CN102956876B - Pyrolytic hard carbon material and its production and use - Google Patents
Pyrolytic hard carbon material and its production and use Download PDFInfo
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Abstract
The invention provides a kind of pyrolytic hard carbon material and its production and use.This pyrolytic hard carbon material be hard carbon precursor pyrolysis is formed, there is average thickness 1-200nm, geometrical surface 10-2000m
2the sheeting of the similar two dimensional surface of/g, there is micropore or mesopore in described pyrolytic hard carbon material inside.Present invention also offers the method for described pyrolytic hard carbon material.This has the pyrolytic hard carbon material purposes and extensively of the platelet morphology of similar Graphene profile, 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 the composite material with height increasing tougheness, the decolorizer in the adsorbent of noxious substance adsorbent, special purpose, food production and gas sensor.
Description
Technical field
The present invention relates to a kind of material with carbon element and preparation method thereof, particularly relate 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, the feature such as cost that power-performance is good, cheap gets more and more people's extensive concerning as lithium ion battery negative material, it as the carrier of the electrode material of the negative material of sodium-ion battery, electrochemical capacitor, chemistry and electro chemical catalyst, can also be applied to gas sensor etc.
The application of hard carbon material and the structure of hard carbon material and shape characteristic, on the impact of effect, are the important contents of this investigation of materials all the time.Numerous research finds, internal pore structure and surface appearance feature have material impact for the application performance of hard carbon material.Therefore, explore more effective preparation method and obtain the hard carbon material with required grain structure characteristic sum shape characteristic, also become one of problem received much attention.Such as, WO01/98209 discloses the pyrolytic hard carbon material of spheroid or spheroid, it is a kind of hard charcoal ball prepared by hydro thermal method, it contains micropore, there is spherical morphology, as the negative material of lithium ion battery, be conducive to the reversible capacity and the cycle characteristics that improve battery, can obtain at its area load nanometer tin antimony alloy the lithium ion battery negative material that specific capacity is higher and cycle performance is excellent.Although the hard carbon material of this spherical morphology had particle size distribution evenly, the advantage of higher bulk density, increasing specific surface area is to increase the limited space of nanomaterial loadings amount further.The hard carbon material utilizing hard charcoal predecessor carrying out pyrolysis to carbonize preparation has more excellent application performance, is in industry admitted gradually.Be applied as example with cathode of lithium battery, the structure of hard charcoal and embedding lithium capacity are considered to very large with cracking technology relation.So, also there are some correlative studys to report the hard carbon material obtained by controlling 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; under hard carbon precursor is placed in protective atmosphere; control corresponding pyrolytical condition, with expect to pyrolysis formed hard product char appearance structure and surface improve.
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 flake of nanometer grade thickness, compared to the pyrolytic hard carbon material of the spheroid recorded in prior art or spheroid, the laminar hard carbon material of this nanometer grade thickness has high geometrical surface, effectively can promote its performance in various practical application.
Present invention also offers a kind of method preparing described pyrolytic hard carbon material, by the adjustment of the pyrolytic process to hard carbon precursor, the laminar pyrolytic hard carbon material of the obtained similar Graphene of profile, and this preparation method has, and technique is simple, cost is low, be easy to the advantage of control.
One aspect of the present invention provides a kind of pyrolytic hard carbon material, wherein, this hard carbon material be hard carbon precursor pyrolysis formed, there is average thickness 1-200nm, geometrical surface 10-2000m
2the sheeting of the similar two dimensional surface of/g, there is micropore or mesopore in described pyrolytic hard carbon material inside.
The research of inventor confirms, the hard charcoal of flaky texture has high geometrical surface, and the hard charcoal of flake of this similar Graphene, due to shape characteristic and the surface characteristic of uniqueness, various performances in actual applications obtain larger lifting.
In the present invention, term " sheeting ", be interpreted as this hard carbon material in size and geometry in obvious laminated structure, relative to larger surface, abutment surface can be used as thickness and has significantly little size, can be seen and substantially present flake distribution, and have certain thickness by SEM figure, so also think similar or close to two dimensional surface (its smallest radial is far longer than the average thickness of thin slice, and thickness is little of compared to larger surface being left in the basket in other words).Term " geometrical surface " can be understood as: this laminar hard carbon material, can be seen by SEM figure and substantially present flake distribution, and have certain thickness, but some regions that are overlapping and fold can be there are simultaneously, we utilize geometrical surface to describe and limit this laminar hard carbon material under approximate ideal state in the present invention, folded the regional implementation with fold, be the surface area under flat expand state.
In the present invention, laminar hard carbon material is formed by the hard carbon precursor of pyrolysis, the bulk composition of described laminar hard carbon material is carbon, also be no more than other element of 10wt% containing mass fraction simultaneously, accountable, the laminar hard carbon material that the present invention proposes all embodies excellent performance in actual applications.
Present invention also offers the method preparing described pyrolytic hard carbon material, the method comprises the pyrolysis in atmosphere of hard carbon precursor, wherein,
The active gases of 1-100% is contained in described atmosphere;
Described hard carbon precursor pyrolytic process at least comprises: control gas flow 0.1-500mL/min to provide atmosphere, hard carbon precursor is made fully to contact formation pyrolysis systems with described gas, and make pyrolysis systems with the ramp of 0.5-10 DEG C/min to 400-2000 DEG C, be cooled to room temperature after maintaining this temperature 0-72 hour;
Described active gases comprises the gas containing protium or the liquid vapour containing 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 systems and be warming up to 400-1500 DEG C.
According to embodiment of the present invention, in hard carbon precursor pyrolytic process, after pyrolysis systems intensification terminates, after holding temperature 0-20 hour, be cooled to room temperature.
Preparation method provided by the invention, hard carbon precursor is placed in the atmosphere carrying out pyrolysis charing containing active gases, beyond thought effect is the thin slice pattern that obtained hard product char shows similar Graphene, thus the higher geometrical surface provided, more excellent performance can be demonstrated in the applied environment of hard carbon material.
Laminar hard carbon material provided by the invention, can be used in such as, 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 the composite material with height increasing tougheness, the decolorizer in the adsorbent of noxious substance adsorbent, special purpose, food production and gas sensor.
Technical scheme of the present invention at least has following beneficial effect:
1, the invention provides the flake that a kind of pyrolytic hard carbon material is nanometer grade thickness, compared to the pyrolytic hard carbon material of the spheroid recorded in prior art or spheroid, the laminar hard carbon material of this nanometer grade thickness has high geometrical surface, effectively can promote its performance in actual applications.
2, the method preparing pyrolytic hard carbon material provided by the invention, by being controlled hard carbon precursor technique of pyrolysis in atmosphere, the obtained laminar pyrolytic hard carbon material similar with Graphene profile, and this preparation method has, and technique is simple, cost is low, be easy to the advantage of control.
3, the pyrolytic hard carbon material purposes with the platelet morphology of similar black alkene profile of the present invention is very extensive, not only can as the negative pole of current serondary lithium battery or sode cell, can also as the electrode of electrochemical capacitor, and can also as key material in fields such as catalytic field, medicine food manufactures, such as carrier, sorbing material etc.
Accompanying drawing explanation
Fig. 1 (a)-Fig. 1 (b) is the stereoscan photograph of the pyrolytic hard carbon material in the embodiment of the present invention 1.
Fig. 2 is the stereoscan photograph of the pyrolytic hard carbon material in the embodiment of the present invention 2.
Fig. 3 is the stereoscan photograph of the pyrolytic hard carbon material in the embodiment of the present invention 3.
Fig. 4 is the stereoscan photograph of the pyrolytic hard carbon material in the embodiment of the present invention 7.
Fig. 5 is the stereoscan photograph of the pyrolytic hard carbon material in the embodiment of the present invention 10.
Fig. 6 (a)-Fig. 6 (b) is the stereoscan photograph of the pyrolytic hard carbon material in comparative example 1 of the present invention.
Fig. 7 is the stereoscan photograph of the pyrolytic hard carbon material in comparative example 2 of the present invention.
Fig. 8 is the X ray diffracting spectrum of the pyrolytic hard carbon material in the embodiment of the present invention 1.
Fig. 9 is the Raman collection of illustrative plates of the pyrolytic hard carbon material in the embodiment of the present invention 1.
Figure 10 is the electron diffraction diagram of the pyrolytic hard carbon material in the embodiment of the present invention 1.
Figure 11 is the charging and discharging curve figure of the pyrolytic hard carbon material in the embodiment of the present invention 1 as lithium cell cathode material.
Figure 12 is the TEM figure of the pyrolytic hard carbon material of the embodiment of the present 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, there is micropore or mesopore in described pyrolytic hard carbon material inside.
According to embodiment of the present invention, the surface structure of the similar two dimensional surface that described laminar hard carbon material has, in the larger plane of this sheeting, smallest radial size is not less than 100:1 with the ratio of the average thickness of material, namely, described sheeting is similar two dimensional surface shape, and the smallest radial size in its plane is far longer than the nanometer grade thickness that this hard charcoal sheeting has.Referred to as " smallest radial size and average thickness ratio " in the present invention.
According to embodiment of the present invention, the control of pyrolytic process makes to be provided with micropore and/or mesopore in sheeting, and particularly, the micropore in this hard carbon material described and/or mesopore, micropore size can be less than 1nm, and mesopore pore size 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 that hard carbon precursor is at the gas containing protium or containing the thermal decomposition product in the atmosphere of the liquid vapour of protium.
According to embodiment of the present invention, in order to obtain the laminar hard carbon material with described feature, make the pyrolysis in the atmosphere containing active gases of hard carbon precursor be necessary condition, described atmosphere can be all be made up of described active gases, also can comprise carrier gas.
Described active gases can be the gas containing protium or the liquid vapour containing protium, and wherein, the described gas containing protium can be H
2, NH
3, or rudimentary hydrocarbon gas, such as CH
4, C
2h
4, C
2h
2in alkane, alkene, the alkynes of gaseous state, the described liquid vapour containing protium, such as H
2o steam, CH
3cOCH
3steam or CH
3cH
2the oxygen-containing organic compound that OH steam etc. are easily vaporized also can be the mist meeting above-mentioned requirements.
Pyrolysis atmosphere can introduce active gases by using carrier gas; described carrier gas can be the various GPF (General Protection False gases not participating in reacting; comprise one or more the combination in inert gas (helium, argon gas, neon, Krypton, xenon, radon gas etc.), carbon dioxide or nitrogen; from economy and the convenient aspect of source of the gas, such as nitrogen, carbon dioxide, argon gas etc. can be selected as carrier gas.
For obtaining the hard charcoal of laminar pyrolysis, the content of active gases at least accounts for the 1%(v/v of the atmosphere providing pyrolytic reaction), can be generally 1-10%.
In specific embodiment of the invention scheme, hard carbon precursor can be that dusty material or liquid form are introduced in pyrolysis systems.Hard carbon precursor usual first ball milling before pyrolysis becomes to have graininess or the powder of certain particle size, can directly use, also can be added in organic solvent, form the decentralized photo that granularity is comparatively homogeneous, such as, hard carbon precursor is made powder through removing the crystallization water or is mixed with organic solvent the solution that precursor concentration is 0.05-10M.Hard carbon precursor is made powder or utilizes decentralized photo to be all to better make itself and atmosphere fully contact, reach the object reacted completely.
Hard carbon precursor adds before pyrolysis systems preferably first dry, can add gas content in pyrolysis systems by Accurate Determining, also through de-crystallization water process or can not carry out de-crystallization water process.The benefit of dry and de-crystallization water process is the realization controlling pyrolytic process better, non-essential program.If utilize undried process or carry out described pyrolysis without the hard carbon precursor of abundant drying and dehydrating, even if pyrolysis systems is only carrier gas, can observes in the hard product char after pyrolysis and can there is minute quantity in laminar hard charcoal.To the conclusion of this phenomenon analysis should be, in 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 be mixed in carrier gas, cause the thermal decomposition product of hard carbon precursor under the display of SEM, local has the broken shape thin slice hard carbon material of minute quantity to occur.Clear and convenient for what state, the present invention is defined as the atmosphere at least containing 1% active gases to pyrolysis atmosphere, this active gases should be (when particularly first the carrying out drying to presoma) that operator specially introduces usually, when determine used presoma self contain certain moisture or other heat can gasify and the composition of hydrogen-containing gas is provided time, as long as this part gas is enough to the requirement meeting described pyrolysis atmosphere, such pyrolysis systems also should belong to the scope that the claims in the present invention define.
In the solution of the present invention, can not particular determination be made to used hard carbon precursor, known or conventional various heat supply solutions can be used to obtain the hard carbon precursor of hard charcoal.In specific embodiments, described hard carbon precursor can be one or more combination of these materials.This presoma can be carbohydrate, synthetic resin containing C, H, O element or soft charcoal presoma be via containing the cross-linking products under the effect of oxygen element crosslinking agent.
Described carbohydrate can be such as monose or polysaccharide, such as, can be glucose, sucrose, fructose, cellulose or starch etc.
According to the embodiment of the present invention, the described synthetic resin containing C, H, O element comprises thermosetting resin or thermoplastic resin through the product containing oxygen cross-linking agents.
According to the specific embodiment of the present invention, the described synthetic resin containing C, 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 oxygen cross-linking agents products therefrom.
Described soft charcoal presoma is via the cross-linking products contained under the effect of oxygen element crosslinking agent, and such as, pitch obtains hard carbon precursor etc. through cumyl peroxide cross-linking agents.
Laminar pyrolytic hard carbon material described in the present invention, be construed as in the thermal decomposition product obtained according to the inventive method, meet the above hard charcoal of flake limited and occupy enough large ratio, and not require thermal decomposition product be all defined flake, but, this hard charcoal of flake occupying enough vast scales is enough to have fully demonstrated the flake performance that charcoal is given firmly when described pyrolytic hard carbon material is employed and improves, or purer lamellar material can be collected by suitable separation completely, can think that thermal decomposition product is required laminar hard carbon material accordingly.
Pyrolytic hard carbon material provided by the invention, there is unique appearance structure, the specific area of remarkable lifting, excellent absorption and load-carrying properties can be provided, may be used for current hard carbon material or other porous material institute applicable each field and occasion, such as, for the manufacture of the electrode (negative pole) of secondary cell (lithium battery or sode cell etc.), as the electrode catalyst support of fuel cell or metal-air batteries, for the manufacture of the electrode of capacitor, and as the application of adsorbent or decolorizer, can also be used to prepare the composite material with height increasing tougheness, noxious substance adsorbent, the adsorbent of special purpose, decolorizer raw material etc. in food production.
Embodiment 1
10g glucose is placed in 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 DEG C with the speed of 2 DEG C/min, after maintaining basic constant temperature 15h, naturally cool to room temperature, obtain average thickness and be about 3nm, geometrical surface is about 623m
2/ g, minimum-value aperture is about 0.7nm, smallest radial size and the laminar pyrolytic hard carbon material of average thickness than about 5200:1.
The SEM photo of this lamellar material under multiplication factor is respectively 5K and 10K, as Fig. 1 (a) and Fig. 1 (b) display, can be clearly seen that from this SEM figure: the pyrolytic hard carbon material pattern made through above-mentioned preparation method is based on flake.
X ray diffracting spectrum as shown in Figure 8, d
002=3.72; Raman collection of illustrative plates as shown in Figure 9, L
a=23nm.
Electronic diffraction as shown in Figure 10, can be learnt from this figure: 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 in powder X-ray RD spectrum.
TEM as shown in figure 12, can clearly be seen that from this figure the situation that thin slice is piled up.
Embodiment 2
Except with Ar-1%H
2(H
2account for Ar-H
2the percent by volume of gaseous mixture is 1%) replace 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, and geometrical surface is about 405m
2/ g, minimum-value aperture is about 0.7nm, gets obtained sheeting, its smallest radial size with average thickness than about 3200:1.
This lamellar material multiplication factor be the SEM photo of 2K as shown in Figure 2, can be clearly seen that from this SEM figure: the pyrolytic hard carbon material made through above-mentioned preparation method is rendered as a large amount of flakes, can obtain through being suitably separated the hard carbon material being mainly thin slice.
According to X ray diffracting spectrum, d
002=3.72; 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%) replace Ar-8%H
2outward, all the other obtain pyrolytic hard carbon material according to method similarly to Example 1, and the sheet output got wherein detects, and its average thickness is about 8nm, and geometrical surface is about 280m
2/ g, minimum-value aperture is about 0.7nm, and smallest radial size and average thickness are than about 1000:1.
This lamellar material multiplication factor be the SEM photo of 1K as shown in Figure 3, can be clearly seen that from this SEM figure: the pyrolytic hard carbon material made through above-mentioned preparation method presents a certain amount of flake, more difficult separated and collected.
According to X ray diffracting spectrum, d
002=3.72; Raman collection of illustrative plates, L
a=20nm.
Embodiment 4
Except replacing except 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, and geometrical surface is about 520m
2/ g, minimum-value aperture is about 0.7nm, and smallest radial size and average thickness are than about 4600:1.
According to X ray diffracting spectrum, d
002=3.71; Raman collection of illustrative plates, L
a=23.1nm.
Embodiment 5
Except replacing except the hard carbon precursor of 10g glucose so that pitch is obtained product through the process of cumyl peroxide cross-linking agents, all the other obtain laminar pyrolytic hard carbon material according to method similarly to Example 1, its average thickness is about 5nm, and geometrical surface is about 401m
2/ g, minimum-value aperture is about 0.7nm, and smallest radial size and average thickness are than about 3800:1.
According to X ray diffracting spectrum, d
002=3.75; Raman collection of illustrative plates, L
a=23nm.
Embodiment 6
Except replacing except 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, and geometrical surface is about 571m
2/ g, minimum-value aperture is about 0.7nm, and smallest radial size and average thickness are than about 3900:1.
According to X ray diffracting spectrum, d
002=3.75; Raman collection of illustrative plates, L
a=24nm.
Embodiment 7
10g glucose is placed in 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 DEG C with the speed of 2 DEG C/min, after maintaining basic constant temperature 15h, naturally cool to room temperature, obtain average thickness and be about 3.2nm, geometrical surface is about 601m
2/ g, minimum-value aperture is about 0.7nm, smallest radial size and the laminar pyrolytic hard carbon material of average thickness than about 5800:1.
This lamellar material is respectively the SEM photo of 2K as shown in Figure 4 in multiplication factor, can be clearly seen that: the pyrolytic hard carbon material made through above-mentioned preparation method presents flake from this SEM figure.
According to X ray diffracting spectrum, d
002=3.71; Raman collection of illustrative plates, L
a=22.1nm.
Embodiment 8
Except replacing except 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, and geometrical surface is about 511m
2/ g, minimum-value aperture is about 0.7nm, smallest radial size and average thickness are than about 4200:1.
According to X ray diffracting spectrum, d
002=3.71; Raman collection of illustrative plates, L
a=23nm.
Embodiment 9
Except pitch being replaced except the hard carbon precursor of 10g glucose through the product that the process of cumyl peroxide cross-linking agents is obtained with 10g, all the other obtain laminar pyrolytic hard carbon material according to method similarly to Example 7, its average thickness is about 4nm, and geometrical surface is about 495m
2/ g, minimum-value aperture is about 0.7nm, smallest radial size and average thickness are than about 4100:1.
According to X ray diffracting spectrum, d
002=3.73; Raman collection of illustrative plates, L
a=23nm.
Embodiment 10
10g glucose is placed in 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 DEG C with the speed of 2 DEG C/min, after maintaining basic constant temperature 10h, naturally cool to room temperature, obtain average thickness and be about 3.2nm, geometrical surface is about 601m
2/ g, minimum-value aperture is about 0.7nm, smallest radial size and the laminar pyrolytic hard carbon material of average thickness than about 5200:1.
This lamellar material is respectively the SEM photo of 5K as shown in Figure 5 in multiplication factor, can be clearly seen that: the pyrolytic hard carbon material made through above-mentioned preparation method presents flake from this SEM figure.
According to X ray diffracting spectrum, d
002=3.72; Raman collection of illustrative plates, L
a=21.0nm.
Embodiment 11
Except replacing except 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, and geometrical surface is about 485m
2/ g, minimum-value aperture is about 0.7nm, and smallest radial size and average thickness are than about 4200:1.
According to X ray diffracting spectrum, d
002=3.71; Raman collection of illustrative plates, L
a=21.2nm.
Embodiment 12
Except pitch being replaced except the hard carbon precursor of 10g glucose through the product that the process of cumyl peroxide cross-linking agents is obtained with 10g, all the other obtain laminar pyrolytic hard carbon material according to method similarly to Example 10, its average thickness is about 4.6nm, and geometrical surface is about 412m
2/ g minimum-value aperture is about 0.8nm, smallest radial size and average thickness are than about 4100:1.
According to X ray diffracting spectrum, d
002=3.68; Raman collection of illustrative plates, L
a=22nm.
Embodiment 13
Except replacing except 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, and geometrical surface is about 420m
2/ g, minimum-value aperture is about 0.7nm, and smallest radial size and average thickness are than about 2300:1.
According to X ray diffracting spectrum, d
002=3.71; Raman collection of illustrative plates, L
a=18.5nm.
Embodiment 14
Except replacing except 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, and geometrical surface is about 450m
2/ g, minimum-value aperture is about 0.7nm, and smallest radial size and average thickness are than about 2100:1.
According to X ray diffracting spectrum, d
002=3.68; Raman collection of illustrative plates, L
a=18.2nm.
Embodiment 15
Except replacing except 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, and geometrical surface is about 325m
2/ g, minimum-value aperture is about 0.7nm, and smallest radial size and average thickness are than about 2000:1.
According to X ray diffracting spectrum, d
002=3.76; Raman collection of illustrative plates, L
a=17.5nm.
Embodiment 16
Except replacing except the heating rate of 2 DEG C/min with the heating rate of 10 DEG C/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, and geometrical surface is about 311m
2/ g, minimum-value aperture is about 0.7nm, and smallest radial size and average thickness are than about 2500:1.
According to X ray diffracting spectrum, d
002=3.71; Raman collection of illustrative plates, L
a=15.5nm.
Embodiment 17
Except replacing except the heating rate of 2 DEG C/min with the heating rate of 10 DEG C/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, and geometrical surface is about 301m
2/ g, minimum-value aperture is about 0.7nm, and smallest radial size and average thickness are than about 2600:1.
According to X ray diffracting spectrum, d
002=3.71; Raman collection of illustrative plates, L
a=15.6nm.
Embodiment 18
Except replacing except the heating rate of 2 DEG C/min with the heating rate of 10 DEG C/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, and geometrical surface is about 310m
2/ g, minimum-value aperture is about 0.7nm, and smallest radial size and average thickness are than about 2760:1.
According to X ray diffracting spectrum, d
002=3.75; Raman collection of illustrative plates, L
a=15.3nm.
Embodiment 19
Except replacing except the gas flow of 50mL/min with the gas flow of 100mL/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, and geometrical surface is about 462m
2/ g, minimum-value aperture is about 0.7nm, and smallest radial size and average thickness are than about 2900:1.
According to X ray diffracting spectrum, d
002=3.75; Raman collection of illustrative plates, L
a=18.5nm.
Embodiment 20
Except replacing except the gas flow of 50mL/min with the gas flow of 100mL/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, and geometrical surface is about 471m
2/ g, minimum-value aperture is about 0.7nm, smallest radial size and average thickness are than about 3100:1.
According to X ray diffracting spectrum, d
002=3.71; Raman collection of illustrative plates, L
a=18.1nm.
Embodiment 21
Except replacing except the gas flow of 50mL/min with the gas flow of 100mL/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, and geometrical surface is about 461m
2/ g, minimum-value aperture is about 0.7nm, smallest radial size and average thickness are than about 2800:1.
According to X ray diffracting spectrum, d
002=3.72; Raman collection of illustrative plates, L
a=18.2nm.
Embodiment 22
Except being warming up to except 750 DEG C to be warming up to 950 DEG C 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, and geometrical surface is about 325m
2/ g, minimum-value aperture is about 0.8nm, smallest radial size and average thickness are than about 1900:1.
According to X ray diffracting spectrum, d
002=3.71; Raman collection of illustrative plates, L
a=24nm.
Embodiment 23
Except being warming up to except 750 DEG C to be warming up to 950 DEG C 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, and geometrical surface is about 365m
2/ g, minimum-value aperture is about 0.7nm, and smallest radial size and average thickness are than about 1950:1.
According to X ray diffracting spectrum, d
002=3.75; Raman collection of illustrative plates, L
a=24.1nm.
Embodiment 24
Except being warming up to except 750 DEG C to be warming up to 950 DEG C 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, and geometrical surface is about 360m
2/ g, minimum-value aperture is about 0.7nm, smallest radial size and average thickness are than about 1860:1.
According to X ray diffracting spectrum, d
002=3.72; Raman collection of illustrative plates, L
a=24.6nm.
Embodiment 25
Except replacing except 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, and geometrical surface is about 301m
2/ g, minimum-value aperture is about 0.8nm, and smallest radial size and average thickness are than about 1200:1.
According to X ray diffracting spectrum, d
002=3.72; Raman collection of illustrative plates, L
a=15.4nm.
Embodiment 26
Except replacing except 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, and geometrical surface is about 298m
2/ g, minimum-value aperture is about 0.8nm, and smallest radial size and average thickness are than about 1100:1.
According to X ray diffracting spectrum, d
002=3.69; Raman collection of illustrative plates, L
a=15.6nm.
Embodiment 27
Except replacing except 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, and geometrical surface is about 286m
2/ g, minimum-value aperture is about 0.8nm, and smallest radial size and average thickness are than about 1190:1.
According to X ray diffracting spectrum, d
002=3.71; Raman collection of illustrative plates, L
a=15.3nm.
Embodiment 28
Replace except 10g glucose except dissolving 10g glucose wiring solution-forming with 100mL ethanol, all the other obtain laminar pyrolytic hard carbon material according to method similarly to Example 1, and its average thickness is about 4nm, and geometrical surface is about 501m
2/ g, minimum-value aperture is about 2.2nm, and smallest radial size and average thickness are than about 4650:1.
According to X ray diffracting spectrum, d
002=3.70; Raman collection of illustrative plates, L
a=23.2nm.
Comparative example 1
10g glucose is placed in pyrolysis reactor, passes into Ar with the gas flow of 50mL/min, and make reactor temperature rise to 750 DEG C with the speed of 2 DEG C/min, after maintaining basic constant temperature 15h, naturally cool to room temperature, collect the pyrolytic hard carbon material obtained.
This material is respectively 300 in multiplication factor, the SEM photo of 1K is as shown in Fig. 6 (a) He Fig. 6 (b), can be clearly seen that from this SEM figure: the pyrolytic hard carbon material made through above-mentioned preparation method is based on graininess, and wherein there is minute quantity is laminar product.
According to X ray diffracting spectrum, d
002=3.71; Raman collection of illustrative plates, L
a=20.1nm.
Comparative example 2
10g glucose is placed in pyrolysis reactor, passes into CO with the gas flow of 50mL/min
2, and make reactor temperature rise to 750 DEG C with the speed of 2 DEG C/min, after maintaining basic constant temperature 15h, naturally cool to room temperature, collect the pyrolytic hard carbon material obtained.
This material is respectively the SEM photo of 3K as shown in Figure 7 in multiplication factor, can be clearly seen that from this SEM figure: the pyrolytic hard carbon material made through above-mentioned preparation method is based on graininess, and wherein there is minute quantity is laminar product.
According to X ray diffracting spectrum, d
002=3.70; Raman collection of illustrative plates, L
a=21.1nm.
From above-described embodiment and comparative example:
1, comparative example 1 and comparative example 2 show: directly joined by the hard carbon precursor of undried process and be only in the pyrolysis systems of carrier gas, can contain a small amount of pattern in the hard charcoal of pyrolysis is laminar product, should be due in high temperature pyrolysis process, hard carbon precursor with moisture and the hydrogeneous elemental gas that goes out of the thermal decomposition of presoma own be mixed in carrier gas, causing the thermal decomposition product of hard carbon precursor under the display of SEM, there is the broken shape thin slice hard carbon material of minute quantity in local; Further, when hard carbon precursor is at carrier gas (Ar or CO
2) atmosphere in carry out the flake that pyrolytic hard carbon material that pyrolytic reaction makes presents minute quantity, find through coherent detection, its average thickness is significantly greater than in above-described embodiment the hard charcoal thin slice using the pyrolysis atmosphere containing active gases to obtain, and its geometric jacquard patterning unit surface sum smallest radial size and average thickness are than the hard charcoal thin slice be all significantly less than in embodiment; Meanwhile, the hard charcoal of flake content in thermal decomposition product is few, just exists with " impurity ".
2, embodiment 1-embodiment 3 and comparative example 1
Comparative example 1 is that hard carbon precursor carries out high temperature pyrolysis in the pyrolysis systems being only carrier gas, and embodiment 3-embodiment 1 is hard carbon precursor at the mist of active gases and carrier gas, and namely atmosphere is respectively Ar-0.5%H
2, Ar-1%H
2and Ar-8%H
2parallel embodiment, be only Ar at atmosphere, until atmosphere alternation becomes Ar-8%H
2process in, only to the active gases H adding content in carrier gas Ar and increase progressively
2, our beyond thought discovery in the process: because of the introducing of active gases, cause the change of thermal decomposition product pattern, namely obtain the thin slice hard carbon material of similar graphene-like.Further, when active gases content reaches 1%, the hard carbon content of the flake in thermal decomposition product has accounted for suitable vast scale, directly can utilize and demonstrate the performance of the hard charcoal of thin slice pattern.
application example 1 lithium battery
A, laminar pyrolytic hard carbon material embodiment 1 made are used as lithium cell cathode material, and its concrete operation method is as follows:
By the aqueous solution of the laminar hard carbon material obtained and binding agent sodium carboxymethylcellulose (CMC) at normal temperatures and pressures mixed grinding form slurry, then even application is on Copper Foil substrate, at vacuum condition, dries 6h, at 20kg/cm at temperature 105 DEG C
2pressure tight, then membrane electrode to be cut into area be 1cm
2circular electric pole piece, and with lithium metal for become button cell to electrode assembling, wherein, in electrode slice, the mass ratio of the hard charcoal of laminar pyrolysis and binding agent sodium carboxymethylcellulose (CMC) is 9:1.
The electrolyte of simulated battery is 1mol LiPF
6be dissolved in the mixed solvent (volume ratio 1:1) of 1L EC and DMC.By positive pole, negative pole, electrolyte, barrier film is assembled into simulated battery in the glove box of argon shield.
Tested on the electric discharge and recharge instrument of indigo plant by the above-mentioned button cell be assembled into, as shown in figure 11, discharge and recharge is 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 Large ratio surface characteristic.
B, the laminar hard carbon material produced out with embodiment 1 are for carrier, and produce the lithium ion battery negative material of SnSb load, concrete operation method is as follows:
First, 22.8g SbCl is dissolved with 1L ethylene glycol
3with 22.6g SnCl
22H
2the mixture of O, then adds the above-mentioned hard carbon material made of 56g and is placed in frozen water, slowly add 16.3g zinc powder reaction 2h after suction filtration, washing, until filtrate meet AgNO
3constant muddiness.The filter cake obtained is heated 12h at 60 DEG C, vacuum, namely obtains the hard carbon composite that Sb and Sn load capacity is respectively 16.5%, 16.2%.Implement the mode described in A to this hard carbon composite and carry out assembled battery, its reversible capacity is up to 550mAh/g.
application example 2 transducer
The laminar hard carbon material produced out with embodiment 7 is for carrier, and produce resistance hydrogen sensor critical material, concrete operation method is as follows:
Hard carbon material is dissolved in phenmethylol, with SnCl
4for presoma microwave process for synthesizing load SnO
2particle, then at 140 DEG C, is that reducing agent reduces H with ethylene glycol with microwave process for synthesizing
2ptCl
6wash after 5min, dry, namely obtain Pt-SnO
2/ C composite.
By chemical analysis (ICP) known Pt-SnO
2pt, SnO in/C composite
2, C mass percent is respectively 20%, 60%, 20%.SnO
2particle is 4nm, Pt particle is 3nm.Due to Pt-SnO
2/ C composite responsive contacting with hydrogen molecule can trigger dissociating of metal, thus at low concentration H
2(0.1%-3%) have extremely responsive response under 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 very suitable as H
2deng the base material of gas sensor.
application example 3Pt-C fuel-cell catalyst carrier
The laminar hard carbon material produced out with embodiment 10 is for carrier, and produce Pt-C fuel-cell catalyst critical material, concrete operation method is as follows:
By the H of 50mg hard carbon material, 10mL0.0096M
2ptCl
6, 25mL ethylene glycol, 4mL0.05MKOH after abundant stirring reaction 3h, be down to room temperature, fully wash with ethanol, dry, namely obtain Pt-C fuel-cell catalyst, its Pt load quality percentage 30% at 135 DEG C.
Take 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 is 3:1, after becoming ink shape, is sprayed on polished glass carbon as work electrode.
At 30 DEG C, with the H of 0.5M
2sO
4for electrolyte, test H with the speed of sweeping of 20mV/s in 0-1.2V interval
2absorption and desorption curve known: at 45 DEG C, with the H of 0.5M
2sO
4be electrolyte with the ethanolic solution of 2M, with 20mV/s to sweep speed test methanol oxidation known: under Pt-C fuel-cell catalyst exists, the electric current of methanol oxidation reduction is 386mA/mg
pt.Because laminar hard carbon material has higher geometrical surface, therefore when a certain amount of Pt load can obtain comparing other material with carbon elements on this hard charcoal thin slice, distribution is more even, has the catalyst material at larger effecting reaction interface.
application example 4MnO2-C ultracapacitor
The laminar hard carbon material produced out with embodiment 5 is for carrier, and produce the lithium ion battery negative material of SnSb load, concrete operation method is as follows:
After getting the ultrasonic 1h of hard charcoal aqueous solution 100mL of 1.5mg/mL, add 0.95g potassium permanganate under agitation microwave heating 5min, then fully wash with deionization, ethanol successively, at 120 DEG C, vacuum, dry 12h, namely obtain MnO
2the hard charcoal sheeting of load, its MnO
2load capacity be 80%.
By obtained MnO
2load hard carbon material and carbon black, polytetrafluoroethylene, mix in ethanol, and uniform application is on nickel screen with the mass ratio of 75:20:5, dries 12h in 120 DEG C, vacuum.MnO will be scribbled
2the nickel screen of-C, as work electrode, is to electrode with platinum electrode, take saturated calomel electrode as reference electrode, with the metabisulfite solution of 1M for electrolyte, at room temperature does cyclic voltammetry scan.
Its result shows: the speed of sweeping with 2mV/s between-0.1 to 0.9V does cyclic voltammetry, and obtaining material specific capacitance is 402F/g.Because this laminar hard carbon material has better intensity than Graphene, and inner existing defects, make load oxide can in more stably load on carbon plate, and high geometrical surface provide not only the conductive network of whole material, also provide great response area simultaneously, therefore with in the catalyst, this hard carbon material is rare carbon carrier.
application example 5C-decolorizer
The laminar hard carbon material produced using embodiment 2 detects its decoloration performance to material as decolorizer, and concrete operation method is as follows:
Get 5 glasss of monosodium glutamate water (every glass of 100mL), add 0.2 respectively, 0.5,0.8, the above-mentioned hard carbon material of 1.0g, 1.3g.Light transmittance measurement is carried out by the monosodium glutamate water adding hard carbon material to above-mentioned 5 glasss, result shows: the monosodium glutamate water light transmittance adding 1.0g hard carbon material is the highest, reach 85%, compare existing material with carbon element and exceed about 5%, laminar hard carbon material demonstrates stronger decoloration performance.
Last it is noted that above embodiment is only in order to illustrate technical scheme of the present invention, be not intended to limit; Although with reference to previous embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that: it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein portion of techniques feature; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (21)
1. a pyrolytic hard carbon material, is characterized in that, its be to hard carbon precursor the gas containing protium or containing protium liquid vapour atmosphere in thermal decomposition product, there is average thickness 1-8nm, geometrical surface 10-2000m
2the sheeting of the similar two dimensional surface of/g, the smallest radial size of the similar two dimensional surface of described sheeting is not less than 1000:1 with the ratio of its average thickness, there is micropore or mesopore in described pyrolytic hard carbon material inside, micropore size is less than 1nm, mesopore pore size is 2-20nm, and described geometrical surface is the surface area under the flat expand state formed after described sheeting being folded the regional implementation with fold.
2. pyrolytic hard carbon material according to claim 1, the geometrical surface 10-1000m of described sheeting
2/ g.
3. prepare a method for pyrolytic hard carbon material as claimed in claim 1 or 2, the method forms by by the reactant be made up of hard carbon precursor step of pyrolysis in atmosphere, wherein,
The active gases of 1-100% is contained in described atmosphere;
Described hard carbon precursor pyrolytic process at least comprises: control gas flow 0.1-500mL/min to provide atmosphere, hard carbon precursor and gas is made fully to contact formation pyrolysis systems, and make pyrolysis systems with the ramp of 0.5-10 DEG C/min to 400-2000 DEG C, be cooled to room temperature after maintaining this temperature 0-72 hour;
Described active gases comprises the gas containing protium or the liquid vapour containing protium.
4. method according to claim 3, in hard carbon precursor pyrolytic process, controls gas flow 10-300mL/min.
5. method according to claim 3, in hard carbon precursor pyrolytic process, controls pyrolysis systems and is warming up to 400-1500 DEG C.
6. the method according to any one of claim 3-5, in hard carbon precursor pyrolytic process, after pyrolysis systems intensification terminates, holding temperature 0-20 hour.
7. method according to claim 3, hard carbon precursor is that dusty material or liquid form are present in pyrolysis systems.
8. method according to claim 3, through taking off crystallization water process or not carrying out de-crystallization water process before hard carbon precursor adds pyrolysis systems.
9. method according to claim 8, hard carbon precursor is made powder through removing the crystallization water or is mixed with organic solvent the solution that precursor concentration is 0.05-10M.
10. method according to claim 3, described hard carbon precursor is carbohydrate, synthetic resin containing C, H, O element or its combination in any.
11. methods according to claim 10, described carbohydrate monosaccharide or polysaccharide.
12. methods according to claim 11, described carbohydrate comprises glucose, sucrose, fructose, cellulose or starch.
13. methods according to claim 10, the described synthetic resin containing C, H, O element comprises thermosetting resin or thermoplastic resin through the product containing oxygen cross-linking agents.
14. methods according to any one of claim 10-13, the described synthetic resin containing C, H, O element comprises phenolic resins, Lauxite, epoxy resin, fluororesin, unsaturated polyester (UP), polyurethane, or polyethylene, polypropylene, polystyrene, polyvinyl chloride is through containing oxygen cross-linking agents products therefrom.
15. methods according to claim 3, described atmosphere is the mist of active gases or active gases and carrier gas, and described carrier gas comprises one or more the combination in inert gas, nitrogen or carbon dioxide.
16. methods according to claim 3, the described gas containing protium comprises H
2, NH
3, or alkane, alkene, alkynes hydrocarbon gas, the described liquid vapour containing protium comprises H
2o steam, CH
3cOCH
3steam or CH
3cH
2oH steam.
17. methods according to any one of claim 3-5, in described atmosphere, the content of active gases is 1-10%.
The application of pyrolytic hard carbon material described in 18. claims 1 or 2 in the electrode manufacturing secondary cell.
Pyrolytic hard carbon material described in 19. claims 1 or 2 is as the application of the electrode catalyst support of fuel cell or metal-air batteries.
Pyrolytic hard carbon material described in 20. claims 1 or 2 is manufacturing the application in electrode for capacitors.
Pyrolytic hard carbon material described in 21. claims 1 or 2 is as the purposes of adsorbent or decolorizer.
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| CN104016512B (en) * | 2014-06-10 | 2016-01-13 | 上海大学 | A kind of method utilizing spartina alterniflora loisel's base charcoal Treatment of Copper waste water |
| 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 |
| 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 |
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| 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 |
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| 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 |
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