CN102956876A - Pyrolytic hard charcoal material and preparation method and use thereof - Google Patents
Pyrolytic hard charcoal material and preparation method and use thereof Download PDFInfo
- Publication number
- CN102956876A CN102956876A CN2012105058118A CN201210505811A CN102956876A CN 102956876 A CN102956876 A CN 102956876A CN 2012105058118 A CN2012105058118 A CN 2012105058118A CN 201210505811 A CN201210505811 A CN 201210505811A CN 102956876 A CN102956876 A CN 102956876A
- Authority
- CN
- China
- Prior art keywords
- hard carbon
- pyrolytic
- carbon material
- average thickness
- carbon precursor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a pyrolytic hard charcoal material and a preparation method and a use thereof. The pyrolytic hard charcoal material is a two dimensional plane-similar sheeting material which is formed by pyrolysing a precursor of the hard charcoal, wherein the average thickness is 1-200nm and the geometric surface area is 10-2000 square meter/g. Micropores or mesopores exist in the pyrolytic hard charcoal material. The invention further provides a method of the pyrolytic hard charcoal material. The sheet pyrolytic hard charcoal material similar to graphene in shape is extremely wide in application and can be applied to preparing a cathode material of a lithium ion battery or a sodium ion battery, an electrode material of an electrochemical capacitor, a carrier for a fuel cell and a metal air battery electrode catalyst, a composite material with great toughness effect, a toxic material absorbent, an absorbent for special use, and a decolorising agent and a gas sensitive element in food production.
Description
Technical field
The present invention relates to a kind of material with carbon element and preparation method thereof, relate in particular to a kind of pyrolytic hard carbon material and its production and use.
Background technology
Hard charcoal refers to difficult graphitized carbon, is the pyrolytic carbon of high molecular polymer.All the time, hard carbon material because of its height ratio capacity, have extended cycle life, characteristics such as cost that power-performance is good, cheap get more and more people's extensive concerning as lithium ion battery negative material, it can also as the carrier of electrode material, chemistry and the electro chemical catalyst of the negative material of sodium-ion battery, electrochemical capacitor, be applied to gas sensor etc.
The application of hard carbon material and the structure of hard carbon material and shape characteristic are the important contents of this investigation of materials on using the impact of effect all the time.Numerous researchs find that internal pore structure and surface appearance feature have material impact for the application performance of hard carbon material.Therefore, explore the hard carbon material that more effective preparation method obtains having needed grain structure feature and shape characteristic, also become one of problem that receives much attention.For example, WO01/98209 discloses the pyrolytic hard carbon material of spheroid or spheroid, it is a kind of hard charcoal ball by the hydro thermal method preparation, it contains micropore, has spherical morphology, as the negative material of lithium ion battery, be conducive to improve reversible capacity and the cycle characteristics of battery, can obtain the higher and good lithium ion battery negative material of cycle performance of specific capacity at its area load nanometer tin antimony alloy.Although the hard carbon material of this spherical morphology had particle size distribution evenly, the advantage of higher bulk density, further increasing specific surface area is to increase the limited space of nano material load capacity.Utilize the hard carbon material of hard charcoal predecessor carrying out pyrolysis charing preparation to have more excellent application performance, in industry admitted gradually.With the example that is applied as of cathode of lithium battery, structure and the embedding lithium capacity of hard charcoal are considered to very large with the cracking technology relation.So, also have some correlative studys to report the hard carbon material that obtains by the control pyrolytic process.The focus of research has been placed on the adjustment of pyrolytic process (temperature and time etc.) and the selection of pyrolysis feed (hard carbon precursor) more; namely; hard carbon precursor is placed under the protective atmosphere; control corresponding pyrolytical condition, with expectation hard product char appearance structure and surface that pyrolysis forms are improved.
Summary of the invention
The object of the present invention is to provide a kind of pyrolytic hard carbon material, described hard carbon material is the laminar of nanometer grade thickness, the spheroid of putting down in writing in the prior art or the pyrolytic hard carbon material of spheroid, the laminar hard carbon material of this nanometer grade thickness has high geometrical surface, can effectively promote its performance in various practical applications.
The present invention also provides a kind of method for preparing described pyrolytic hard carbon material, by the adjustment to the pyrolytic process of hard carbon precursor, make the laminar pyrolytic hard carbon material of the similar Graphene of profile, and this preparation method has the advantage that technique is simple, cost is low, be easy to control.
One aspect of the present invention provides a kind of pyrolytic hard carbon material, wherein, this hard carbon material be that hard carbon precursor pyrolysis forms, have average thickness 1-200nm, a geometrical surface 10-2000m
2The sheeting of the similar two dimensional surface of/g, described pyrolytic hard carbon material inside exists micropore or mesopore.
The inventor studies confirm that, the hard charcoal of flaky texture has high geometrical surface, and the laminar hard charcoal of this similar Graphene, because unique shape characteristic and surface characteristic, various performances in actual applications obtain larger lifting.
In the present invention, term " sheeting ", be interpreted as this hard carbon material and be obvious laminated structure in geometry, with respect to larger surface, abutment surface can be used as thickness and has significantly little size, can see by SEM figure substantially presenting laminar distribution, and certain thickness is arranged, so also think similar or near two dimensional surface (its smallest radial is far longer than the average thickness of thin slice, and thickness is little of being left in the basket than larger surface in other words).Term " geometrical surface " can be understood as: this laminar hard carbon material, can see by SEM figure and substantially to present laminar distribution, and certain thickness arranged, but can there be simultaneously some overlapping and zones fold, we utilize geometrical surface to describe and limit this laminar hard carbon material under the approximate ideal state in the present invention, launch in zone it is folding and fold, is the surface area under the flat expand state.
In the present invention, form laminar hard carbon material by the hard carbon precursor of pyrolysis, the main body composition of described laminar hard carbon material is carbon, also contain simultaneously other element that mass fraction is no more than 10wt%, accountable is that the laminar hard carbon material that the present invention proposes all embodies excellent performance in actual applications.
The present invention also provides the method for preparing described pyrolytic hard carbon material, and the method comprises the pyrolysis in atmosphere of hard carbon precursor, wherein,
The active gases that has comprised 1-100% in the described atmosphere;
Described hard carbon precursor pyrolytic process comprises at least: control gas flow 0.1-500mL/min is to provide atmosphere, hard carbon precursor and described gas are fully contacted form the pyrolysis system, and make the pyrolysis system be warming up to 400-2000 ℃ with the speed of 0.5-10 ℃/min, keep this temperature and be cooled to room temperature after 0-72 hour;
Described active gases comprises the gas that contains protium or the liquid vapour that contains protium.
According to embodiment of the present invention, in hard carbon precursor pyrolytic process, control gas flow 10-300mL/min.
According to embodiment of the present invention, in hard carbon precursor pyrolytic process, control pyrolysis system is warming up to 400-1500 ℃.
According to embodiment of the present invention, in hard carbon precursor pyrolytic process, after the pyrolysis system heats up end, be cooled to room temperature after holding temperature 0-20 hour.
Preparation method provided by the invention, hard carbon precursor is placed the atmosphere carrying out pyrolysis charing that contains active gases, beyond thought effect is the thin slice pattern that resulting hard product char shows similar Graphene, thereby the higher geometrical surface that provides can both demonstrate more excellent performance in the applied environment of hard carbon material.
Laminar hard carbon material provided by the invention, for example can be used in, the carrier of the negative material of lithium ion battery or sodium-ion battery, the electrode material of electrochemical capacitor, fuel cell and metal-air cell electrode catalyst, be used for preparing have the height increasing tougheness composite material, the adsorbent of noxious substance adsorbent, special purpose, the decolorizer in the food production and gas sensor.
Technical scheme of the present invention has following beneficial effect at least:
1, the invention provides a kind of pyrolytic hard carbon material and be the laminar of nanometer grade thickness, the spheroid of putting down in writing in the prior art or the pyrolytic hard carbon material of spheroid, the laminar hard carbon material of this nanometer grade thickness has high geometrical surface, can effectively promote its performance in actual applications.
2, the method for preparing pyrolytic hard carbon material provided by the invention, by hard carbon precursor technique of pyrolysis in atmosphere is controlled, make and the similar laminar pyrolytic hard carbon material of Graphene profile, and this preparation method has the advantage that technique is simple, cost is low, be easy to control.
3, the pyrolytic hard carbon material purposes of the laminar pattern with similar black alkene profile of the present invention is very extensive, not only can be used as present serondary lithium battery or the negative pole of sode cell, can also be as the electrode of electrochemical capacitor, and can also be as key material in fields such as catalytic field, medicine food manufacturings, such as carrier, sorbing material etc.
Description of drawings
Fig. 1 (a)-Fig. 1 (b) is the stereoscan photograph of the pyrolytic hard carbon material in the embodiment of the invention 1.
Fig. 2 is the stereoscan photograph of the pyrolytic hard carbon material in the embodiment of the invention 2.
Fig. 3 is the stereoscan photograph of the pyrolytic hard carbon material in the embodiment of the invention 3.
Fig. 4 is the stereoscan photograph of the pyrolytic hard carbon material in the embodiment of the invention 7.
Fig. 5 is the stereoscan photograph of the pyrolytic hard carbon material in the embodiment of the invention 10.
Fig. 6 (a)-Fig. 6 (b) is the stereoscan photograph of the pyrolytic hard carbon material in the Comparative Examples 1 of the present invention.
Fig. 7 is the stereoscan photograph of the pyrolytic hard carbon material in the Comparative Examples 2 of the present invention.
Fig. 8 is the X ray diffracting spectrum of the pyrolytic hard carbon material in the embodiment of the invention 1.
Fig. 9 is the Raman collection of illustrative plates of the pyrolytic hard carbon material in the embodiment of the invention 1.
Figure 10 is the electron diffraction diagram of the pyrolytic hard carbon material in the embodiment of the invention 1.
Figure 11 is that pyrolytic hard carbon material in the embodiment of the invention 1 is as the charging and discharging curve figure of lithium cell cathode material.
Figure 12 is the TEM figure of the pyrolytic hard carbon material of the embodiment of the invention 1.
Embodiment
The invention provides the laminar pyrolytic hard carbon material of the similar Graphene of a kind of appearance structure, average thickness 1-200nm, geometrical surface 10-2000m
2/ g, described pyrolytic hard carbon material inside exists micropore or mesopore.
According to embodiment of the present invention, the surface structure of the similar two dimensional surface that described laminar hard carbon material has, the smallest radial size is not less than 100:1 with the ratio of the average thickness of material on the larger plane of this sheeting, namely, described sheeting is similar two dimensional surface shape, and the smallest radial size on its plane is far longer than the nanometer grade thickness that this hard charcoal sheeting has.Among the present invention referred to as " smallest radial size and average thickness ratio ".
According to embodiment of the present invention, the control of pyrolytic process makes has had micropore and/or mesopore in the sheeting, particularly, micropore and/or mesopore in described this hard carbon material, micropore size can be less than 1nm, and the mesopore aperture is generally 2-20nm.
According to embodiment of the present invention, the average thickness 2-50nm of described laminar pyrolytic hard carbon material.
According to embodiment of the present invention, the geometrical surface 10-1000m of described sheeting
2/ g.
According to embodiment of the present invention, described sheeting is hard carbon precursor at the gas that contains protium or contains thermal decomposition product in the atmosphere of liquid vapour of protium.
According to embodiment of the present invention, in order to obtain having the laminar hard carbon material of described feature, making the pyrolysis in the atmosphere that has comprised active gases of hard carbon precursor is necessary condition, and described atmosphere can be all to be comprised of described active gases, also can comprise carrier gas.
Described active gases can be the liquid vapour that contains the gas of protium or contain protium, and wherein, the described gas that contains protium can be H
2, NH
3, or rudimentary hydrocarbon gas, for example CH
4, C
2H
4, C
2H
2In alkane, alkene, the alkynes of gaseous state, the described liquid vapour that contains protium, for example H
2O steam, CH
3COCH
3Steam or CH
3CH
2OH steam etc. are the oxygen-containing organic compound of vaporization easily, also can be the mist that meets above-mentioned requirements.
Pyrolysis atmosphere can be introduced active gases by using carrier gas; described carrier gas can be the various GPF (General Protection False gases that react of not participating in; comprise one or more the combination in inert gas (helium, argon gas, neon, Krypton, xenon, radon gas etc.), carbon dioxide or the nitrogen; from economy and the convenient aspect of source of the gas, can select such as nitrogen, carbon dioxide, argon gas etc. as carrier gas.
For obtaining the hard charcoal of laminar pyrolysis, the content of active gases accounts for the 1%(v/v of the atmosphere that pyrolytic reaction is provided at least), generally can be 1-10%.
In the specific embodiments of the present invention, hard carbon precursor can be in dusty material or the liquid form introducing pyrolysis system.Hard carbon precursor common first ball milling before pyrolysis becomes to have graininess or the powder of certain particle size, can directly use, also it can be added in the organic solvent, form the comparatively decentralized photo of homogeneous of granularity, for example, hard carbon precursor is made powder or is mixed with precursor concentration as the solution of 0.05-10M take organic solvent through removing the crystallization water.Hard carbon precursor is made powder, and still to utilize decentralized photo all be for it fully being contacted with atmosphere, reaching the purpose that reacts completely.
Hard carbon precursor adds before the pyrolysis system preferably dry first, can Accurate Determining adds the gas content in the pyrolysis system, also can process or does not take off the crystallization water and process through taking off the crystallization water.Dry benefit with taking off crystallization water processing is to control better the realization of pyrolytic process, and nonessential program.If utilize undried to process or carry out described pyrolysis without the abundant hard carbon precursor of drying and dehydrating, even the pyrolysis system only is carrier gas, can observes in the hard product char after the pyrolysis and can exist minute quantity to be laminar hard charcoal.Conclusion to this phenomenon analysis should be, in the high temperature pyrolysis process, hard carbon precursor with the hydrogeneous elemental gas that moisture can be vaporized and the thermal decomposition of presoma own goes out sneaked in the carrier gas, cause the thermal decomposition product of hard carbon precursor under the demonstration of SEM, the part has the broken shape thin slice hard carbon material of minute quantity to occur.Clear and convenient for what explain, the present invention is defined as the atmosphere that contains at least 1% active gases to pyrolysis atmosphere, this active gases should be (particularly presoma being carried out first in the dry situation) that the operator specially introduces usually, when definite presoma that uses self contain certain moisture or other meet heat can gasification and when the composition of hydrogen-containing gas is provided, as long as this part gas is enough to satisfy the requirement of described pyrolysis atmosphere, such pyrolysis system also should belong to the defined scope of claim of the present invention.
In the solution of the present invention, can not make particular determination to employed hard carbon precursor, can use various heat supply solutions known or commonly used to obtain the hard carbon precursor of hard charcoal.In the specific embodiments, described hard carbon precursor can be one or more combination of these materials.This presoma can be carbohydrate, contain the synthetic resin of C, H, O element or soft charcoal presoma via the cross-linking products that contains under the effect of oxygen element crosslinking agent.
Described carbohydrate for example can be monose or polysaccharide, for example, can be glucose, sucrose, fructose, cellulose or starch etc.
According to the embodiment of the present invention, the synthetic resin of the described C of containing, H, O element comprises that thermosetting resin or thermoplastic resin are through containing the crosslinked product of oxygen crosslinking agent.
According to the specific embodiment of the present invention, the synthetic resin of the described C of containing, H, O element can be the thermosetting resins such as phenolic resins, Lauxite, epoxy resin, fluororesin, unsaturated polyester (UP), polyurethane, or the thermoplastic resin such as polyethylene, polypropylene, polystyrene, polyvinyl chloride is through containing the crosslinked products therefrom of oxygen crosslinking agent.
Described soft charcoal presoma is via the cross-linking products that contains under the effect of oxygen element crosslinking agent, and for example, pitch is through the crosslinked hard carbon precursor etc. that makes of peroxidating diisopropylbenzene (DIPB) crosslinking agent.
Laminar pyrolytic hard carbon material described in the present invention, be construed as in the thermal decomposition product that obtains according to the inventive method, satisfy the above laminar hard charcoal that limits and occupied enough large ratio, and do not require that thermal decomposition product all is defined laminar, but, this laminar hard charcoal that has occupied enough vast scales is enough to can demonstrate fully the performance raising that laminar hard charcoal is given when described pyrolytic hard carbon material is employed, perhaps can collect purer lamellar material by suitable separation fully, can think that accordingly thermal decomposition product is needed laminar hard carbon material.
Pyrolytic hard carbon material provided by the invention, has unique appearance structure, the specific area that significantly promotes, excellent absorption and load-carrying properties can be provided, can be used for present hard carbon material or other porous material applicable each field of institute and occasion, for example, electrode (negative pole) for the manufacture of secondary cell (lithium battery or sode cell etc.), the electrode catalyst agent carrier of battery or metal-air batteries acts as a fuel, electrode for the manufacture of capacitor, and as the application of adsorbent or decolorizer, can also be used to prepare the composite material with height increasing tougheness, the noxious substance adsorbent, the adsorbent of special purpose, decolorizer raw material in the food production etc.
10g glucose is placed in the pyrolysis reactor through washing, oven dry, ball-milling treatment, passes into Ar-8%H with the gas flow of 50mL/min
2(H
2Account for Ar-H
2The percent by volume of gaseous mixture is 8%), and make reactor temperature rise to 750 ℃ with the speed of 2 ℃/min, keep basic constant temperature 15h after, naturally cool to room temperature, obtain the about 3nm of average thickness, the about 623m of geometrical surface
2/ g, the about 0.7nm in minimum-value aperture, smallest radial size and the laminar pyrolytic hard carbon material of average thickness than about 5200:1.
This lamellar material is respectively SEM photo under 5K and the 10K such as Fig. 1 (a) and Fig. 1 (b) in multiplication factor and shows, can be clearly seen that from this SEM figure: the pyrolytic hard carbon material pattern of making through above-mentioned preparation method is take laminar as main.
X ray diffracting spectrum as shown in Figure 8, d
002=3.72; The Raman collection of illustrative plates as shown in Figure 9, L
a=23nm.
Electronic diffraction can be learnt from this figure as shown in figure 10: the electronic diffraction SAED style of the thin slice hard carbon material that degree of graphitization is not high only has the diffraction ring of two disperses to correspond respectively to (002) and (100) diffraction surfaces the powder X-ray RD spectrum.
TEM can clearly be seen that the situation that thin slice is piled up from this figure as shown in figure 12.
Except with Ar-1%H
2(H
2Account for Ar-H
2The percent by volume of gaseous mixture is 1%) replacement Ar-8%H
2Outward, all the other obtain laminar pyrolytic hard carbon material according to method similarly to Example 1, and its average thickness is about 5nm, the about 405m of geometrical surface
2/ g, the about 0.7nm in minimum-value aperture gets resulting sheeting, and its smallest radial size and average thickness are than about 3200:1.
This lamellar material multiplication factor be 2K the SEM photo as shown in Figure 2, can be clearly seen that from this SEM figure: the pyrolytic hard carbon material of making through above-mentioned preparation method is rendered as a large amount of laminar, can obtain being mainly the hard carbon material of thin slice through suitable separation.
According to X ray diffracting spectrum, d
002=3.72; The Raman collection of illustrative plates, L
a=20nm.
Embodiment 3
Except with Ar-0.5%H
2(H
2Account for Ar-H
2The percent by volume of gaseous mixture is 0.5%) replacement Ar-8%H
2Outward, all the other obtain pyrolytic hard carbon material according to method similarly to Example 1, and the sheet product of getting wherein detects, and its average thickness is about 8nm, the about 280m of geometrical surface
2/ g, the about 0.7nm in minimum-value aperture, smallest radial size and average thickness are than about 1000:1.
This lamellar material multiplication factor be 1K the SEM photo as shown in Figure 3, can be clearly seen that from this SEM figure: the pyrolytic hard carbon material of making through above-mentioned preparation method presents a certain amount of laminar, more difficult separated and collected.
According to X ray diffracting spectrum, d
002=3.72; The Raman collection of illustrative plates, L
a=20nm.
Embodiment 4
Except replacing the hard carbon precursor of 10g glucose with 10g phenolic resins, all the other obtain laminar pyrolytic hard carbon material according to method similarly to Example 1, and its average thickness is about 3.8nm, the about 520m of geometrical surface
2/ g, the about 0.7nm in minimum-value aperture, smallest radial size and average thickness are than about 4600:1.
According to X ray diffracting spectrum, d
002=3.71; The Raman collection of illustrative plates, L
a=23.1nm.
Embodiment 5
Except replacing the hard carbon precursor of 10g glucose so that pitch is made product through peroxidating diisopropylbenzene (DIPB) crosslinking agent crosslinking Treatment, all the other obtain laminar pyrolytic hard carbon material according to method similarly to Example 1, its average thickness is about 5nm, the about 401m of geometrical surface
2/ g, the about 0.7nm in minimum-value aperture, smallest radial size and average thickness are than about 3800:1.
According to X ray diffracting spectrum, d
002=3.75; The Raman collection of illustrative plates, L
a=23nm.
Embodiment 6
Except replacing the hard carbon precursor of 10g glucose with 5g phenolic resins and 5g glucose mixture, all the other obtain laminar pyrolytic hard carbon material according to method similarly to Example 1, and its average thickness is about 3.5nm, the about 571m of geometrical surface
2/ g, the about 0.7nm in minimum-value aperture, smallest radial size and average thickness are than about 3900:1.
According to X ray diffracting spectrum, d
002=3.75; The Raman collection of illustrative plates, L
a=24nm.
Embodiment 7
10g glucose is placed in the pyrolysis reactor through washing, oven dry, ball-milling treatment, passes into CH with the gas flow of 50mL/min
4Gas, and make reactor temperature rise to 750 ℃ with the speed of 2 ℃/min, keep basic constant temperature 15h after, naturally cool to room temperature, obtain average thickness and be about 3.2nm, the about 601m of geometrical surface
2/ g, the about 0.7nm in minimum-value aperture, smallest radial size and the laminar pyrolytic hard carbon material of average thickness than about 5800:1.
The SEM photo that this lamellar material is respectively 2K in multiplication factor as shown in Figure 4, can be clearly seen that from this SEM figure: the pyrolytic hard carbon material of making through above-mentioned preparation method presents laminar.
According to X ray diffracting spectrum, d
002=3.71; The Raman collection of illustrative plates, L
a=22.1nm.
Embodiment 8
Except replacing the hard carbon precursor of 10g glucose with 10g phenolic resins, all the other obtain laminar pyrolytic hard carbon material according to method similarly to Example 7, and its average thickness is about 3.9nm, the about 511m of geometrical surface
2/ g, the about 0.7nm in minimum-value aperture,, smallest radial size and average thickness are than about 4200:1.
According to X ray diffracting spectrum, d
002=3.71; The Raman collection of illustrative plates, L
a=23nm.
Embodiment 9
Except with 10g pitch being replaced the hard carbon precursor of 10g glucose through the product that peroxidating diisopropylbenzene (DIPB) crosslinking agent crosslinking Treatment makes, all the other obtain laminar pyrolytic hard carbon material according to method similarly to Example 7, its average thickness is about 4nm, the about 495m of geometrical surface
2/ g, the about 0.7nm in minimum-value aperture,, smallest radial size and average thickness are than about 4100:1.
According to X ray diffracting spectrum, d
002=3.73; The Raman collection of illustrative plates, L
a=23nm.
10g glucose is placed in the pyrolysis reactor through washing, oven dry, ball-milling treatment, passes into H with the gas flow of 50mL/min
2O steam, and make reactor temperature rise to 750 ℃ with the speed of 2 ℃/min, keep basic constant temperature 10h after, naturally cool to room temperature, obtain average thickness and be about 3.2nm, the about 601m of geometrical surface
2/ g, the about 0.7nm in minimum-value aperture, smallest radial size and the laminar pyrolytic hard carbon material of average thickness than about 5200:1.
The SEM photo that this lamellar material is respectively 5K in multiplication factor as shown in Figure 5, can be clearly seen that from this SEM figure: the pyrolytic hard carbon material of making through above-mentioned preparation method presents laminar.
According to X ray diffracting spectrum, d
002=3.72; The Raman collection of illustrative plates, L
a=21.0nm.
Embodiment 11
Except replacing the hard carbon precursor of 10g glucose with 10g phenolic resins, all the other obtain laminar pyrolytic hard carbon material according to method similarly to Example 10, and its average thickness is about 4.1nm, the about 485m of geometrical surface
2/ g, the about 0.7nm in minimum-value aperture, smallest radial size and average thickness are than about 4200:1.
According to X ray diffracting spectrum, d
002=3.71; The Raman collection of illustrative plates, L
a=21.2nm.
Embodiment 12
Except with 10g pitch being replaced the hard carbon precursor of 10g glucose through the product that peroxidating diisopropylbenzene (DIPB) crosslinking agent crosslinking Treatment makes, all the other obtain laminar pyrolytic hard carbon material according to method similarly to Example 10, its average thickness is about 4.6nm, the about 412m of geometrical surface
2The about 0.8nm in/g minimum-value aperture,, smallest radial size and average thickness are than about 4100:1.
According to X ray diffracting spectrum, d
002=3.68; The Raman collection of illustrative plates, L
a=22nm.
Embodiment 13
Except replacing the constant temperature 15h with constant temperature 1h, all the other obtain laminar pyrolytic hard carbon material according to method similarly to Example 1, and its average thickness is about 4.5nm, the about 420m of geometrical surface
2/ g, the about 0.7nm in minimum-value aperture, smallest radial size and average thickness are than about 2300:1.
According to X ray diffracting spectrum, d
002=3.71; The Raman collection of illustrative plates, L
a=18.5nm.
Embodiment 14
Except replacing the constant temperature 15h with constant temperature 1h, all the other obtain laminar pyrolytic hard carbon material according to method similarly to Example 4, and its average thickness is about 4.4nm, the about 450m of geometrical surface
2/ g, the about 0.7nm in minimum-value aperture, smallest radial size and average thickness are than about 2100:1.
According to X ray diffracting spectrum, d
002=3.68; The Raman collection of illustrative plates, L
a=18.2nm.
Embodiment 15
Except replacing the constant temperature 15h with constant temperature 1h, all the other obtain laminar pyrolytic hard carbon material according to method similarly to Example 5, and its average thickness is about 6nm, the about 325m of geometrical surface
2/ g, the about 0.7nm in minimum-value aperture, smallest radial size and average thickness are than about 2000:1.
According to X ray diffracting spectrum, d
002=3.76; The Raman collection of illustrative plates, L
a=17.5nm.
Embodiment 16
Except the heating rate with 10 ℃/min replaces the heating rate of 2 ℃/min, all the other obtain laminar pyrolytic hard carbon material according to method similarly to Example 1, and its average thickness is about 6.5nm, the about 311m of geometrical surface
2/ g, the about 0.7nm in minimum-value aperture, smallest radial size and average thickness are than about 2500:1.
According to X ray diffracting spectrum, d
002=3.71; The Raman collection of illustrative plates, L
a=15.5nm.
Embodiment 17
Except the heating rate with 10 ℃/min replaces the heating rate of 2 ℃/min, all the other obtain laminar pyrolytic hard carbon material according to method similarly to Example 4, and its average thickness is about 7.1nm, the about 301m of geometrical surface
2/ g, the about 0.7nm in minimum-value aperture, smallest radial size and average thickness are than about 2600:1.
According to X ray diffracting spectrum, d
002=3.71; The Raman collection of illustrative plates, L
a=15.6nm.
Embodiment 18
Except the heating rate with 10 ℃/min replaces the heating rate of 2 ℃/min, all the other obtain laminar pyrolytic hard carbon material according to method similarly to Example 5, and its average thickness is about 6.5nm, the about 310m of geometrical surface
2/ g, the about 0.7nm in minimum-value aperture, smallest radial size and average thickness are than about 2760:1.
According to X ray diffracting spectrum, d
002=3.75; The Raman collection of illustrative plates, L
a=15.3nm.
Embodiment 19
Except the gas flow with 100mL/min replaces the gas flow of 50mL/min, all the other obtain laminar pyrolytic hard carbon material according to method similarly to Example 1, and its average thickness is about 4.2nm, the about 462m of geometrical surface
2/ g, the about 0.7nm in minimum-value aperture, smallest radial size and average thickness are than about 2900:1.
According to X ray diffracting spectrum, d
002=3.75; The Raman collection of illustrative plates, L
a=18.5nm.
Except the gas flow with 100mL/min replaces the gas flow of 50mL/min, all the other obtain laminar pyrolytic hard carbon material according to method similarly to Example 4, and its average thickness is about 4.2nm, the about 471m of geometrical surface
2/ g, the about 0.7nm in minimum-value aperture,, smallest radial size and average thickness are than about 3100:1.
According to X ray diffracting spectrum, d
002=3.71; The Raman collection of illustrative plates, L
a=18.1nm.
Embodiment 21
Except the gas flow with 100mL/min replaces the gas flow of 50mL/min, all the other obtain laminar pyrolytic hard carbon material according to method similarly to Example 5, and its average thickness is about 4.3nm, the about 461m of geometrical surface
2/ g, the about 0.7nm in minimum-value aperture,, smallest radial size and average thickness are than about 2800:1.
According to X ray diffracting spectrum, d
002=3.72; The Raman collection of illustrative plates, L
a=18.2nm.
Embodiment 22
Except being warming up to 750 ℃ to be warming up to 950 ℃ of replacements, all the other obtain laminar pyrolytic hard carbon material according to method similarly to Example 1, and its average thickness is about 6nm, the about 325m of geometrical surface
2/ g, the about 0.8nm in minimum-value aperture,, smallest radial size and average thickness are than about 1900:1.
According to X ray diffracting spectrum, d
002=3.71; The Raman collection of illustrative plates, L
a=24nm.
Embodiment 23
Except being warming up to 750 ℃ to be warming up to 950 ℃ of replacements, all the other obtain laminar pyrolytic hard carbon material according to method similarly to Example 4, and its average thickness is about 5.2nm, the about 365m of geometrical surface
2/ g, the about 0.7nm in minimum-value aperture, smallest radial size and average thickness are than about 1950:1.
According to X ray diffracting spectrum, d
002=3.75; The Raman collection of illustrative plates, L
a=24.1nm.
Embodiment 24
Except being warming up to 750 ℃ to be warming up to 950 ℃ of replacements, all the other obtain laminar pyrolytic hard carbon material according to method similarly to Example 5, and its average thickness is about 5.3nm, the about 360m of geometrical surface
2/ g, the about 0.7nm in minimum-value aperture,, smallest radial size and average thickness are than about 1860:1.
According to X ray diffracting spectrum, d
002=3.72; The Raman collection of illustrative plates, L
a=24.6nm.
Embodiment 25
Except replacing the constant temperature 15h with constant temperature 0h, all the other obtain laminar pyrolytic hard carbon material according to method similarly to Example 1, and its average thickness is about 7nm, the about 301m of geometrical surface
2/ g, the about 0.8nm in minimum-value aperture, smallest radial size and average thickness are than about 1200:1.
According to X ray diffracting spectrum, d
002=3.72; The Raman collection of illustrative plates, L
a=15.4nm.
Embodiment 26
Except replacing the constant temperature 15h with constant temperature 0h, all the other obtain laminar pyrolytic hard carbon material according to method similarly to Example 4, and its average thickness is about 7.2nm, the about 298m of geometrical surface
2/ g, the about 0.8nm in minimum-value aperture, smallest radial size and average thickness are than about 1100:1.
According to X ray diffracting spectrum, d
002=3.69; The Raman collection of illustrative plates, L
a=15.6nm.
Embodiment 27
Except replacing the constant temperature 15h with constant temperature 0h, all the other obtain laminar pyrolytic hard carbon material according to method similarly to Example 5, and its average thickness is about 7.2nm, the about 286m of geometrical surface
2/ g, the about 0.8nm in minimum-value aperture, smallest radial size and average thickness are than about 1190:1.
According to X ray diffracting spectrum, d
002=3.71; The Raman collection of illustrative plates, L
a=15.3nm.
Embodiment 28
Except replacing the 10g glucose with 100mL ethanol dissolving 10g glucose wiring solution-forming, all the other obtain laminar pyrolytic hard carbon material according to method similarly to Example 1, and its average thickness is about 4nm, the about 501m of geometrical surface
2/ g, the about 2.2nm in minimum-value aperture, smallest radial size and average thickness are than about 4650:1.
According to X ray diffracting spectrum, d
002=3.70; The Raman collection of illustrative plates, L
a=23.2nm.
Comparative Examples 1
10g glucose is placed pyrolysis reactor, passes into Ar with the gas flow of 50mL/min, and make reactor temperature rise to 750 ℃ with the speed of 2 ℃/min, keep basic constant temperature 15h after, naturally cool to room temperature, collect resulting pyrolytic hard carbon material.
This material is respectively 300 in multiplication factor, the SEM photo of 1K is shown in Fig. 6 (a) and Fig. 6 (b), can be clearly seen that from this SEM figure: the pyrolytic hard carbon material that the above-mentioned preparation method of process makes wherein exists minute quantity to be laminar product take graininess as main.
According to X ray diffracting spectrum, d
002=3.71; The Raman collection of illustrative plates, L
a=20.1nm.
Comparative Examples 2
10g glucose is placed pyrolysis reactor, pass into CO with the gas flow of 50mL/min
2, and make reactor temperature rise to 750 ℃ with the speed of 2 ℃/min, keep basic constant temperature 15h after, naturally cool to room temperature, collect resulting pyrolytic hard carbon material.
The SEM photo that this material is respectively 3K in multiplication factor can be clearly seen that from this SEM figure as shown in Figure 7: the pyrolytic hard carbon material of making through above-mentioned preparation method wherein exists minute quantity to be laminar product take graininess as main.
According to X ray diffracting spectrum, d
002=3.70; The Raman collection of illustrative plates, L
a=21.1nm.
From above-described embodiment and Comparative Examples as can be known:
1, comparative example 1 and comparative example 2 show: the hard carbon precursor that undried is processed directly joins only in the pyrolysis system of carrier gas, can comprise a small amount of pattern in the hard charcoal of pyrolysis and be laminar product, should be because in the high temperature pyrolysis process, hard carbon precursor with moisture and the hydrogeneous elemental gas that goes out of the thermal decomposition of presoma own sneak in the carrier gas, cause the thermal decomposition product of hard carbon precursor under the demonstration of SEM, there is the broken shape thin slice hard carbon material of minute quantity in the part; Further, when hard carbon precursor at carrier gas (Ar or CO
2) atmosphere in carry out the pyrolytic hard carbon material that pyrolytic reaction makes and present the laminar of minute quantity, find through coherent detection, significantly greater than using the resulting hard charcoal thin slice of pyrolysis atmosphere that contains active gases in above-described embodiment, its geometrical surface and smallest radial size are all remarkable in the hard charcoal thin slice among the embodiment with the average thickness ratio for its average thickness; Simultaneously, laminar hard charcoal content in thermal decomposition product is few, just exists with " impurity ".
2, embodiment 1-embodiment 3 and Comparative Examples 1
Comparative Examples 1 is only being carried out high temperature pyrolysis in the pyrolysis system of carrier gas for hard carbon precursor, embodiment 3-embodiment 1 be hard carbon precursor at the mist of active gases and carrier gas, namely atmosphere is respectively Ar-0.5%H
2, Ar-1%H
2And Ar-8%H
2Parallel embodiment, only be Ar at atmosphere, until the atmosphere alternation becomes Ar-8%H
2Process in, only to having added the active gases H that content increases progressively among the carrier gas Ar
2, our beyond thought discovery in this process: because of the introducing of active gases, caused the variation of thermal decomposition product pattern, namely obtained the thin slice hard carbon material of similar graphene-like.And when active gases content reaches 1%, the laminar hard carbon content in the thermal decomposition product has accounted for suitable vast scale, can directly utilize and demonstrates the performance of the hard charcoal of thin slice pattern.
Application example 1 lithium battery
A, the laminar pyrolytic hard carbon material that embodiment 1 is made are used as lithium cell cathode material, and its concrete operation method is as follows:
With the aqueous solution of the laminar hard carbon material that obtains and binding agent sodium carboxymethylcellulose (CMC) at normal temperatures and pressures mixed grinding form slurry, evenly be coated in again on the Copper Foil substrate, at vacuum condition, 105 ℃ of lower oven dry 6h of temperature are at 20kg/cm
2Pressure under compress, membrane electrode being cut into area is 1cm again
2The circular electric pole piece, and take lithium metal as electrode assembling is become button cell, wherein, the mass ratio of the hard charcoal of laminar pyrolysis and binding agent sodium carboxymethylcellulose (CMC) is 9:1 in the electrode slice.
The electrolyte of simulated battery is 1mol LiPF
6Be dissolved in the mixed solvent (volume ratio 1:1) of 1L EC and DMC.With positive pole, negative pole, electrolyte, barrier film is assembled into simulated battery in the glove box of argon shield.
The above-mentioned button cell that is assembled into is discharged and recharged instrument at blue electricity test, as shown in figure 11, discharge and recharge interval at 0-3V, with the electric current constant current charge-discharge of 37mA/g.First all discharge capacity 583mAh/g, first all charging capacity 165mAh/g fully show this laminar hard carbon material and have the Large ratio surface characteristic.
B, the laminar hard carbon material produced out take embodiment 1 are produced the lithium ion battery negative material of SnSb load as carrier, and concrete operation method is as follows:
At first, with 1L ethylene glycol dissolving 22.8g SbCl
3With 22.6g SnCl
22H
2Then the mixture of O adds the above-mentioned hard carbon material of making of 56g and is placed in the frozen water, slowly adds suction filtration behind the 16.3g zinc powder reaction 2h, washing, until filtrate is met AgNO
3Constant muddiness.The filter cake that obtains at 60 ℃ of lower heating 12h of vacuum, is namely obtained Sb and Sn load capacity and is respectively 16.5%, 16.2% hard carbon composite.This hard carbon composite is implemented the mode described in the A carry out assembled battery, its reversible capacity is up to 550mAh/g.
Application example 2 transducers
The laminar hard carbon material of producing out take embodiment 7 is produced resistance hydrogen sensor critical material as carrier, and concrete operation method is as follows:
Hard carbon material is dissolved in the phenmethylol, with SnCl
4Be presoma microwave process for synthesizing load SnO
2Particle then under 140 ℃, reduces H with microwave process for synthesizing take ethylene glycol as reducing agent
2PtCl
6Washing behind the 5min, oven dry namely obtain Pt-SnO
2/ C composite material.
By chemical analysis (ICP) Pt-SnO as can be known
2Pt in the/C composite material, SnO
2, the C mass percent is respectively 20%, 60%, 20%.SnO
2Particle is 4nm, and the Pt particle is 3nm.Because Pt-SnO
2/ C composite material can contacting with hydrogen molecule of sensitivity trigger dissociating of metal, thereby at low concentration H
2(0.1%-3%) extremely responsive response is arranged under the environment, its response time 2-6s, recovery time 1-5s.In this composite material, similar graphene platelet shape hard carbon material is good conductive network, and compares traditional carbon black conductive body, also has higher geometrical surface, is suitable as very much H
2Base material Deng gas sensor.
Application example 3Pt-C fuel-cell catalyst carrier
The laminar hard carbon material of producing out take embodiment 10 is produced Pt-C fuel-cell catalyst critical material as carrier, and concrete operation method is as follows:
H with 50mg hard carbon material, 10mL0.0096M
2PtCl
6, 25mL ethylene glycol, 4mL0.05MKOH behind 135 ℃ of lower abundant stirring reaction 3h, be down to room temperature, fully wash, dry with ethanol, namely obtain the Pt-C fuel-cell catalyst, its Pt load quality percentage 30%.
Take by weighing 10mg Pt-C fuel-cell catalyst, add Nafion solution and the aqueous isopropanol of 5% mass percent, ultrasonic 30min, the mass ratio of its catalyst and Nafion are 3:1, after becoming the ink shape, are sprayed on the polished glass carbon as work electrode.
Under 30 ℃, with the H of 0.5M
2SO
4Be electrolyte, test H with the speed of sweeping of 20mV/s in the 0-1.2V interval
2Absorption and the desorption curve as can be known: under 45 ℃, with the H of 0.5M
2SO
4With the ethanolic solution of 2M be electrolyte, sweep speed test methanol oxidation as can be known with 20mV/s: in the presence of the Pt-C fuel-cell catalyst, the electric current that methanol oxidation reduces is 386mA/mg
PtBecause laminar hard carbon material has higher geometrical surface, so can obtain comparing other material with carbon elements when a certain amount of Pt loads on this hard charcoal thin slice, it is more even to distribute, and has the catalyst material at larger effecting reaction interface.
Application example 4MnO2-C ultracapacitor
The laminar hard carbon material of producing out take embodiment 5 is produced the lithium ion battery negative material of SnSb load as carrier, and concrete operation method is as follows:
After getting the ultrasonic 1h of hard charcoal aqueous solution 100mL of 1.5mg/mL, add under agitation microwave heating 5min of 0.95g potassium permanganate, then fully wash with deionization, ethanol successively, at 120 ℃ of lower baking 12h of vacuum, namely obtain MnO
2The hard charcoal sheeting of load, its MnO
2Load capacity be 80%.
With prepared MnO
2Load hard carbon material and carbon black, polytetrafluoroethylene with mass ratio mixing in ethanol of 75:20:5, and evenly spread upon on the nickel screen, at 120 ℃ of bakings of vacuum 12h.To scribble MnO
2The nickel screen of-C is as work electrode, take platinum electrode as to electrode, take saturated calomel electrode as reference electrode, take the metabisulfite solution of 1M as electrolyte, at room temperature does cyclic voltammetry scan.
Its result shows: the speed of sweeping with 2mV/s between-0.1 to 0.9V is done cyclic voltammetry, and obtaining the material specific capacitance is 402F/g.Because this laminar hard carbon material has better intensity than Graphene, and there is defective in inside, so that in the more stably load of load oxide on the carbon plate, and high geometrical surface not only provides the conductive network of whole material, great response area also is provided simultaneously, so be used in the catalyst, this hard carbon material is rare carbon carrier.
Application example 5C-decolorizer
The laminar hard carbon material of producing with embodiment 2 detects it to the decoloration performance of material as decolorizer, and concrete operation method is as follows:
Get 5 glasss of monosodium glutamate water (every glass of 100mL), add respectively 0.2,0.5,0.8, the above-mentioned hard carbon material of 1.0g, 1.3g.Carry out the light transmittance measurement by the monosodium glutamate water that adds hard carbon material to above-mentioned 5 glasss, the result shows: the monosodium glutamate water light transmittance that adds the 1.0g hard carbon material is the highest, reach 85%, compare existing material with carbon element and exceed approximately 5%, laminar hard carbon material demonstrates stronger decoloration performance.
It should be noted that at last: above embodiment only in order to technical scheme of the present invention to be described, is not intended to limit; Although with reference to previous embodiment the present invention is had been described in detail, those of ordinary skill in the art is to be understood that: it still can be made amendment to the technical scheme that aforementioned each embodiment puts down in writing, and perhaps part technical characterictic wherein is equal to replacement; And these modifications or replacement do not make the essence of appropriate technical solution break away from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (25)
1. a pyrolytic hard carbon material is characterized in that, its for hard carbon precursor pyrolysis is formed, have average thickness 1-200nm, a geometrical surface 10-2000m
2The sheeting of the similar two dimensional surface of/g, described pyrolytic hard carbon material inside exists micropore or mesopore.
2. pyrolytic hard carbon material according to claim 1, the smallest radial size of the similar two dimensional surface of described sheeting is not less than 100:1 with the ratio of its average thickness.
3. pyrolytic hard carbon material according to claim 1, described hard carbon material inside exists micropore and/or mesopore, and micropore size is less than 1nm, and the mesopore aperture is 2-20nm.
4. pyrolytic hard carbon material according to claim 1 and 2, the average thickness 2-50nm of described sheeting.
5. pyrolytic hard carbon material according to claim 1, the geometrical surface 10-1000m of described sheeting
2/ g.
6. each described pyrolytic hard carbon material according to claim 1-5, described sheeting are hard carbon precursor at the gas that contains protium or contain thermal decomposition product in the atmosphere of liquid vapour of protium.
7. method for preparing such as each described pyrolytic hard carbon material of claim 1-6, the method comprise the pyrolysis in atmosphere of hard carbon precursor, wherein,
The active gases that has comprised 1-100% in the described atmosphere;
Described hard carbon precursor pyrolytic process comprises at least: control gas flow 0.1-500mL/min is to provide atmosphere, hard carbon precursor and gas are fully contacted form the pyrolysis system, and make the pyrolysis system be warming up to 400-2000 ℃ with the speed of 0.5-10 ℃/min, keep this temperature and be cooled to room temperature after 0-72 hour;
Described active gases comprises the gas that contains protium or the liquid vapour that contains protium.
8. method according to claim 7 in hard carbon precursor pyrolytic process, is controlled gas flow 10-300mL/min.
9. method according to claim 7 in hard carbon precursor pyrolytic process, is controlled the pyrolysis system and is warming up to 400-1500 ℃.
10. each described method according to claim 7-9, in hard carbon precursor pyrolytic process, until the pyrolysis system heat up finish after, holding temperature 0-20 hour.
11. method according to claim 7, hard carbon precursor is that dusty material or liquid form are present in the pyrolysis system.
12. it is front through taking off crystallization water processing or not taking off the crystallization water and process that method according to claim 7, hard carbon precursor add the pyrolysis system.
13. method according to claim 12, hard carbon precursor is made powder or is mixed with precursor concentration as the solution of 0.05-10M take organic solvent through removing the crystallization water.
14. method according to claim 7, described hard carbon precursor are carbohydrate, contain the synthetic resin of C, H, O element, soft charcoal presoma in the cross-linking products or its combination in any that contain under the effect of oxygen element crosslinking agent.
15. method according to claim 14, described carbohydrate monose or polysaccharide.
16. method according to claim 15, described carbohydrate comprises glucose, sucrose, fructose, cellulose or starch.
17. method according to claim 14, the synthetic resin of the described C of containing, H, O element comprise that thermosetting resin or thermoplastic resin are through containing the crosslinked product of oxygen crosslinking agent.
18. each described method according to claim 14-17, the synthetic resin of the described C of containing, H, O element comprises phenolic resins, Lauxite, epoxy resin, fluororesin, unsaturated polyester (UP), polyurethane, and perhaps polyethylene, polypropylene, polystyrene, polyvinyl chloride are through containing the crosslinked products therefrom of oxygen crosslinking agent.
19. method according to claim 7, described atmosphere are the mist of active gases or active gases and carrier gas, described carrier gas comprises one or more the combination in inert gas, nitrogen or the carbon dioxide.
20. method according to claim 7, the described gas that contains protium comprises H
2, NH
3, or alkane, alkene, alkynes class gas, the described liquid vapour that contains protium comprises H
2O steam, CH
3COCH
3Steam or CH
3CH
2OH steam.
21. each described method according to claim 7-19, the content of active gases is 1-10% in the described atmosphere.
22. the application of each described pyrolytic hard carbon material of claim 1-6 in the electrode of making secondary cell.
The application of the electrode catalyst agent carrier of battery or metal-air batteries 23. each described pyrolytic hard carbon material of claim 1-6 acts as a fuel.
24. the application of each described pyrolytic hard carbon material of claim 1-6 in making electrode for capacitors.
25. each described pyrolytic hard carbon material of claim 1-6 is as the purposes of adsorbent or decolorizer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210505811.8A CN102956876B (en) | 2012-11-30 | 2012-11-30 | Pyrolytic hard carbon material and its production and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210505811.8A CN102956876B (en) | 2012-11-30 | 2012-11-30 | Pyrolytic hard carbon material and its production and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102956876A true CN102956876A (en) | 2013-03-06 |
| CN102956876B CN102956876B (en) | 2015-09-16 |
Family
ID=47765370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210505811.8A Active CN102956876B (en) | 2012-11-30 | 2012-11-30 | Pyrolytic hard carbon material and its production and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102956876B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014082191A1 (en) * | 2012-11-30 | 2014-06-05 | 中国科学院物理研究所 | Pyrolytic hard charcoal material and preparation method and use thereof |
| CN104016512A (en) * | 2014-06-10 | 2014-09-03 | 上海大学 | Method for treating copper-containing wastewater by utilizing spartina-alterniflora-loisel-based charcoal |
| CN104103808A (en) * | 2014-07-31 | 2014-10-15 | 中国科学院上海硅酸盐研究所 | Flake-like tin-carbon composite material for lithium ion battery and preparation method for flake-like tin-carbon composite material |
| CN104377346A (en) * | 2014-11-04 | 2015-02-25 | 辽宁工程技术大学 | Method for preparing modified graphite negative electrode material of sodium ion battery |
| CN106099109A (en) * | 2016-06-22 | 2016-11-09 | 大连理工大学 | A kind of preparation method and applications of asphaltic base hard charcoal nanometer sheet |
| CN108136365A (en) * | 2015-08-22 | 2018-06-08 | 恩特格里斯公司 | Microcrystalline cellulose is pyrolyzed adsorbent and its manufacture and use method |
| US10113095B2 (en) | 2015-07-20 | 2018-10-30 | Microsoft Technology Licensing, Llc | Reinforced graphitic material |
| CN109742383A (en) * | 2018-12-28 | 2019-05-10 | 中国科学院物理研究所 | Sodium-ion battery hard carbon cathode material based on phenolic resin and its preparation method and application |
| CN113321199A (en) * | 2021-03-04 | 2021-08-31 | 上海大学 | Polybenzoxazine-co-cresol-based polymer-derived hard carbon microspheres, and preparation method and application thereof |
| CN114684808A (en) * | 2022-05-10 | 2022-07-01 | 大连理工大学 | Preparation method of porous nano carbon material and application of porous nano carbon material in separation of propylene/propane |
| CN114956043A (en) * | 2022-06-30 | 2022-08-30 | 广东邦普循环科技有限公司 | Preparation method and application of high-performance hard carbon material |
| CN116354335A (en) * | 2023-01-16 | 2023-06-30 | 中国科学院山西煤炭化学研究所 | Preparation method and application of asphalt-based hard carbon nano sheet |
| CN116947492A (en) * | 2023-06-13 | 2023-10-27 | 湖南大学 | High-density high-strength special carbon material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001098209A1 (en) * | 2000-04-27 | 2001-12-27 | Institute Of Physics, Chinese Academy Of Sciences | Pyrolyzed hard carbon material, preparation and its applications |
| CN102227020A (en) * | 2011-05-20 | 2011-10-26 | 田东 | Preparation method of modified graphite cathode material for lithium ion battery |
| CN102557009A (en) * | 2012-02-29 | 2012-07-11 | 北京化工大学 | Hierarchical porous structure carbon material for negative electrode of power lithium-ion battery and preparation method of hierarchical porous structure carbon material |
-
2012
- 2012-11-30 CN CN201210505811.8A patent/CN102956876B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001098209A1 (en) * | 2000-04-27 | 2001-12-27 | Institute Of Physics, Chinese Academy Of Sciences | Pyrolyzed hard carbon material, preparation and its applications |
| CN102227020A (en) * | 2011-05-20 | 2011-10-26 | 田东 | Preparation method of modified graphite cathode material for lithium ion battery |
| CN102557009A (en) * | 2012-02-29 | 2012-07-11 | 北京化工大学 | Hierarchical porous structure carbon material for negative electrode of power lithium-ion battery and preparation method of hierarchical porous structure carbon material |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014082191A1 (en) * | 2012-11-30 | 2014-06-05 | 中国科学院物理研究所 | Pyrolytic hard charcoal material and preparation method and use thereof |
| CN104016512A (en) * | 2014-06-10 | 2014-09-03 | 上海大学 | Method for treating copper-containing wastewater by utilizing spartina-alterniflora-loisel-based charcoal |
| CN104103808A (en) * | 2014-07-31 | 2014-10-15 | 中国科学院上海硅酸盐研究所 | Flake-like tin-carbon composite material for lithium ion battery and preparation method for flake-like tin-carbon composite material |
| CN104103808B (en) * | 2014-07-31 | 2016-07-27 | 中国科学院上海硅酸盐研究所 | A kind of lithium ion battery lamellar stannum carbon composite and preparation method thereof |
| CN104377346A (en) * | 2014-11-04 | 2015-02-25 | 辽宁工程技术大学 | Method for preparing modified graphite negative electrode material of sodium ion battery |
| CN104377346B (en) * | 2014-11-04 | 2017-05-03 | 辽宁工程技术大学 | Method for preparing modified graphite negative electrode material of sodium ion battery |
| US10113095B2 (en) | 2015-07-20 | 2018-10-30 | Microsoft Technology Licensing, Llc | Reinforced graphitic material |
| CN108136365A (en) * | 2015-08-22 | 2018-06-08 | 恩特格里斯公司 | Microcrystalline cellulose is pyrolyzed adsorbent and its manufacture and use method |
| CN106099109A (en) * | 2016-06-22 | 2016-11-09 | 大连理工大学 | A kind of preparation method and applications of asphaltic base hard charcoal nanometer sheet |
| CN106099109B (en) * | 2016-06-22 | 2018-12-21 | 大连理工大学 | A kind of preparation method and applications of asphaltic base hard charcoal nanometer sheet |
| CN109742383A (en) * | 2018-12-28 | 2019-05-10 | 中国科学院物理研究所 | Sodium-ion battery hard carbon cathode material based on phenolic resin and its preparation method and application |
| CN109742383B (en) * | 2018-12-28 | 2021-05-25 | 中国科学院物理研究所 | Sodium ion battery hard carbon negative electrode material based on phenolic resin and preparation method and application thereof |
| CN113321199A (en) * | 2021-03-04 | 2021-08-31 | 上海大学 | Polybenzoxazine-co-cresol-based polymer-derived hard carbon microspheres, and preparation method and application thereof |
| CN113321199B (en) * | 2021-03-04 | 2022-10-18 | 上海大学 | Polybenzoxazine-co-cresol-based polymer-derived hard carbon microspheres, and preparation method and application thereof |
| CN114684808A (en) * | 2022-05-10 | 2022-07-01 | 大连理工大学 | Preparation method of porous nano carbon material and application of porous nano carbon material in separation of propylene/propane |
| CN114956043A (en) * | 2022-06-30 | 2022-08-30 | 广东邦普循环科技有限公司 | Preparation method and application of high-performance hard carbon material |
| CN114956043B (en) * | 2022-06-30 | 2023-09-08 | 广东邦普循环科技有限公司 | Preparation method and application of high-performance hard carbon material |
| WO2024000815A1 (en) * | 2022-06-30 | 2024-01-04 | 广东邦普循环科技有限公司 | Preparation method for and use of high-performance hard carbon material |
| GB2625211A (en) * | 2022-06-30 | 2024-06-12 | Guangdong Brunp Recycling Technology Co Ltd | Preparation method for and use of high-performance hard carbon material |
| CN116354335A (en) * | 2023-01-16 | 2023-06-30 | 中国科学院山西煤炭化学研究所 | Preparation method and application of asphalt-based hard carbon nano sheet |
| CN116947492A (en) * | 2023-06-13 | 2023-10-27 | 湖南大学 | High-density high-strength special carbon material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102956876B (en) | 2015-09-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102956876B (en) | Pyrolytic hard carbon material and its production and use | |
| Feng et al. | Carbon foam with microporous structure for high performance symmetric potassium dual-ion capacitor | |
| EP3299337B1 (en) | Method for preparing graphene using coal as raw material | |
| Yu et al. | Sustainable application of biomass by-products: Corn straw-derived porous carbon nanospheres using as anode materials for lithium ion batteries | |
| CN104538595B (en) | Embedded nano metal load type carbon nano-sheet lithium ion battery negative material and its preparation method and application | |
| Yadegari et al. | On rechargeability and reaction kinetics of sodium–air batteries | |
| Sun et al. | Hierarchical macroporous/mesoporous NiCo 2 O 4 nanosheets as cathode catalysts for rechargeable Li–O 2 batteries | |
| CN110330016A (en) | An a kind of step cooperative development method of anthracite-base porous carbon graphite microcrystal and hole | |
| CN109742489B (en) | Lithium-oxygen/air battery and preparation method thereof | |
| Chen et al. | Improving the supercapacitor performance of activated carbon materials derived from pretreated rice husk | |
| CN112794324B (en) | High-mesoporosity lignin hierarchical pore carbon material and preparation method and application thereof | |
| CN106099108A (en) | A kind of preparation method of LITHIUM BATTERY graphite/absorbent charcoal composite material | |
| CN108767272A (en) | A kind of nitrogen co-doped porous carbon materials of cobalt and its preparation and application | |
| Deng et al. | Electrochemical performance of expanded graphite prepared from anthracite via a microwave method | |
| Zhang et al. | One-step synthesis of polymer based N-doped porous carbon with enriched nitrogen content and its enhanced electrochemical properties in supercapacitors | |
| Mo et al. | Hierarchical porous carbon with three dimensional nanonetwork from water hyacinth leaves for energy storage | |
| Liu et al. | Modulating pore nanostructure coupled with N/O doping towards competitive coal tar pitch-based carbon cathode for aqueous Zn-ion storage | |
| Dai et al. | Facile synthesis and high lithium storage properties of mesoporous polypyrrole coated CoFe2O4 nanofibers | |
| Gao et al. | Mechanochemistry induced pore regulation and pyridinic nitrogen doping in anthracite derived carbon for sodium storage | |
| Wang et al. | Pyrolytic gas exfoliation and template mediation inducing defective mesoporous carbon network from industrial lignin for advanced lithium-ion storage | |
| Tonoya et al. | Microporous activated carbon derived from azulmic acid precursor with high sulfur loading and its application to lithium-sulfur battery cathode | |
| Cheng et al. | Hazel shell-based biomass-derived carbon modified diaphragm for high-performance lithium-sulfur batteries | |
| Zhao et al. | Fabrication of 3D micro-flower structure of ternary Ni-Co-Cu hydroxide based on Co-MOF for advanced asymmetric supercapacitors | |
| Liu et al. | V-MOF@ carbon nanotube derived three-dimensional V2O5@ carbon nanotube as high-performance cathode for aqueous zinc-ion batteries | |
| Hou et al. | Coal tar phenols based hierarchical porous carbon nanospheres for high performance supercapacitor anodes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |