CN106986322A - A kind of preparation method and application of nitrogenous carbon material - Google Patents
A kind of preparation method and application of nitrogenous carbon material Download PDFInfo
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- CN106986322A CN106986322A CN201710285489.5A CN201710285489A CN106986322A CN 106986322 A CN106986322 A CN 106986322A CN 201710285489 A CN201710285489 A CN 201710285489A CN 106986322 A CN106986322 A CN 106986322A
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- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
- A24D3/06—Use of materials for tobacco smoke filters
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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Abstract
A kind of preparation method of nitrogenous carbon material, it is characterised in that：It is the method for preparing the nitrogenous step hole Carbon Materials of high porosity after being hydrolyzed using tobacco rod as raw material through solid acid catalysis through oxidation, ammonification, carbonization.By the addition successively of nitric acid hydrogen peroxide or hypochlorite hydrogen peroxide and subsequent step organic amine, prepare and be rich in N element carbon material.Nitrogenous step hole carbon material prepared by the present invention, there is certain distribution in the range of micropore, mesoporous, macropore, more suitable for the absorption of the wider coke tar in cigarette of particle diameter distribution, prepared nitrogenous step hole carbon material is made an addition into cigarette filter, the reducing effect to main flume Cd and tar is notable.It is an advantage of the invention that：Organic acid and alcohol reaction produced by solid acid catalysis cellulose hydrolysis generates ester, can avoid organic acid to the etching problem of reactor.The increase of element N content, is conducive to N to the cnmplexation adsorbability of Cd in flue gas, has obvious effect to the reduction of Cd in cigarette smoke.
Description
Technical field
The present invention relates to a kind of preparation method of nitrogenous carbon material, be specifically by tobacco rod crush after after catalyzing hydrolysis through oxygen
The method that change, ammonification, carbonization prepare the nitrogenous step hole carbon material of high porosity.The material can make an addition to cigarette filter, to flue gas
The reducing effect of Cd and tar is notable.
Background technology
China is World tobacco big country, and its cultivated area, total output, cigarette output and sales volume occupy first place in the world.
Substantial amounts of discarded object is inevitably produced in tobacco leaf and process, according to statistics, the cigarette stalk produced for only 2015 is just up to 1.163
×106Ton.Because cigarette stalk availability is relatively poor, the overwhelming majority is handled in the way of burying and abandoning or burn, comprehensive utilization ratio
It is extremely low, environmental pollution is not only caused, and waste substantial amounts of existing resource.
Heavy metal is mainly derived from the soil containing heavy metal, water and air etc. during tobacco planting in tobacco.Tobacco
In the heavy metal element such as lead, arsenic, chromium, cadmium human body can be entered by flue gas in the form of aerosol or metal oxide, pass through
Accumulate and then the healthy of people is caused harm.Research finds that in numerous heavy metals contained by tobacco, cadmium is to be easiest to
Absorbed element.With the continuous improvement of people's health consciousness, cadmium content has turned into smoking and paid close attention to health field in flue gas
Focus.Activated carbon is a class porosu solid carbon material, because it has flourishing gap structure and huge specific surface area, thus
Its unique strong absorption property is assigned, its chemical property stabilization is added, water insoluble and other most of solvents are inhaling it
It is used widely in the fields such as attached, separation, catalysis.Conventional acetate fiber filter tip has certain adsorptivity to cadmium and coke tar in cigarette
Can, research, which shows to make an addition to activated carbon after cigarette filter, can significantly lift it to cadmium and the absorption property of tar, it is seen then that living
Property charcoal is with a wide range of applications in terms of the absorption of cigarette smoke cadmium and tar..
Preparing activated carbon by tobacco rod generally includes the processes such as dry, carbonization, activation, wherein activation is the key of pore-creating,
Conventional method can be divided into two kinds of physical process and chemical process.
Physical activation method is related to the oxidizing gas such as vapor, carbon dioxide, air.In the comprehensive utilization of tobacco rod, the summer
Flood, which is answered et al., is respectively adopted carbon dioxide and vapor activation is prepared for pore type cigarette stalk base granular activated carbon（Full in summer is answered, Peng
Research [J] gold .2006 (07) of the preparation of granular activated carbon from tobacco stems with carbon dioxide such as Jin Hui, Zhang Libo:38-41.
Full in summer is answered, Peng Jinhui, and research [J] the ion exchanges of the Preparation of Granular Activated Carbon From Tobacco Stems Activation By Steam such as Zhang Libo are with inhaling
Attached .2007 (02):112-118. fulls in summer are answered, Peng Jinhui, and the microwave radiations-steam method such as Zhang Libo prepares the work of tobacco rod base particle
Property charcoal [J] Chemical Engineerings .2007 (01):48-51.）.Carbon material BET specific surface area prepared by this method is relatively low, and
The hole overwhelming majority belongs to micropore, and mesoporous and macropore content is very low.
Chemical activation method is that highly basic, strong acid or strong oxidizer chemical reagent, such as HNO are added into raw material in activation stage3、
KOH、MnO2、ZnCl2Deng a kind of method.On March 3rd, 2004, " microwave radiation tobacco rod solid waste manufactured the side of activated carbon
Method "（Application number CN02113270.4, publication number CN1140449C）One kind is disclosed by tobacco rod with being passed through after liquor zinci chloridi dipping
Heat the method for obtaining activated carbon product.There is the volatilization pollution problem of zinc chloride in actual production process in this method.2005
On September 21, " a kind of method for producing active carbon with high specific surface area "（Application number CN200510010670.2, publication number
CN1669918A）Disclose a kind of side that tobacco rod and potassium hydroxide solution are impregnated again to heated production active carbon with high specific surface area
Method.On 2 17th, 2010 " a kind of preparation method of high mesoporous activated carbon "（Application number CN200910184645.4, publication number
CN101648707A）, disclose a kind of high by biomass material, phosphoric acid and assistant activator（Peroxide or over cure compound）Mixing leaching
The method that stain, heating activation prepare activated carbon product.CN1669918A and publication number CN101648707A due to alkali or acid make
Be under the high temperature conditions, it is therefore serious to the etching problem of equipment.
The content of the invention：
A kind of preparation method for nitrogenous carbon material that the purpose of the present invention is exactly provided for the deficiency or defect of above technology,
Specifically tobacco rod first carries out partial hydrolysis in the presence of solid acid, and filter residue is carbonized, then oxidized, amine hot two
Secondary carbonization can obtain step hole N doping carbon materials.Material effect in terms of Cd in reducing cigarette smoke and tar is notable.
（Referring to bibliography：Heavy metal cadmium and regulation measure progress in tobacco, Chinese agriculture science and technology Leader, 2011,13
(2):93-98.）
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of nitrogenous carbon material, is the method that the nitrogenous carbon material in step hole is prepared by raw material of tobacco rod, specific step
It is rapid as follows：
1）Pretreatment of raw material：Tobacco rod raw material is dried to moisture content at 60 ~ 120 DEG C below 5%, the mesh of particle size 200 is crushed to
Hereinafter, preferably 20-150 mesh；
2) mix：By 1）Gained powder stock is added to ball milling with alcohol solution, solid acid in mass ratio 1: 5-15: 0.05-0.2
Ball milling is carried out in tank（Rotating speed 200-500 turns/min）Mixing, time 2-5 hour；
3）Hydrolysis：By 2）Middle feed liquid is transferred in reactor after being separated with grinding bead, in 100 ~ 200 DEG C, 5 ~ 20 MPa stirring conditions
1 ~ 24 h of lower reaction；
4）Carbonization：By 3）Reacting liquid filtering or centrifuge it is residue obtained, insert in high temperature furnace nitrogen or helium atmosphere 600 ~
Be carbonized 1-5h at 800 DEG C；
5）Purification：By 4）Products obtained therefrom is soaked in nitric acid-hydrogen peroxide or hypochlorite-hydroperoxide solution, soaking temperature
30-100 DEG C, time 0.5-12h is washed afterwards, standby；In nitric acid-hydrogen peroxide or hypochlorite-hydroperoxide solution
Concentration of nitric acid is 1-8M, and hypochlorite concentration is 1-8M, and concentration of hydrogen peroxide is 0.5-8 M.
6）Secondary carbonization：5) gained solid is placed in water heating kettle, Amine Solutions are added, addition is 5）Middle raw material body
Under long-pending 1-4 times, 150-500 DEG C of self-generated pressure（Because be in closed water heating kettle reactor, when temperature is higher, the inside
Material is substantially at subcritical or supercriticality, and pressure following temperature change is obvious, therefore the confined reaction pressure under high temperature
It is the automatic pressure of system）Carry out secondary carbonization 1-24 h；Solute in Amine Solutions is diethylamine, triethylamine, butanediamine,
Any one in hexamethylene diamine, propylamine, butylamine, amylamine, the solvent in Amine Solutions is one kind of water, alcohol or ethers.
7）Washing：By 6）Room temperature is cooled to after carbonization, is then separated, and is washed with deionized for several times, step hole is produced
Nitrogenous carbon material.
In the present invention, solid acid used be Si-Al molecular sieve include HY, Hbeta, HZSM-5, HZSM-22, HZSM-11,
MCM-22、HZSM-35；The silane-modified mesoporous material of sulfonic acid includes SO3H-SBA-15、SO3H-SBA-16、SO3H-MCM-41、
SO3H-MCM-48、SO3H-MCM-50.The concentration of the alcohol solution is 5 ~ 10%wt；Alcohol solution is methanol aqueous solution, ethanol
Any one in the aqueous solution, aqueous propanol solution, glycol water.
Grinding bead in ball grinder is agate bead.
Nitrogenous carbon material prepared by the present invention is applied in cigarette filter, and the reducing effect to flue gas Cd and tar shows
Write.
Advantages of the present invention is as follows：
1st, tobacco rod is handled using solid acid and alcoholic solution, it is to avoid to the etching problem of equipment in preparation process.Nitric acid-peroxidating
The addition successively of hydrogen or hypochlorite-hydrogen peroxide and subsequent step organic amine, prepares and is rich in N element carbon material.
2nd, prepared step hole carbon material, in micropore（<2 nm）, mesoporous hole（2~50 nm）, macropore（>50 nm）Scope
Inside there is certain distribution, the increase of element N content is conducive to N to the cnmplexation adsorbability of Cd in flue gas, in cigarette smoke
The reducing effect of Cd and tar is notable.
3rd, the use of solid acid has reached that tobacco rod is carbonized and obtains the purpose of step hole carbon products.
Embodiment
The present invention is described further with reference to embodiments:
Embodiment 1
Tobacco rod raw material is placed in baking oven at 60 DEG C and is dried to moisture content below 5%, 20 ~ 40 mesh is crushed to, weighs 10 g samples, press
According to solid-liquid volume ratio 1:15 and methanol aqueous solution（Methanol concentration 5%wt）Mixed and be transferred in ball grinder, add HY molecules
Sieve 1.0 g（The 10% of tobacco rod weight）The h of mixed at room temperature 5 is carried out under 300 turns/min rotational speed of ball-mill, feed liquid is obtained.By feed liquid with
It is transferred to after agate bead separation under autoclave, nitrogen atmosphere and 24 h is reacted under 100 DEG C, 5 MPa.Reacting liquor while hot mistake
Filter, deionized water is washed three times, and progress 5 h of carbonization under the conditions of lower 600 DEG C of nitrogen atmosphere in tube furnace are placed in after filter residue and drying, are obtained
Char-forming material.Char-forming material is immersed in 200 ml 1 M HNO3-0.5 M H2O2100 DEG C are returned in mixed solution
12 h are flowed, centrifugation after room temperature, deionized water is down to and washs three times, be transferred in water heating kettle, add 20 ml ethylenediamine solutions
（Ethylenediamine volumetric concentration is 50%）, Mobile state is entered at 150 DEG C（Dynamic belongs to the term of preparation process, and expression is being stirred or rocked
Reacted under state, its antisense reverse side is exactly static.）24 h of secondary carbonization, by filtering, wash, are drying to obtain step hole
Nitrogenous carbon material 1#.Texture parameter and the element composition of prepared carbon material are shown in Table 1.
Embodiment 2
Tobacco rod raw material is placed in 80 DEG C of baking oven and is dried to moisture content below 5%, 40 ~ 60 mesh are crushed to, 10 g samples are weighed, according to solid
Liquid volume ratio 1:5 and aqueous propanol solution（Propanol concentration 10%wt）Carry out mixing to be transferred in ball grinder, add SO3H-MCM-41
The g of mesoporous material 0.5（The 5% of tobacco rod weight）The h of mixed at room temperature 2 under 200 turns/min rotational speed of ball-mill.By feed liquid and agate bead
It is transferred to after separation under autoclave, nitrogen atmosphere and 1 h is reacted under 200 DEG C, 5 MPa.Reacting liquor while hot is filtered, deionization
Water washing three times, is placed under the conditions of lower 800 DEG C of nitrogen atmosphere in tube furnace 1 h that is carbonized, obtains a char-forming material after filter residue and drying.
Char-forming material of gained is immersed in 200 ml 4 MHNO3-2 M H2O270 DEG C of 8 h of backflow, are down to room temperature in mixed solution
After centrifuge, and be washed with deionized three times, be transferred in water heating kettle, the 40 ml hexamethylene diamine aqueous solution are added, at 250 DEG C
Enter Mobile state 15 h of secondary carbonization, by filtering, wash, be drying to obtain the nitrogenous carbon material 2# in step hole.Prepared carbon material
Texture parameter and element composition are shown in Table 1.
Embodiment 3
Tobacco rod raw material is placed in baking oven 100 DEG C and is dried to moisture content below 5%, 60 ~ 90 mesh is crushed to, weighs 10 g samples, according to
Solid-liquid volume ratio 1:10 and ethanol water（Concentration of alcohol 8%wt）Mixed and be transferred in ball grinder, add HZSM-5 points
2.0 g of son sieve（The 20% of tobacco rod weight）The h of mixed at room temperature 4 under 400 turns/min rotational speed of ball-mill.Feed liquid is separated with agate bead
After be transferred in autoclave, 14 h are reacted under nitrogen atmosphere under 150 DEG C, 12 MPa.Reacting liquor while hot is filtered, deionization
Water washing three times, is placed in progress 2 h of carbonization under the conditions of lower 700 DEG C of nitrogen atmosphere in tube furnace, obtains and be once carbonized after filter residue and drying
Material.Carbon material of gained is immersed in 200 ml 8 MHNO3-8 M H2O230 DEG C of 0.5 h of stirring in mixed solution, then
Washing three times, is transferred in water heating kettle, adds the ethanol solution of 30 ml n-butylamines, Mobile state 1 h of secondary carbonization is entered at 500 DEG C,
By filtering, wash, be drying to obtain the nitrogenous carbon material 3# in step hole.Texture parameter and the element composition of prepared carbon material are shown in Table
1。
Embodiment 4
Tobacco rod raw material is placed in baking oven 120 DEG C and is dried to moisture content below 5%, 100 ~ 120 mesh is crushed to, weighs 10 g samples, press
According to solid-liquid volume ratio 1:10 and ethanol water（Concentration of alcohol 8%wt）Mixed and be transferred in ball grinder, add HZSM-
The g of 11 molecular sieve 2.0（The 20% of tobacco rod weight）The h of mixed at room temperature 2, obtains feed liquid under 400 turns/min rotational speed of ball-mill.By feed liquid
It is transferred to after being separated with agate bead under autoclave, nitrogen atmosphere and 24 h is reacted under 200 DEG C, 20 MPa.Reacting liquor while hot
Filtering, deionized water is washed three times, and progress 4 h of carbonization under the conditions of lower 750 DEG C of nitrogen atmosphere in tube furnace are placed in after filter residue and drying,
Obtain a char-forming material.Char-forming material of gained is immersed in the MHNO of 200 ml 43-6 M H2O230 DEG C of stirrings in mixed solution
0.5 h, then deionization washing three times, is transferred in water heating kettle, the ml n-butylamine aqueous solution of tobacco rod volume 40 is added, at 500 DEG C
Enter Mobile state 3 h of secondary carbonization, by filtering, wash, be drying to obtain the nitrogenous carbon material 4# in step hole.Prepared carbon material is knitted
Structure parameter and element composition are shown in Table 1.(element composition is the composition of the essential element of prepared carbon material（Surveyed by elemental analyser
）, it is primarily intended to react N element content higher in prepared N doping carbon material)
Prepared carbon material is made an addition into cigarette filter, addition is every 20 mg, and comparative sample is convention filter cigarette.Will
Corresponding cigarette testing sample balances 48 h, the cigarette total amount of screening under the conditions of temperature (22 ± 1) DEG C, relative humidity (60 ± 1) %
Difference scope is ± 0.01 g, with 20 H type carousel-type smoking machines according to GB/T 16450-2004 smoking machines and its testing standard
Condition（Wind speed is (200 ± 30) mm/s, pumping volume (35 ± 0.3) ml, the s of duration 2, the s of puff interval 60）Suction
Cigarette, with the middle granule phase substance of electrostatic paved set pipe paved set main flume, gas phase is collected with 20 ml10% (v/v) salpeter solution.According to
According to YC/T379-2010《The measure inductively coupled plasma mass spectrometry of chromium, nickel, arsenic, selenium, cadmium, lead in cigarette mainstream flue gas》
Determine the Cd in cigarette mainstream flue gas.The tar content in cigarette sample gas phase is measured according to GB/T 19609-2004.
As a result it is as shown in table 2.Result can be seen that compared with control sample from table 2, the carbon material Cd and tar side in reduction flue gas
Significantly, highest is respectively up to 48.7% and 34.9% for face effect.
。
Claims (9)
1. a kind of preparation method of nitrogenous carbon material, it is characterised in that：It is that the nitrogenous carbon material in step hole is prepared by raw material of tobacco rod
Method, comprise the following steps that：
1）Pretreatment of raw material：Tobacco rod raw material is dried to moisture content at 60 ~ 120 DEG C below 5%, the mesh of particle size 200 is crushed to
Below；
2）Mixing：By 1）Gained powder stock is added to ball milling with alcohol solution, solid acid in mass ratio 1: 5-15: 0.05-0.2
Ball milling mixing, time 2-5 hour are carried out in tank；
3）Hydrolysis：By 2）Middle feed liquid is transferred in reactor after being separated with grinding bead, in 100 ~ 200 DEG C, 5 ~ 20 MPa stirring conditions
1 ~ 24 h of lower reaction；
4）Carbonization：By 3）Reacting liquid filtering or centrifuge it is residue obtained, insert in high temperature furnace nitrogen or helium atmosphere 600 ~
Be carbonized 1-5h at 800 DEG C；
5）Purification：By 4）Products obtained therefrom is soaked in nitric acid-hydrogen peroxide or hypochlorite-hydroperoxide solution, soaking temperature
30-100 DEG C, time 0.5-12h is washed afterwards, standby；
6）Secondary carbonization：5) gained solid is placed in water heating kettle, Amine Solutions are added, addition is 5）Middle raw material volume
1-4 times, secondary carbonization 1-24 h are carried out under 150-500 DEG C of self-generated pressure；
7）Washing：By 6）Room temperature is cooled to after carbonization, is then separated, and is washed with deionized for several times, step hole is produced nitrogenous
Carbon material.
2. the preparation method of nitrogenous carbon material according to claim 1, it is characterised in that：Solid acid used is silicoaluminophosphate molecular
Sieve includes HY, Hbeta, HZSM-5, HZSM-22, HZSM-11, MCM-22, HZSM-35；The silane-modified mesoporous material of sulfonic acid includes
SO3H-SBA-15、SO3H-SBA-16、SO3H-MCM-41、SO3H-MCM-48、SO3H-MCM-50。
3. the preparation method of nitrogenous carbon material according to claim 1, it is characterised in that：The concentration of the alcohol solution is
5~10%wt；Alcohol solution is any one in methanol aqueous solution, ethanol water, aqueous propanol solution, glycol water.
4. the preparation method of nitrogenous carbon material according to claim 1, it is characterised in that：Step 2）In ball milling when turn
Speed turns/min for 200-500.
5. the preparation method of nitrogenous carbon material according to claim 1, it is characterised in that：Grinding bead in ball grinder is agate
Nao pearls.
6. the preparation method of nitrogenous carbon material according to claim 1, it is characterised in that：Step 1）In particle size it is excellent
Elect 20-150 mesh as.
7. the preparation method of nitrogenous carbon material according to claim 1, it is characterised in that：Step 5）Described in nitric acid-
Concentration of nitric acid in hydrogen peroxide or hypochlorite-hydroperoxide solution is 1-8M, and hypochlorite concentration is 1-8M, peroxide
Change hydrogen concentration is 1-8 M.
8. the preparation method of nitrogenous carbon material according to claim 1, it is characterised in that：Step 6）In Amine Solutions
In solute be diethylamine, triethylamine, butanediamine, hexamethylene diamine, propylamine, butylamine, amylamine in any one, in Amine Solutions
Solvent be water, alcohol or ethers one kind.
9. a kind of application of nitrogenous carbon material, it is characterised in that：Nitrogenous carbon material application prepared by claim 1 methods described
In cigarette filter, the reducing effect to flue gas Cd and tar is notable.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112551505A (en) * | 2020-12-11 | 2021-03-26 | 广东凯金新能源科技股份有限公司 | Preparation method of hard carbon-based negative electrode material |
| CN112645328A (en) * | 2020-12-21 | 2021-04-13 | 中国烟草总公司郑州烟草研究院 | Preparation method and application of nitrogen-containing porous carbon material |
| CN113694892A (en) * | 2021-08-27 | 2021-11-26 | 伯克利南京医学研究有限责任公司 | Carbon aerogel composite structure, composite filter element, preparation methods of carbon aerogel composite structure and composite filter element, and application of carbon aerogel composite structure and composite filter element |
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|---|---|---|---|---|
| CN101407323A (en) * | 2008-09-16 | 2009-04-15 | 上海第二工业大学 | Method for preparing pressed active carbon from tobacco stalk |
| CN106475052A (en) * | 2016-11-16 | 2017-03-08 | 中国科学院烟台海岸带研究所 | A kind of application seaweed biomass prepares nano-sized magnesium hydroxide/N doping porous carbon composite material and preparation method thereof |
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2017
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407323A (en) * | 2008-09-16 | 2009-04-15 | 上海第二工业大学 | Method for preparing pressed active carbon from tobacco stalk |
| CN106475052A (en) * | 2016-11-16 | 2017-03-08 | 中国科学院烟台海岸带研究所 | A kind of application seaweed biomass prepares nano-sized magnesium hydroxide/N doping porous carbon composite material and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112551505A (en) * | 2020-12-11 | 2021-03-26 | 广东凯金新能源科技股份有限公司 | Preparation method of hard carbon-based negative electrode material |
| WO2022121141A1 (en) * | 2020-12-11 | 2022-06-16 | 广东凯金新能源科技股份有限公司 | Method for preparing hard carbon-based negative electrode material |
| CN112645328A (en) * | 2020-12-21 | 2021-04-13 | 中国烟草总公司郑州烟草研究院 | Preparation method and application of nitrogen-containing porous carbon material |
| CN113694892A (en) * | 2021-08-27 | 2021-11-26 | 伯克利南京医学研究有限责任公司 | Carbon aerogel composite structure, composite filter element, preparation methods of carbon aerogel composite structure and composite filter element, and application of carbon aerogel composite structure and composite filter element |
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