicon compound and surfactant is heated to 70 ~ 90 DEG C and is incubated 10 ~ 40 hours in oil bath pan, reaction terminates, and obtains product;
Step 4: use centrifugal mode collecting reaction product, respectively with ethanol and deionized water product is washed, dry, obtain dry product;
Step 5: the product of drying added in acetonitrile hydrochloric acid mixed solution, stirs 4 ~ 8 hours, rear deionized water cleans again, dry, obtains individual layer hollow ball-shape silica template;
Step 6: individual layer hollow ball-shape silica template is added in the surfactant mixed solution of neopelex obtained by step one and dodecyl sulfobetaine, repeat step 2 again to step 5, i.e. obtained double-layer hollow spherical silicon dioxide template;
Step 7: join in the aqueous solution of organic RESEARCH OF PYROCARBON raw material by list/double-layer hollow spherical silicon dioxide template, stirs 0.5 ~ 2 hour, obtains mixed liquor;
Step 8: mixed liquor is poured in reactor, the cumulative volume of mixed liquor accounts for 1/2 ~ 3/4 of reactor internal volume, is warming up to 170 ~ 200 DEG C and is incubated 2 ~ 8 hours, obtaining hydro-thermal reaction product;
Step 9: use centrifugation to collect hydro-thermal reaction product, respectively with ethanol and deionized water washing, dry, obtain desciccate;
Step 10: desciccate is placed in refractory container, is warming up to 600 ~ 900 DEG C of calcinings under inert atmosphere protection, and calcination time is 2 ~ 10 hours, then obtain the hollow Nano composite material with carbon-silica-carbon " sandwich " shell structurre feature;
Step 11: add in hydrofluoric acid solution by hollow Nano composite material, stirs 1 ~ 8 hour, rear deionized water cleans again, dry, then obtain bilayer/tetra-layer carbon hollow ball.
More preferably, in step one, neopelex and dodecyl sulfobetaine take by equal molar quantities, and the mol ratio of deionized water and surfactant total amount is 2000:1 ~ 15000:1.
More preferably, in step 2, the 3-aminopropyl triethoxysilane added and the mol ratio of surfactant total amount are 2:1 ~ 2:5, and the mol ratio of the tetraethoxysilane added and surfactant total amount is 2:1 ~ 10:1.
More preferably, in step 5, acetonitrile hydrochloric acid mixed solution is that 1:1 ~ 1:3 configures and forms with volume ratio by concentrated hydrochloric acid and acetonitrile, concentrated hydrochloric acid to be mass percent be 36% ~ 38% hydrochloric acid.
More preferably, in step 7, the mass ratio of hollow ball-shape silica template and organic RESEARCH OF PYROCARBON raw material is 1:3 ~ 1:20, and organic RESEARCH OF PYROCARBON raw material is selected from glucose or sucrose; Inert atmosphere comprises nitrogen and argon gas.
More preferably, in step 11, the mass fraction of hydrofluoric acid is 5% ~ 40%.
In better embodiment of the present invention, the embedding first lithium capacity of products obtained therefrom is 2496mAh/g, and reversible de-lithium capacity is 1254mAh/g, and after 40 circulations, Reversible lithium insertion capacity is 978mAh/g.
The invention has the beneficial effects as follows:
The invention provides a kind of multilayer carbon hollow ball negative material, this material not only keeps the advantage of single wall hollow carbon nanosphere, has thin carbon shell, and there is hollow structure; And inner containing multilayer carbon structure due to it, volume utilization is high, effectively can improve the shortcoming that single wall hollow carbon balls energy density is low, specific capacity is low.And the method technique of this material of preparation provided by the invention is simple, and environmental friendliness, is easy to realize suitability for industrialized production.
Be described further below with reference to the technique effect of accompanying drawing to design of the present invention, concrete structure and generation, to understand object of the present invention, characteristic sum effect fully.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of the negative material that embodiments of the invention 3 obtain;
Fig. 2 is the high power TEM Electronic Speculum figure of the hollow ball of double-layer carbon shown in Fig. 1 negative material;
Fig. 3 is the low power TEM Electronic Speculum figure of the hollow ball of double-layer carbon shown in Fig. 1 negative material;
The lithium ion battery charging and discharging curve figure 3 times that Fig. 4 assembles for the hollow ball of double-layer carbon shown in Fig. 1 negative material;
The capacity versus cycle frequency curve (current density is 50mA/g) of front 40 circulations of lithium ion battery that Fig. 5 assembles for negative material shown in Fig. 1;
Fig. 6 is the high power TEM Electronic Speculum figure of four layers of carbon hollow ball negative material that embodiment 4 obtains;
Fig. 7 is the low power TEM Electronic Speculum figure of four layers of carbon hollow ball negative material of embodiment 4;
Fig. 8 is the lithium ion battery charging and discharging curve figure 3 times of four layers of carbon hollow ball negative material assembling shown in Fig. 6;
The capacity versus cycle frequency curve (current density is 50mA/g) of front 40 circulations of lithium ion battery that Fig. 9 is four layers of carbon hollow ball negative material assembling shown in Fig. 6.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.
Embodiment 1
The preparation of individual layer hollow silica ball template:
At room temperature, by 0.088g neopelex and 0.087g dodecyl sulfobetaine, add in 10ml deionized water, this solution is heated to 40 DEG C in water bath, stir 1 hour; 3-aminopropyl triethoxysilane 55 μ l, tetraethoxysilane 400 μ l is instilled above-mentioned solution respectively, stirs 2 hours; Then mixed solution is heated to 70 DEG C in oil bath pan, is incubated 40 hours; After reaction terminates, the centrifugal mode of product is collected, use ethanol and deionized water repeatedly washed product respectively, dry; Then product is added 50ml concentrated hydrochloric acid (mass percent 36%) acetonitrile mixed solution (hydrochloric acid acetonitrile volume ratio is 1:3), stir 4 hours, again with deionized water washing, dry, obtain individual layer silicon dioxide hollow sphere material.
Embodiment 2
The preparation of double-deck hollow silica ball template:
At room temperature, 0.044g neopelex and 0.043g dodecyl sulfobetaine are pressed 1:1 mixed in molar ratio, add in 10ml deionized water, magnetic agitation 1.5h; Then, 5ml individual layer hollow silica ball suspension (5mg/mL) is dropwise instilled in above-mentioned mixed surfactants solutions, Keep agitation in the process; Above-mentioned solution is heated to 50 DEG C in water bath, stirs 2h; 3-aminopropyl triethoxysilane 80 μ l, tetraethoxysilane 400 μ l is instilled above-mentioned solution respectively, stirs 1 hour; Then mixed solution is heated to 90 DEG C in oil bath pan, is incubated 15 hours; After reaction terminates, the centrifugal mode of product is collected, use ethanol and deionized water washed product respectively, dry; Then product is added 50ml concentrated hydrochloric acid (38%) acetonitrile mixed solution (hydrochloric acid acetonitrile volume ratio is 1:5), stir 7 hours, again wash, dry, obtain double-deck silicon dioxide hollow sphere material.
Embodiment 3
The preparation of double-layer carbon hollow ball negative material:
The individual layer hollow silica ball template of gained in 0.1g embodiment 1 is added in 10ml pure water and stirs, add 0.5g glucose, stir 1 hour, solution is poured in 15ml reactor, in baking oven, 170 DEG C are incubated 8 hours, after reaction terminates, product ethanol and deionized water are repeatedly washed, dry.Be laid in by dried product (other refractory containers available replace corundum porcelain boat) in corundum porcelain boat, the lower 650 DEG C of calcinings of argon gas atmosphere 8 hours, after cooling, obtain intermediate product.Again products therefrom is added in 40% hydrofluoric acid solution, stir 1 hour, namely obtain double-layer carbon hollow ball negative material.
Fig. 1 is the X-ray diffractogram of gained sample, can find out from Fig. 1, and 23 ° have outside a broad peak, 43
°also have a little broad peak, be the diffraction maximum of carbon, this shows that this kind of structure is agraphitic carbon, there is no other impurity.
Fig. 2 is the high power TEM electron microscopic picture of gained sample, and obviously can find out that from Fig. 2 this material is hollow-core construction, shell is the two-layer carbon-coating be separated from each other, and carbon layers having thicknesses is about 7nm.Fig. 3 is the low power TEM electron microscopic picture of gained sample, and as can be seen from Figure 3, sample is hollow-core construction, and pattern is clear, and the size of ball is 50 ~ 150nm.
The preparation of electrode: products therefrom is mixed according to the weight ratio of 6:2:2 with carbon black, polyvinylidene fluoride, mix with nitrogen methylpyrrolidone solution again, slurry viscosity is regulated with nitrogen methyl pyrrolidone, then by slurry with scraper uniform application on the Copper Foil through alcohol washes, vacuumize 10 hours at 120 DEG C, then through compressing tablet, cutting, obtained Electrode.
Electrode performance is tested: in fastening lithium ionic cell, carry out performance test.Battery assembling mode is as follows: using lithium sheet as to electrode, and Celgard2300 is as barrier film, and electrolyte adopts concentration to be the LiPF of 1M
6eC-DEC-EMC (1:1:1) solution, LiPF
6be lithium hexafluoro phosphate, EC is ethylene carbonate, and DEC is diethyl carbonate, and EMC is methyl ethyl ester.During test, temperature is room temperature, and adopt constant current charge-discharge, current density is 50mA/g, and control reference voltage is 0 ~ 3V.
Fig. 4 is above-mentioned lithium ion battery charging and discharging curve figure 3 times, shows in Fig. 4, and by this implementation Process, the embedding first lithium capacity of products obtained therefrom is 1746mAh/g, and reversible de-lithium capacity is 855mAh/g; Fig. 5 is the capacity versus cycle frequency curve of lithium ion battery front 40 circulations under current density is 50mA/g, and after 40 circulations, Reversible lithium insertion capacity is 712mAh/g.
Embodiment 4
The preparation of four layers of carbon hollow ball negative material:
The double-deck hollow silica ball template of gained in 0.2g embodiment 2 is added in 10ml pure water and stirs, add 2g sucrose, stir 2 hours, solution is poured in 15ml reactor, in baking oven, 180 DEG C are incubated 4 hours, product ethanol and deionized water are repeatedly washed after reaction terminates, dry.Be laid in porcelain boat by dried product, the lower 800 DEG C of sintering of argon gas atmosphere 4 hours, after cooling, obtain intermediate product.Again products therefrom is added in 10% hydrofluoric acid solution, stir 5 hours, namely obtain four layers of carbon hollow ball negative material.
Fig. 6 is the high power TEM electron microscopic picture of gained sample, obviously can find out that this material is hollow-core construction from Fig. 6, and shell is the four layers of carbon-coating be separated from each other, and carbon layers having thicknesses is about 5nm.Fig. 7 is the low power TEM electron microscopic picture of gained sample, and as can be seen from Figure, sample is hollow-core construction, and pattern is clear, and the size of ball is 100 ~ 200nm.
Using four layers of carbon hollow ball particle as active material, metal lithium sheet becomes fastening lithium ionic cell as to electrode assembling.Fig. 8 is battery charging and discharging curve figure 3 times for this reason, shows in Fig. 8, and the embedding first lithium capacity of products obtained therefrom is 2496mAh/g, and reversible de-lithium capacity is 1254mAh/g; Fig. 9 is battery front capacity versus cycle frequency curve circulated for 40 times under current density is 50mA/g for this reason, and after its 40 times circulations, Reversible lithium insertion capacity is 978mAh/g.
More than describe preferred embodiment of the present invention in detail.Should be appreciated that those of ordinary skill in the art just design according to the present invention can make many modifications and variations without the need to creative work.Therefore, all technical staff in the art, all should by the determined protection range of claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (10)
1. a multilayer carbon hollow ball negative material, it is characterized in that, described negative material is the carbon spherical structure of hollow, states negative material and comprises multilayer carbon shell, described carbon shell is the armorphous nano carbon-coating that organic substance is formed after polycondensation, carbonization, and described multilayer is double-deck or four layers.
2. multilayer carbon hollow ball negative material as claimed in claim 1, it is characterized in that, the diameter of described multilayer carbon hollow ball is 50 ~ 300nm, and the thickness of described carbon shell is 3 ~ 20nm.
3. the preparation method of a kind of multilayer carbon hollow ball negative material as described in any one of claim 1 to 2, is characterized in that, comprise the steps:
Steps A: organo-silicon compound are hydrolyzed in the aqueous solution of surfactant, obtain individual layer hollow ball-shape silica template, organo-silicon compound are added in the aqueous surfactant solution being mixed with individual layer hollow ball-shape silica spheres, obtain double-layer hollow spherical silicon dioxide template through hydrolysis;
Step B: the list that steps A is obtained/double-layer hollow spherical silicon dioxide surfaces externally and internally adheres to organic RESEARCH OF PYROCARBON raw material, described organic RESEARCH OF PYROCARBON raw material is through hydro-thermal reaction aftercondensated;
Step C: organic RESEARCH OF PYROCARBON raw material of polycondensation is coated on described hollow ball-shape silicon dioxide surfaces externally and internally under inert atmosphere protection after carbonization, obtained hollow shape nano composite material has carbon-silica-carbon " sandwich " shell structurre;
Step D: etched by the silica template hydrofluoric acid solution in described hollow shape nano composite material, obtains bilayer/tetra-layer carbon hollow ball.
4. preparation method as claimed in claim 3, it is characterized in that, described organo-silicon compound are 3-aminopropyl triethoxysilane and tetraethoxysilane, and described surfactant is neopelex and dodecyl sulfobetaine.
5. the preparation method of a kind of multilayer carbon hollow ball negative material as claimed in claim 4, is characterized in that, comprise the steps:
Step one: under room temperature, adds in deionized water using neopelex and dodecyl sulfobetaine as surfactant, magnetic agitation 0.5 ~ 2 hour, forms surfactant solution;
Step 2: described surfactant solution is heated to 40 ~ 50 DEG C, then 3-aminopropyl triethoxysilane and tetraethoxysilane are instilled respectively, stir 0.5 ~ 2 hour, be formed with the mixed solution of organic silicon compound and surfactant;
Step 3: the solution of described organo-silicon compound and surfactant is heated to 70 ~ 90 DEG C and is incubated 10 ~ 40 hours in oil bath pan, reaction terminates, and obtains product;
Step 4: use centrifugal mode to collect the product of described step 3, respectively with ethanol and deionized water described product is washed, dry, obtain dry product;
Step 5: the product of described drying added in acetonitrile hydrochloric acid mixed solution, stirs 4 ~ 8 hours, rear deionized water cleans again, dry, obtains described individual layer hollow ball-shape silica template;
Step 6: described individual layer hollow ball-shape silica template is added in the surfactant mixed solution of neopelex obtained by step one and dodecyl sulfobetaine, repeat step 2 again to step 5, i.e. obtained double-layer hollow spherical silicon dioxide template;
Step 7: described list/double-layer hollow spherical silicon dioxide template is joined in the aqueous solution of described organic RESEARCH OF PYROCARBON raw material, stir 0.5 ~ 2 hour, obtain mixed liquor;
Step 8: described mixed liquor is poured in reactor, the cumulative volume of described mixed liquor accounts for 1/2 ~ 3/4 of described reactor internal volume, is warming up to 170 ~ 200 DEG C and is incubated 2 ~ 8 hours, obtaining hydro-thermal reaction product;
Step 9: use centrifugation to collect described hydro-thermal reaction product, respectively with ethanol and deionized water washing, dry, obtain desciccate;
Step 10: described desciccate is placed in refractory container, 600 ~ 900 DEG C of calcinings are warming up under inert atmosphere protection, calcination time is 2 ~ 10 hours, then obtain the hollow Nano composite material with carbon-silica-carbon " sandwich " shell structurre feature;
Step 11: add in hydrofluoric acid solution by described hollow Nano composite material, stirs 1 ~ 8 hour, rear deionized water cleans again, dry, then obtain bilayer/tetra-layer carbon hollow ball.
6. preparation method as claimed in claim 5, it is characterized in that, in described step one, described neopelex and described dodecyl sulfobetaine take by equal molar quantities, and the mol ratio of described deionized water and described surfactant total amount is 2000:1 ~ 15000:1.
7. preparation method as claimed in claim 5, it is characterized in that, in described step 2, the described 3-aminopropyl triethoxysilane added and the mol ratio of described surfactant total amount are 2:1 ~ 2:5, and the mol ratio of the described tetraethoxysilane added and described surfactant total amount is 2:1 ~ 10:1.
8. preparation method as claimed in claim 5, is characterized in that, in described step 5, described acetonitrile hydrochloric acid mixed solution is that 1:1 ~ 1:3 configures and forms with volume ratio by concentrated hydrochloric acid and acetonitrile, described concentrated hydrochloric acid to be mass percent be 36% ~ 38% hydrochloric acid.
9. preparation method as claimed in claim 5, it is characterized in that, in described step 7, the mass ratio of described hollow ball-shape silica template and described organic RESEARCH OF PYROCARBON raw material is 1:3 ~ 1:20, described organic RESEARCH OF PYROCARBON raw material is selected from glucose or sucrose, and described inert atmosphere comprises nitrogen and argon gas.
10. preparation method as claimed in claim 5, it is characterized in that, in described step 11, the mass fraction of described hydrofluoric acid is 5% ~ 40%.
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