CN107580587A - Micropore/mesoporous carbon - Google Patents

Micropore/mesoporous carbon Download PDF

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Publication number
CN107580587A
CN107580587A CN201580079601.9A CN201580079601A CN107580587A CN 107580587 A CN107580587 A CN 107580587A CN 201580079601 A CN201580079601 A CN 201580079601A CN 107580587 A CN107580587 A CN 107580587A
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precursor
carbon
porous carbon
group
polymer
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鲍哲南
J·杜
何嘉俊
J·威尔考科斯
梅建国
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Leland Stanford Junior University
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Leland Stanford Junior University
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Priority claimed from US14/701,322 external-priority patent/US20150232340A1/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof

Abstract

Classifying porous graphite (HPG) carbon is provided by improved method.First scheme is to be based on forming 3D polymer networks by the first precursor and the second precursor and make its carbonization.Carbon in obtained carbon structure comes from the first precursor, and volatilization is known from experience before second to form hole.However, the second precursor is heat-resisting, thus when the second precursor volatilizees, the first precursor is carbonized.Alternative plan is to be based on forming structuring polymer by the first and second precursors.More specifically, the second precursor forms the second polymer with micellar structure, and the first precursor forms the first polymer of coating second polymer micellar structure.Structuring polymer is carbonized.Herein, obtain the carbon in carbon structure and also come from the first precursor, and volatilization is known from experience before second to form hole.

Description

Micropore/mesoporous carbon
Technical field
The present invention relates to the manufacture of porous carbon.
Background technology
Have studied porous carbon and porous carbon containing hetero atom and a variety of applications of a period of time, for example, for example store up Can device, CO2Capture, purification for gas and separation, catalysis, water purifying and deodorization.However, economically fabricate with entirely controlled property The porous carbon of energy is still challenging.May be relatively cheap for example, manufacturing porous carbon by biomaterial, but it is likely difficult to Control processing result.Another program is more accurately to be controlled using template with providing the hole in porous carbon.However, the template scheme It is difficult to be intended to, and therefore cost is high.Therefore it provides in the art will for the improved method for manufacturing porous carbon It can be a progress.
The content of the invention
The research has two aspects, and it is related to two different modes for providing classifying porous graphite (HPG carbon).
In a first aspect, illustrative methods comprise the following steps：1) the first precursor is provided, first precursor includes one kind Or a variety of aromatic monomers；2) the second precursor is provided；3) 3D polymer networks are formed by the first precursor and the second precursor, wherein, the Two precursors provide crosslinking for one or more polymer from the first precursor；4) 3D polymer networks are dried to provide Drying structure；And 5) drying structure is carbonized to provide porous carbon structure, wherein, the carbon of porous carbon structure is at least partly There is provided by the carbonization of the first precursor, wherein the hole of porous carbon structure is at least partly provided by the volatilization of the second precursor, and wherein The volatilization of second precursor at least partly occurs when drying structure is partially carbonized.
In other words, the second precursor is with respect to having temperature tolerance, thus the second precursor before drying structure carbonization It will not volatilize completely.Because it is held in place (at least in part) during carbonization, when hole is formed during carbonization, this is helped Caved in preventing hole.By considering that reverse situation can be clearly understood this point, wherein, when the first precursor starts The second precursor all volatilizees during carbonization.In the case of (undesirable), the mechanical support that crosslinking is provided by the second precursor will It is not present during fabrication, wherein there's almost no or provide alternate configurations supporting in the absence of carbon.As a result it will reduce and be obtained The porosity of carbon structure.
The porous carbon structure obtained by the above method of first aspect can be activated further to increase its porosity. If activated, the activation preferably at 1200 DEG C or lower, more preferably 1000 DEG C or lower, even more preferably 800 DEG C or Carried out under lower temperature.The aromatic monomer and the second crosslinking agent can include one or more hetero atoms (that is, non-carbon or hydrogen Atom) to provide the functional group in porous carbon structure.The aromatic monomer can form one or more conjugated polymers.Institute It is preferably at least partly graphite to state loose structure.The 3D polymer networks can be by between the first precursor and the second precursor Covalently or non-covalently interaction formed.The noncovalent interaction can include hydrogen bond, metal-ligand key, and/or ion Key.Include but is not limited to suitable for the suitable material of the second precursor：Phytic acid, phytic acid derivative, inositol monophosphate, inositol monophosphate derive Thing, the phosphonate derivative containing two or more phosphonic acids, boroxine, four [phenyl -4- boryls (dihydroxy)] methane, contain The boronic acid derivatives and metal or H, H- phthalocyanine tetrasulfonic acid of two or more boric acid and contain two or more sulphurs The sulfonic acid of acid.
In second aspect, illustrative methods comprise the following steps：1) the first precursor is provided, first precursor has one Or multiple B groups are attached to the A-B structures on A skeletons；Wherein, A is hydrophobic aromatic monomer or the aromatic monomer being selected from the group Chemical combination：Pyrroles, thiazole, pyridine, aniline, thiophene, furans and their derivative；And wherein B is to be selected from the group Functional group：Hydroxy-acid group (- COOH), oh group (- OH), amino group (- NH2), nitrile group (- CN), sulfonic acid group (- SO3H), phosphonyl group (- PO4H), boric acid (- BO2H2), amide group (- C (=O)-NH-) and amino acid group (- CH (NH2)-COOH)；2) the second precursor is provided；3) structuring polymer is formed by first precursor and the second precursor, wherein tying The micellar structure that the structure of structure fluidized polymer is formed by the second precursor determines, and wherein, sets formed by the first precursor One polymer is to apply the micellar structure formed by the second precursor；And 4) structuring polymer is carbonized porous to provide Carbon structure, wherein, the carbon of porous carbon structure is at least partly provided by the carbonization of the first precursor, and the wherein hole of porous carbon structure At least partly provided by the volatilization of the second precursor.
B group can be hydrophilic, also, in this case, for formed second polymer micellar structure it is molten Agent can also be hydrophilic.Or B group can be hydrophobic, also, in this case, for forming the second polymerization The solvent of the micellar structure of thing is also hydrophobic.The porous carbon structure obtained by the above method of second aspect can be lived Change further to increase its porosity.If activated, the activation preferably at 1200 DEG C or lower, more preferably 1000 DEG C or It is lower, carried out under even more preferably 800 DEG C or lower temperature.The aromatic monomer can include one or more hetero atoms with Functional group in porous carbon structure is provided.The aromatic monomer can form one or more conjugated polymers.The porous knot Structure is preferably at least partly graphite.
According to these principles, offer exemplary experiment described further below proves.In chapters and sections B (being related to first aspect), First precursor is aniline, and the second precursor is phytic acid.In chapters and sections C (being related to second aspect), the first precursor be 4- (pyrroles- 1- yls) butyric acid (Py-COOH) monomer, and the second precursor is triblock copolymerP-123.It is however, of the invention Practice be not limited to these specific materials.The second precursor with temperature tolerance during carbonization to provide mechanical support The overall conception of (first aspect) and using micellar structure with effectively provide template be used for hole (second aspect) overall conception It can be used in other materials selection, portion of material is as detailed above.In addition, these aspects can individually be implemented or combine real Apply.
Other examples of suitable material are as follows.For in a first aspect, include suitable for the suitable material of the first precursor but It is not limited to：Pyrroles, azole derivatives, aniline, anil, thiophene, thiophene derivant, PEDOT:PSS (poly- (3,4- ethene Dioxy thiophene) PSS), PEDOT:PSS derivatives, phenol formaldehyde (PF), melamino-formaldehyde, have under acid conditions The conjugated polymer of positive charge and the melamine resol with negative electrical charge.Suitable for the suitable of the second precursor Material includes but is not limited to：Three acid, phytic acid, tannic acid, PSS, sulfoxidation graphene, alginic acid, phosphorous acid, sulphur Acid, boric acid and crosslinking agent have opposite charges with what the first precursor formed that electrically charged polymeric electrostatic interacts Salt.
For second aspect, include but is not limited to suitable for the suitable material of the first precursor：Pyrroles, azole derivatives, benzene Amine, anil, thiophene, thiophene derivant, PEDOT:PSS and PEDOT:PSS derivatives.Suitable for the second precursor Suitable material includes but is not limited to：CTAB (cetab),Composition series,System Row composition andComposition series.
Definition：
1) conjugated structure has alternate double bond and singly-bound.
2) it is covalently bound with multiple π delocalized electrons to be included in one or more of its chemical constitution for aromatic monomer Planar rings, the number of the multiple π delocalized electrons are even number but are not 4 multiples.
3) phytic acid has IUPAC (International Union of Pure and Applied Chemistry, IUPAC) title six [dihydrogen phosphoric acid] (1R, 2R, 3S, 4S, 5R, 6S)-hexamethylene -1,2,3,4,5, The own esters of 6-.It includes six phosphate groups.
4) inositol is six alcohol of hexamethylene, has formula C6H12O6。
5) inositol monophosphate substitutes one or more of inositol-OH groups to obtain by phosphate group.Example includes：Inositol Diphosphonic acid (2 substitution), inositoltriphosphoric acid (3 substitution), IP5 (5 substitution) and phytic acid (6 substitution).
6) phytic acid derivative substitutes 1 to 5 phosphate group in phytic acid to obtain by other chemical groups.Inositol monophosphate (inositol phosphate) derivative substitutes some (but being not all of) phosphorus in inositol monophosphate by other chemical groups Acid groups obtain.
7) Graphitic carbon structure is all or part of is configured to the weak binding plane layer of the carbon atom of honeycomb crystal lattice arrangement.
8) pyrroles has IUPAC title 1H- pyrroles, and its formula is C4H4NH。
9) thiazole has IUPAC title 1,3-thiazoles, and its formula is C3H3NS。
10) pyridine is standard IUPAC nomenclatures, and its formula is C5H5N。
11) aniline (aniline) has IUPAC titles phenyl amine (phenylamine), and its formula is C6H5NH2。
12) thiophene is standard IUPAC nomenclatures, and its formula is C4H4S。
13) furans is standard IUPAC nomenclatures, and its formula is C4H4O。
14) above-mentioned 8-13 arbitrary derivative substitutes one or more of these compounds by other chemical groups Hydrogen atom obtains.
15) micellar structure is the structure formed by scattered surfactant molecule in a liquid.
Brief Description Of Drawings
Figure 1A-C show the synthesis general introduction of Part I of the present invention.
Fig. 2A-B show the porosity and composition of 3D HPG carbon.
Fig. 3 A-F show the structure and form of 3D HPG carbon.
Fig. 4 A-D show the experimental result on 3D HPG carbon.
Fig. 5 A-F are shown in 0.5M H2SO4The performance of the supercapacitor of HPG carbon in aqueous electrolyte.
Fig. 6 A-C show the chemical property of the 3D HPG carbon for Li-S batteries.
Fig. 7 is the SEM image of dry PANi polymer backbones.
Fig. 8 A-F are the TEM images of the PANi polymer of carbonization at different temperatures.
Fig. 9 shows the CO of 3D HPG carbon2Absorption/desorption isotherm.
Figure 10 shows the pore-size distribution of commercially available porous carbon.
Figure 11 A-B show the N of commercially available porous carbon2Absorption/desorption isotherm and pore-size distribution.
Figure 12 A-D show other HRTEM images of 3D HPG carbon.
Figure 13 A-B show the XPS results on 3D HPG carbon.
Figure 14 shows the XPS spectrum of polymer backbone.
Figure 15 shows the XPS spectrum of carbonized polymers skeleton.
Figure 16 A-D are shown in organic 1M TEABF4Performance of the supercapacitor based on HPG carbon in/ACN electrolyte.
Figure 17 is shown in 0.5M H2SO4The long-term stable circulation of symmetrical ultracapacitor based on HPG carbon in electrolyte Property.
Figure 18 is the H in 0.5M2SO4In symmetrical ultracapacitor based on HPG carbon before and after 1000 circulations Nyquist curves.
Figure 19 is the signal for using 3D HPG carbon as the Li- polysulfide battery structures of sulphur main body (sulfur host) Property is shown.
Figure 20 A-B show the chemical property of 3D HPG carbon in Li-S batteries.
Figure 21 is shown in the Nyquist curves of the Li-S batteries based on HPG carbon under different recurrent states.
Figure 22 is the form for the summary for providing the different porous carbons synthesized at different conditions.
Figure 23 is the form for showing all kinds activated carbon price.
Figure 24 A show the synthesis general introduction of Part II of the present invention.
Figure 24 B-E are the SEM and TEM image on Figure 24 A synthesis.
Figure 25 A-D show the sign and gas absorption property of SU-MC1 porous carbons.
Figure 26 A-D show the sign and gas absorption property of SU-MAC1 porous carbons.
Figure 27 shows the scanning electron microscopy of SU-MC1 porous carbons.
Figure 28 shows the X-ray diffraction of SU-MC1 porous carbons.
Figure 29 A-D show SU-MC1 and SU-MAC1 porous carbon samples CO2And N2Isothermal initial slope.
Figure 30 shows SU-MC1 and SU-MAC1 CO2Isosteric heat of adsorption.
Figure 31 is shown in the N of SU-MAC1 under 77K2Adsorption-desorption isothermal.
Figure 32 A-B are shown in the N of two kinds of commercially available porous carbon samples under 77K2Absorption/desorption isotherm.
Figure 33 shows the CO of the SU-MAC1 compared with Conventional porous carbon sample2And N2Adsorption-desorption isothermal.
Figure 34 shows the Setup Experiments that (dynamic column breakthrough) experiment is penetrated for dynamic column.
Figure 35 shows the CO by SU-MC12Multi-cycle dynamic column adsorption capacity.
Figure 36 A-C show the mark detected in the dynamic column breakthrough experiment of several samples and humidity environment by mass spectrograph Standardization CO2Composition.
Figure 37 is shown on the SUM-MAC1 with acid impurities by for CO2Penetrate the mass spectrum of (breakthrough) The standardization CO that instrument is detected2Composition.
Figure 38 is 4- (pyrroles -1- bases) butyric acid1H-NMR is composed.
Figure 39 is the texture attribute and CO of the SU-MC1 and SU-MAC1 compared with the mesoporous carbon described in document2Capture property The form of energy.
Figure 40 is the form of the texture attribute of SU-MC1, SU-MAC1 and two kinds of commercially available porous carbon samples.
Embodiment
The chapters and sections include three parts.In the first portion, detailed mark is provided for accompanying drawing.Part II is related to by being conjugated Polymer molecule skeleton manufactures the experimental work of porous graphitic carbon.Part III is related to porous by the polypyrrole manufacture rationally designed The experimental work of graphitic carbon.
A) drawings in detail marks
Figure 1A-C show 3D HPG synthesis.Figure 1A is shown by the synthetically produced 3D HPG of nanostructured polymers molecular skeleton The schematic diagram of carbon network.Phytic acid helps be carbonized and maintaining 3D structures in activation process, prevents hole from caving in, and retain volatility Low molecular weight substance.Figure 1B is the chemical synthesis figure that wherein phytic acid has the PANi hydrogels as dopant and crosslinking agent concurrently.Figure 1C is the figure that the PANi (left side) of phytic acid crosslinking is converted into the graphite-like carbon plate (right side) of doping.Generally obtain 30wt% polymerization Thing is converted into the gross production rate of 3D HPG carbon.
Fig. 2A-B show the porosity and composition of 3D HPG carbon.Fig. 2A shows the N of HPG carbon2Absorption/desorption isotherm, clearly Show to Chu the effect of graded porous structure.In the relative pressure (P/P less than 0.010) under significant quantity N2Absorption is micropore Feature shows.P/P between 0.05-0.30Under continuous N2Absorption is attributed to N2Absorption is in mesoporous.With then 0.9 P/P0The N in the relatively flat region of lower abruptly increase2Absorb and represent the big mesoporous and presence of macropore.Commercially available high surface area AC is also provided (AC-1, for 1970m2 g-1High SBETSupercapacitor applications) thermoisopleth be used for compare.Between 0.05-3 P/P0Lower no obvious continuous N2Absorb represent to lack it is enough mesoporous.Fig. 2 B show N2And CO2The accumulation pore volume of absorption and Pore-size distribution (interior illustration).Pore-size distribution is by assuming that the slit hole geometry of micropore and mesoporous cylindrical geometries hole Calculated by non-linear density functional theory (nonlinear density functional theory, NLDFT).
Fig. 3 A-F show the structure and form of 3D HPG carbon.Fig. 3 A are the SEM figures of the carbonization PANi polymer at 700 DEG C Picture.Fig. 3 B and 3C are the macro network (main) and macroporous for the 3D HPG carbon that (difference) is shown in after being activated at 800 DEG C SEM and TEM image.Fig. 3 D be disclosed in 800 DEG C activation after graphite network (secondary) meso-hole structure TEM image.Fig. 3 E are Display generally has the TEM image of the graphene film network of several nanometers of lateral dimensions.Fig. 3 F are that display has clear and orderly six side The HRTEM images of the relatively large graphene film of shape carbon atom accumulation.Interior illustration shows the enlarged drawing at Fig. 3 F centers.
Fig. 4 A are shown in the drawing for making 3D HPG carbon made of the activation of carbonization PANi aeroges at 400 DEG C, 700 DEG C and 900 DEG C Graceful spectrum.Fig. 4 B show the I of the carbonization PANi and 3D HPG carbon from different carburizing temperaturesD/IGSummary.Fig. 4 C are to represent HPG Most of sp in carbon2With reference to HPG carbon and graphite EELS compose comparison.Fig. 4 D are indicated in different chemical environments in carbon skeleton N1s XPS spectrums existing for N dopants.
Fig. 5 A-F are shown in 0.5M H2SO4The performance of the supercapacitor of HPG carbon in aqueous electrolyte.Fig. 5 A display scannings Speed is 100,500 and 1000mV s-1When HPG carbon supercapacitors representative CV curves.The electrode quality load of CV measure For~1.5mg cm-2.Fig. 5 B show that current density is 10A g-1When single HPG carbon electrodes (in three-electrode battery) generation Table constant current charge/discharge curve.Fig. 5 C show made of different porous carbons the current density of electrode of super capacitor with The relation of specific capacitance.HPG carbon shows the electric capacity higher than AC and significantly more preferable high rate performance (rate capability). Fig. 5 D are the Nyquist curves of the symmetrical supercapacitor device manufactured by HPG carbon.Insertion figure shows high-frequency range.Fig. 5 E show Show the impedance angle of ultracapacitor based on HPG carbon and two commercially available ultracapacitors based on AC relative to frequency.City The electrolytic condenser sold also is compared.Characteristic frequency f0At 45 ° of phase angles equal resistance and capacitive impedance.Such as Desired, electrolytic condenser shows 1000Hz high characteristic frequency f due to no ion DIFFUSION TREATMENT0.The f of HPG carbon0 Appear in~7Hz, AC-1 f0Appear in 1Hz, and AC-2 f0Appear in~0.1Hz.(f) 0.2 and 2A g-1Current density Under the quality load of HPG carbon electrodes and the relation of area capacity.The area capacity of commercially available ultracapacitor is~1F cm-2, and The high-performance electric of most of recent report have relatively low or moderate area capacity (<1F cm-2)。
Fig. 6 A-C show the chemical property of the 3D HPG carbon for Li-S batteries.Fig. 6 A show HPG carbon/polysulfide and KB/ polysulfide electrodes balance respectively after under C/5 current rates charging/discharging voltages distribution.Discharge curve is from 2.4V Start with the platform at 2.05V, and charging curve show it is overlapping with the platform since 2.4V.Fig. 6 shows carbon/more sulphur respectively Compound (3.2mg cm-2), AC-1/ polysulfides (2.56mg cm-2) and KB/ polysulfides (1.28mg cm-2) electrode length Phase cyclical stability.After initial activation, during all circulations, the high coulombic efficiency of HPG carbon electrodes holding (CE ,~ 99.8%).Fig. 6 C show the area capacity and cycle life of HPG carbon/between sulfur electrode and the high-performance sulfur electrode of recent report Comparison.The sulfur electrode being previously reported by, which often has, is less than 3mAh g-1Area capacity, and less than 200 times circulation circulation Life-span.
Fig. 7 is the SEM image of dry PANi polymer backbones.Macropore and network structure are produced by rapid polymerization technique.
Fig. 8 A-F are in a nitrogen atmosphere in different temperatures (400 DEG C (Fig. 8 A-B), 700 DEG C (Fig. 8 C-D) and 900 DEG C (Fig. 8 E-F)) under the TEM image of PANi polymer that is carbonized 2 hours." embryo " graphene layer in carbonized polymers is with carbonization Temperature is improved and increased.
Fig. 9 is shown in the CO of the 3D HPG carbon (in 700 DEG C of carbonizations) under 273K2Absorption/desorption isotherm.
Figure 10, which is shown, comes from N2The AC-1 of absorption/desorption pore-size distribution.
Figure 11 A show the N of AC-2 (activated carbon for coming from Sigma-Aldrich company (Sigma-Aldrich))2Inhale Attached/desorption isotherm.Figure 11 B show AC-2's (activated carbon for coming from Sigma-Aldrich company (Sigma-Aldrich)) Pore-size distribution, show limited mesoporous and macropore.
Figure 12 A-D show the extra HRTEM images of graphene nanometer sheet in 3D HPG carbon (being carbonized at 700 DEG C).Arrow Represent clear lonsdaleite atom packing.
Figure 13 A-B show XPS results.More specifically, Figure 13 A show C1s XPS spectrums, and Figure 13 B show HPG carbon The O1s XPS spectrums of (being carbonized at 700 DEG C).
Figure 14 shows the XPS N1s spectrums of PANi polymer backbones.Most of n-signal is derived from NH4+(carrying out autoxidator), and Do not have signal to come from N-O.
Figure 15 is shown in the XPS N1s spectrums for the PANi polymer being carbonized at 700 DEG C.Most of n-signal is derived from and comes from aniline N -5 of monomer, and carbonization/pyrolytic process of the N-Q and N-O under high temperature.
Figure 16 A-D are shown in organic 1M TEABF4Performance of the supercapacitor based on HPG carbon in/ACN electrolyte.Figure 16A shows that sweep speed is 100,500 and 1000mV s-1When HPG carbon supercapacitors representative CV curves.Close to perfection The CV curves of rectangle can be in up to 1000mV s-1Potential scan rate under obtain, represent quick electrode kinetics (electrode kinetics).Figure 16 B show that current density is 10A g-1When single HPG carbon electrodes (in three-electrode battery In) representative constant current charge/discharge curve.Linear GC curves are shown reduces the purely capacitive of (0.036V) with smaller IR Charge/discharge.Figure 16 C are the Nyquist curves of the symmetrical supercapacitor device manufactured by HPG carbon.Insertion figure shows high frequency Scope.Figure 16 D show the impedance angle of HPG carbon supercapacitors relative to the relation of frequency.- 45 ° of phase angles appear in about~ 2.6Hz, represent fast ionic response.
Figure 17 is shown in 0.5M H2SO4The long-term cycle stability of symmetrical super capacitor based on HPG carbon in electrolyte. Charge/discharge current speed is 5A g-1。
Figure 18 is the H in 0.5M2SO4In symmetrical super capacitor based on HPG carbon before and after 1000 circulations Nyquist curves.Insertion figure shows high-frequency range.Battery ESR shows and had almost no change after long-term circulation.
Figure 19 is schematically showing for the Li- polysulfide battery structures that use 3D HPG carbon as sulphur main body (host). In this example, 1902 be lithium, and 1904 be barrier film, and 1906 be polysulfide, and 1908 be aluminium electrojet device, and 1910 refer to HPG provides the sub-component of sulphur main body.HPG carbon (stain on figure) is evenly coated on current collector and barrier film, and by more sulphur Compound active material is added on current collector.
Figure 20 A-B show the chemical property of 3D HPG carbon in Li-S batteries.Figure 20 A show that sweep speed is 0.5mV/s When HPG carbon/polysulfide CV curves (initial 6 circulations).HPG carbon/polysulfide the electrode determined in initial cycle The CV curves measured show two step reducing/oxidizing techniques of standard.It is observed that peak intensity and electricity during repetitive cycling Position offsets no significant changes, shows the redox reaction of high reversible and good cyclical stability.2.3V and 1.9V Two peak cathodes at place correspond to elemental sulfur (S8) it is reduced to long-chain polysulphides (Li2Sn, 4≤n≤8) and long-chain staying more It (is Li respectively that compound, which is reduced to short-chain polysulphides,2S2And Li2S).Two overlapping oxidation peaks are related to the more sulphur of short chain at 2.4V Compound is changed into long-chain polysulphides (Li2Sn,n≥2).Figure 20 B show that in sulphur quality load be 3.2mg cm-2When HPG The high rate performance of carbon/polysulfide electrode.After being circulated with higher rate, initial low range performance almost can be by returning to Recovered compared with low rate.
Figure 21 is shown in the Nyquist curves of the Li-S batteries based on HPG carbon under different recurrent states.Battery ESR is in work Change and slightly reduced after initial cycle, maintain stable cycle performance of battery.The performance is probably because in recharge/put Effective capture of lithium sulfide and it is uniformly distributed in ultra-high surface area porous, electrically conductive network during electricity.The sulphur quality load of the battery is 3.2mg cm-2。
Figure 22 is the form for the summary for providing the different porous carbons synthesized at different conditions.All surface product measure uses BET method is carried out in 87K by argon gas into narrow micropore.Pore volume is based on Nonlocal D FT (non-local density Functional theory, NLDFT) calculate be measured.
Figure 23 is the form for showing all kinds activated carbon price.
Figure 24 A-E show the synthetic schemes and sign of the doped meso-porous carbon of N.Figure 24 A are the synthesis and classification of SU-MC1 materials Loose structure is schematically shown.Figure 24 B and 24C are the SU-MC1 synthesized under pH=1 and pH=3.5 scanning electron respectively Micro- (SEM) image.The transmitted electron that Figure 24 D-E are the SU-MC1 for showing six square arrays [110] and [100] direction respectively shows Micro- (TEM) image (insertion figure：Fast Fourier diffraction pattern).
Figure 25 A-D show SU-MC1 sign and gas absorption property.Figure 25 A show N1s (398.4eV:N-6, 399.8eV:N-5,400.8eV:N-Q the x-ray photoelectron spectroscopy (XPS) on).The N2 adsorption that Figure 25 B are shown under 77K-take off Attached thermoisopleth.Figure 25 C are shown based on the CO under the nitrogen thermoisopleth (filled symbols) and 273K under 77K2Thermoisopleth (open symbols) The accumulation pore volume calculated by Nonlocal D FT (NLDFT) and pore-size distribution (insertion scheme).Figure 25 D are shown 273rd, the CO under 298 and 323K2Thermoisopleth and the N under 298K2Thermoisopleth.
Figure 26 A-D show SU-MAC1 sign and gas absorption property.Figure 26 A show N1s (398.1eV:N-6, 400.0eV:N-5,403.4eV:N- oxides) on x-ray photoelectron spectroscopy (XPS).Figure 26 B are shown based on the nitrogen under 77K CO under thermoisopleth (filled symbols) and 273K2Thermoisopleth (open symbols) is counted by Nonlocal D FT (NLDFT) The accumulation pore volume and pore-size distribution (insertion figure) of calculation.Figure 26 C show the CO under 273,298 and 323K2Thermoisopleth and N under 298K2Thermoisopleth.Figure 26 D are shown under dry environment and wet environment in 0.1 bar of CO2Partial pressure and balance N2Under CO2 Multi-cycle dynamic column adsorption capacity (298K).
Figure 27 is shown in the scanning electron microscopy (SEM) of the SU-MC1 materials synthesized under pH=1.
Figure 28 shows SU-MC1 small angle x-ray diffraction (SAXD) (XRD) pattern.
Figure 29 A-D show CO of two kinds of samples under 298K2And N2Isothermal initial slope.Figure 29 A are related to SU-MC1, CO2.Figure 29 B are related to SU-MC1, N2.Figure 29 C are related to SU-MAC1, CO2.Figure 29 D are related to SU-MAC1, N2。
Figure 30 shows the CO based on 273,298 and 323K2Thermoisopleth is calculated using Clausius-Clapeyron equation SU-MC1 and SU-MAC1 CO2Isosteric heat of adsorption.
Figure 31 is shown in the N of SU-MAC1 under 77K2Adsorption-desorption isothermal.
Figure 32 A-B are shown in the N of two kinds of samples under 77K2Absorption/desorption isotherm.Figure 32 A are related to CMK-3, and (display is provided Have the isothermal ordered mesopore carbon of IV types of the mesoporous hysteresis loop of feature), and Figure 32 B are related to Maxsorb and (shown with micro- The isothermal high surface area activated carbon of I types of hole characteristic), insertion figure is based on N2The pore-size distribution that thermoisopleth passes through NLDFT.Figure The x of insertion figure and y-axis are hole width (mm) and dV/dD (cm respectively in 32A3 nm-1 g-1)。
Figure 33 is shown in the CO of the SU-MAC1 compared with Maxsorb and CMK-3 under 298K2And N2Adsorption isotherm.
Figure 34 shows the Setup Experiments for dynamic column breakthrough experiment.
Figure 35 is shown in 0.1 bar of CO2Partial pressure and balance N2Under pass through SU-MC1 CO2Multi-cycle dynamic column adsorption capacity (298K)。
Figure 36 A show the standardization detected under dry environment on SU-MC1 in dynamic column breakthrough experiment by mass spectrograph CO2Composition.Figure 36 B-C are shown in the accordingly result of SU-MAC1 under dry environment (Figure 36 B) and wet environment (Figure 36 C).
Figure 37 is shown on the SUM-MAC1 with acid impurities by for CO2The standard that the mass spectrograph penetrated is detected Change CO2Composition.
Figure 38 is 4- (pyrroles -1- bases) butyric acid1H-NMR spectrum.
Figure 39 is the texture attribute and CO of the SU-MC1 and SU-MAC1 compared with the mesoporous carbon described in document2Capture property Can form.
Figure 40 is SU-MC1, SU-MAC1, CMK-3 and Maxsorb texture attribute form.
B the porous graphitic carbon) from conjugated polymer molecular skeleton
B1) introduce
High surface area porous carbon material has pole due to its diversified function and outstanding physical/chemical reliability High technical significance.Its high electron conduction, high surface area and good chemistry and electrochemical stability are for electrochemistry Energy accumulating device (for example, electrochemical capacitor (or ultracapacitor) and battery) is very interesting.From basic Upper theory, the performance of the device depend primarily on the ability of carbon material and ionic interaction and conveying electronics.For example, preferably Ultracapacitor carbon material need the high conductivity for electric transmission, the high surface area for effective ion absorption/desorption, with And the suitable pore structure of the fast path for ion from electrolyte solution to carbon surface.Traditional porous carbon materials, for example, it is living Property charcoal (AC) have high surface area (up to 3000m2/ g), but their larger hole warping properties (pore tortuosity) and Bad hole is connective, and seriously limiting electrolyte ion is transferred to surface.In addition, they generally by coal or contain a large amount of impurity Biomass (for example, coconut husk, rice husk) synthesis.Therefore, it is necessary to purify extensively to obtain high quality ultracapacitor level AC, significantly Add cost.Soft template or hard template can be used for manufacturing mesoporous carbon, to realize more preferable pore size control and adjustable Kong Lian It is logical；However, it is necessary to complicated and expensive synthesis, hinders its practical application.
Porous graphitic carbon, such as three-dimensional (3D) porous graphene network is due to its higher intrinsic electron conduction and larger Surface area and increasingly cause the rise of people.However, the blocky graphite alkene powder that manufacture is randomly stacked by single heap is usual There is Severe aggregation, this significantly reduces its surface area, hole connectedness and electron conduction, causes medium charge storge quality.Though Some right specially designed 3D porous graphenes networks show that good hole is connective and electric conductivity, but the graphene network Extensive and inexpensive manufacture be still challenge.Universal method for above-mentioned graphene network is to use graphene oxide (GO) it is used as construction unit (building block).However, Hu Mo (is generally passed through by GO construction units manufacture conductive graphene Method (Hummer ' s method)) Strong oxdiative chemicals and (then) reduction chemicals are needed, when this is for large-scale production not Profit.Herein, it is highly desirable to keep 3D to be connected with each other being effectively synthesized for graphitic carbon network.
Herein, we describe the 3D porous graphitic carbon networks for being connected with each other pore structure with ultra-high surface area and classification Low cost and low temperature synthesis expand synthesis.Our scheme is using the 3D crosslinkings from conjugated polymer molecular skeleton Precursor, and without using any sacrifice template (Fig. 1).As shown in Figure 1B-C, we from crosslinking conjugated polymer molecular skeleton conjunction Into beginning, the crosslinking conjugated polymer molecular skeleton can be easily converted to porous carbon by thermal annealing (carbonization).With The chemical activating process at a temperature of as little as 800 DEG C further increases surface area and porosity afterwards, causes have high surface Product (up to 4073m2 g-1), macropore volume (up to 2.26cm3 g-1) and high electronic conductivity (＞ 3 times higher than conventional AC) Connective classifying porous graphite (HPG) carbon skeleton with good hole.Compared with the porous carbon reported before, the HPG that is obtained Carbon material shows unprecedented energy storage capacity and high rate performance, can obtain high quality load ultracapacitor and height Stable lithium-sulfur cell.
B2) result
B2a) the synthesis of the ultra-high surface area under low temperature and high graphite skeleton
Our polymer network is because its rigidity and cross-linked structure are referred to as " molecular skeleton ".In the presence of a crosslinking agent Form Rigid conjugated polymer main chain, PANi.Hydrogel network is easily formed when mixing monomer, oxidant and crosslinking agent (referring to experiment).After water removal is gone by freeze-drying, transform hydrogel is the holding initial macrostructure of polymer network Aeroge.From scanning electron microscopy (SEM) image (Fig. 7), dry polymer shows diameter about 100~200nm's The coralloid nano fiber of interconnection.
Selection phytic acid has two reasons as crosslinking agent：1) it includes six phosphate groups, the phosphate group and proton Change aniline and carry out electrostatical binding so that whole network is crosslinked, form the 3D macrostructures of molecular skeleton.With for low decomposition temperature 300 DEG C of selection soft templates of ＜ are different, and phytic acid degradation temperature is of a relatively high ,~380 DEG C, prevents carbonisation mesopore from caving in.2) with Phytic acid carbonization, organophosphorus ester formed in situ is by forming the phosphate for connecting polymer segments and being further crosslinked Connection produces polymeric layer.This, which can have been helped, is effectively retained more volatile low-molecular-weight materials.In fact, we obtain High char yield (~50wt%), more than twice of biomass carbonization.
At the temperature (450 DEG C of ＞) of even more high, by the fracture of P-O-C keys, cyclisation and condensation reaction cause poly- virtue Aromaticity and the size increase of compounds of group unit.These virtue group compound units or " embryo " graphene layer in carbonized polymers A large amount of productions can be observed in transmission electron microscopy (TEM) image (Fig. 8 A-8F).Subsequent passes through above-mentioned graphitization The chemical activating process that carbon is mixed and then is heat-treated at 800 DEG C with potassium hydroxide (KOH) further increases porosity And surface area.After activation, it can generally realize~30wt% total carbon yield (relative to polymer quality).By comparing, Commercially available AC conventional carbon yield is only~8% made of the activation of biomass under similar temperature.
The surface area and pore structure of porous graphitic carbon from polymer can by adjust synthetic environment (such as annealing temperature Degree and activation environment) easily it is adjusted (referring to Figure 22).For example, 900 DEG C are increased to from 400 DEG C by carburizing temperature, BET (Robert Brenner-Emmett-Teller (Brunauer-Emmett-Telle)) surface area (SBET) can be from 20m2 g-1It is increased to 423m2 g-1.Meanwhile pore volume (VAr, determined with argon gas) and can be from 0.04cm3 g-1It is increased to 0.38cm3 g-1.These carbon Subsequent chemical activation is further by SBETRaising up to 4073m2 g-1, and VArImprove to 2.26cm3 g-1.The effect can be with Contribution with caused organophosphorus ester partial activation during being decomposed by phosphate group and phytic acid.It should be noted that obtain highest face temperature Product is the sample for having minimum carburizing temperature (400 DEG C), and due to carburizing temperature be increased to 900 DEG C and activation temperature and KOH/ C ratio is fixed, SBETFirst reduce then rise.Which demonstrate unique effect of the phytic acid as crosslinking agent, and it is in mild temperature The effect of lower holding structure integrality.The high SBETWith big VArIt is the peak obtained in graphitic carbon.The value is even above previous Activated graphene (the S of reportBET=3100m2 g-1,VAr=2.14cm3 g-1)。
Detailed pore structure passes through the N under 77K2Absorption/desorption technology detection (Fig. 2A), appears clearly from our 3D The feature that the micropore of HPG carbon, mesoporous and macropore coexist.In 273K CO2Absorption/desorption isotherm show further in low pressure Lower CO2The stable increase (Fig. 9) of absorption.Fig. 2 B summarize N2And CO2The accumulation pore volume and pore-size distribution of absorption.By comparing, The high surface area AC (Fig. 2A) of conventional commercial is only shown with compared with small leak aperture (~0.6nm, Figure 10 and 11A-B) and medium VAr(0.997cm3 g-1) micropore.Coexisting for a large amount of mesopore/macropores enables to mass transport to be better than only having in HPG carbon The conventional AC of micropore.The high flexibility of the synthesis mode causes unprecedented performance to can be used in broad range of application, example Such as electrochemical energy storage.
B2) the physics and chemical characterization of HPG carbon
The 3D HPG carbon synthesized under different carburizing temperatures has similar form and structure.Detailed Microstructure characterization Disclose their hierarchy.Representative SEM (Fig. 3 A) and TEM image (Fig. 3 B), which show to have, is formed at the PANi polymerization phases Between (Fig. 7) large hole (hundreds of nanometers) interconnection carbon skeleton (main).The close research of carbon backbone chain shows have The small mesoporous foam-like porous structures (figure C) of pore diameter range number nanometer.It was observed that thread carbon structure represent carbon plate it is further Tangle in continuous stephanoporate framework (secondary).High-resolution TEM (HRTEM) image (Fig. 3 D-E) is further identified with number The graphene film of the interconnection of nanometer lateral dimensions.Orderly six side of carbon atom is apparent that in graphene nanometer sheet Accumulation, represents the high-graphitized of carbon skeleton.The porous graphite structure height is similar to and is derived from graphite oxide at the same temperature The porous graphene of the chemical activation of alkene, show small graphene domain and a large amount of edge sites (edge site).However, I HPG carbon show that good hole from rigid 3D conjugated polymers network is connective, can prevent particle aggregation or layer with Layer stacks.The HPG carbon structures are different from the pyrolysis porous carbon being previously reported by, the pyrolysis porous carbon being previously reported by shape Largely contain amorphous carbon under similar or even more high carburizing temperature.
Raman spectrum, which has further confirmed that, is characterized as~1590cm-1Strong carbonization (the figure of all 3D HPG carbon of strong G- bands 4A).Although the graphite-structure that all samples obtain, degree of graphitization improves as carburizing temperature raises.For 400 DEG C, the HPG carbon that is carbonized by PANI at 700 DEG C and 900 DEG C, the volume efficiency (I of the relative G- bands of D- bandsD/IG) be calculated as respectively 1.12nd, 0.94 and 0.88 (Fig. 4 B, Figure 22), it is consistent with their different surfaces product and porosity.Even ID/IGMaximum is less than The activation graphite (~1.2) from GO under similar activation environment, shows higher degree of graphitization.sp2The amount of carbon is led to Cross and be compared to further with π * and the σ * that the graphite reference material with equal thickness is combined using Electron Energy Loss spectrum pair It is determined that.For example it is assumed that graphite is 100% with reference to spectrum, the sp in HPG carbon (from 900 DEG C of carbonizations) is found2Carbon plate section is up to 94% (± 5%, Fig. 4 C).It was noticed that more edge defects may be projected electron beam due to existing in threadlike network A large amount of small graphene films (Fig. 3 B-D and 12A-D), the value may be underestimated, and thus reduce sp2The detection limit of carbon.
X-ray photoelectron spectrum (XPS) shows that HPG carbon contains C, N and O dopant (Figure 13 A-B).The horizontal spectrum of N1s cores (Fig. 4 D) shows the presence of three kinds of nitrogen：The oxide of pyrroles's nitrogen (N -5,399.5eV), season N (N-Q, 400.6eV) and pyridine-N Peak (N-O, 402.9eV).N -5 (relative to total N, 25 atom %) limits from structure, and low molecule amount PANi is by rapid polymerization Produce.Due to N-Q highest heat endurances, N-Q occupies an leading position (61 atom %).N-O (14 atom %) presence can return Because in the oxidation environment of activation process.The research and development being doped in HPG carbon also by analysis PANi and be carbonized PANi into (Figure 14-15) is divided to be illustrated.
B2c the chemical property of the ultracapacitor) based on HPG carbon
High surface area and the 3D pore structure of HPG carbon is advantageous to application of electrode.In addition, relatively small carbon granules degree provides for processing Can amplification and high flexibility.Substantially, the electrode based on HPG carbon can easily be manufactured on a variety of base materials.Example Such as, micro- pattern electrode can be painted on PET (PET) piece, flexibility by the alcohol suspension ink of carbon On polyimide film or silicon wafer.Very thick electrode (100 μm of ＞) can be used easily in METHYLPYRROLIDONE Carbon slurries scraper for coating is on metal base (such as Ti, Al).Because carbon particle includes the coralloid nano fiber being connected with each other, They provide good mechanical flexibility for electrode.The electrode obtained also has high conductivity (~300S m-1), close to work Graphite alkene (500S m-1), it is significantly higher than support graphite alkene (strutted graphene) (1S m-1) and commercial AC (10- 100S m-1).Plus big active surface area, the electrode has for ultracapacitor, battery, elctro-catalyst and other application Great potential.
HPG carbon electrodes and super capacitor have been manufactured on different base materials.Interdigital ultracapacitor (interdigital supercapacitor) is made by being sprayed on HPG carbon printing inks in the PET film for applying deposit (50nm) Make.Flexible super capacitor with interdigitated electrodes by by HPG carbon printing inks be sprayed on aluminium coat (50nm) with 50nm aluminium conductive layersOn polyimide film.Ten manufactures simultaneously on silicon there are interdigitated electrodes Flexible super capacitor is produced using removable PDMS (dimethyl silicone polymer) mask.By by HPG carbon pastes scraper for coating The electrode of 4cm*5cm sizes is manufactured on Ti base materials (thickness is~100 μm).
In order to assess performance of the supercapacitor, we manufacture electrode using the method for conventional coating slurry.Device is shown The high-performance (Figure 16 A-D) gone out on water-based and organic bath.For example, the prototype equipment based on HPG carbon is in 0.5M H2SO4In Even in 1000mV s-1Very high voltage scan rate under also maintain rectangle cyclic voltammetry (CV) curve (Fig. 5 A), One feature observed only on preferable ultracapacitor.The constant current charge of measure/electric discharge distribution is shown with smaller The linearity curve of voltage (IR) drop, such as in up to 10A g-1Current density under only 0.014V decline (Fig. 5 B).The value is only For the 1/5 of AC-1 (usually used ultracapacitor carbon), and it is less than graphene film ultracapacitor (0.018V).0.5- 50A g-1Different current densities under HPG carbon and commercially available AC specific capacitance summarize in figure 5 c.HPG carbon is in 0.5 and 50A g-1 225 and 162F g are shown under current density respectively-1Electric capacity, the electric capacity retentivity equal to 72%.By comparison, with electric current Density is from 0.5A g-1Increase to 50A g-1, AC-1 only keeps~44% initial capacitance, and (198 arrive 88F g-1).Even for thin Film graphene, macroporous/mesoporous graphene and 3D support graphite alkene ultracapacitors, as current density increases formed objects, electricity Hold retentivity only~50%.
Quick electrode kinetics further confirms that the Nyquist that HPG carbon determines is bent using electrochemical impedance spectroscopy (EIS) Line (Fig. 5 D) discloses low-down Electrode Series Resistance (ESR ,~0.7 ohm), and this is attributed to high-graphitized porous web Network.The near vertical line shown at low-frequency range has been further demonstrated that due to the ideal capacitance property of dexterous ion transmission. Significantly more, baud curve compares the response time of different ultracapacitors shown in Fig. 5 E.For commercially available AC, characteristic frequency (f0) it is about 0.1-1Hz.Obviously, our HPG carbon devices show~7Hz high f0, equal to only~0.14s time constant τ0(=1/f0).The value is also less than activated graphene (~0.25s), liquid intervention solid graphite alkene (liquid-mediated Dense graphene) (0.51~3.85s) He Duodong (holey) graphene skeletons (0.17-0.49s).The less time is normal The graded porous structure that number is connected with each other mainly due to 3D, this provides fast ionic transmission in block type electrode.
The practical application of ultracapacitor needs high effective mass load (active mass loading), big to obtain Area capacitance.Our HPG carbon can be manufactured easily with a gram rank in powder form, and can be readily available height Quality load electrode.Due to effective porous, electrically conductive structure, in 0.5A g-1Under as quality load is from 1mg cm2Increase to 11mg cm2, HPG carbon electrodes can keep initial capacitance~83% (from 225 to 187F g-1), equal to 2.12F cm-2Area capacitance (Fig. 5 F).In 2A g-1Under current density, area capacity still can remain 1.62F g-1.The high area capacitance and high magnification Performance meet commercially available ultracapacitor demand (for example,>1F cm-2).However, the high-performance porous graphitic carbon being previously reported by Electrode can only realize relatively low/medium quality load (<5mg cm-2), it is difficult to for large-scale industrial production.
In addition, HPG carbon electrodes show highly stable cycle performance, in 5A g-110000 times circulation after have 96% Electric capacity retentivity (Figure 17).(the figure that had almost no change on ESR is shown in the EIS measure of the front and rear prototype equipment of circulation 18), it was confirmed that the high electrochemical stability of our HPG carbon.
B2d) HPG carbon is used for the chemical property of Li-S batteries
Except ultracapacitor, due to said structure advantage, HPG carbon can realize high-performance lithium-sulphur (Li-S) battery. One significant challenge of Li-S batteries be to provide big conductive surface area be used in the electrodes activate and capture insulation sulphur, lithium sulfide and Polysulfide species.Although a variety of porous carbons are used for into Li-S negative electrodes, due to medium surface area and lack effective hole For structure to keep active sulfur species and electrode activity thus, they generally show cyclical stability deficiency and/or sulphur matter Loading gage lotus it is low (<2mg cm-2).Further, since the bad electric conductivity of carbon electrode, before and high quality load is not implemented.
The schematic diagram of battery structure is as shown in figure 19.The charging/discharging voltages distribution of HPG carbon/polysulfide shows spy The two step electric discharge phenomena (Fig. 6 A, Figure 20 A) of sign property.Electrode shows the electro-chemical activity of brilliance.Initially putting under C/5 speed Capacitance (sulphur load：3.2mg cm-2) it is~1270mAh g-1, close to theoretical capacity (1466mAh g-1,Li2S8To Li2S) ~90%.Therefore, area capacity reaches up to 4.2mAh cm-2Value.920th, 740 and~600mAh g-1 capacity respectively can (Figure 20 B) is transmitted with 0.5C, 1C and 2C speed, shows the high rate capability under high quality load.Initially putting down After weighing apparatus circulation, electrode can keep 980mAh g after 200 circulations under C/5-1High power capacity (~80% initial appearance Amount) (Fig. 6 B).The height ratio capacity obtained under high quality load can be attributed to effective classifying porous conductive structure and be used for Strong LixN the and O foreign atoms of S-phase interaction, the strong LixS-phase interaction control lithium sulfide material forms and keeps high activity Materials application.The performance be better than report so far be mostly based on porous carbon sulfur electrode (<3mAh cm-2,<Follow for 200 times Ring, Fig. 6 C).
As a comparison, reference electrode (the sulphur load manufactured by AC-1：2.52mg cm-2) show low capacity (<400mAh g-1).This is probably low electric conductivity and the wetting of bad electrode and diffusion because in micropore AC particles.Similarly, by carbon black (Kejten black,1200m2 g-1SBET) made of electrode even in low-sulfur load (1.28mg cm-2) under also show that 890mAh g-1Low initial capacity.In addition, the electrode only possesses 600mAh g after 200 circulations-1Capacity.They are faster The capacity of speed declines the uncontrolled deposition that can be attributed to insulating sulfuration thing material, and this causes larger non-active particles and electrode The loss of activity.In our HPG carbon electrodes, ultra-high surface area and polarity foreign atom (N, O) provide for lithium sulfide deposition More avtive spots, and the skeleton being connected with each other can effectively keep conductor path, thus provide high circulation stability.This The support of (Figure 21) is tested by EIS, the ESR of wherein HPG carbon/polysulfide keeps smaller during circulation.It is it should be noted that super The cyclical stability for crossing 500 circulations only exists<1mg cm-2Sulphur quality load in the case of be recorded.However, manufacture high quality Load electrode frequently results in the life-span and is remarkably decreased.Therefore, our high-sulfur load HPG carbon electrodes extremely may be used for practical application Lean on.
B3) discuss
Because the high graphite-structure with ultra-high surface area of 3D HPG carbon skeletons, macropore volume and be connected with each other Pore structure, 3D HPG carbon skeletons have surmounted the porous carbon of other reports, commercially available activated carbon in terms of electrochemical charge storage volume With other 3D porous graphenes.Even if it has been reported that with~3000m2 g-1High SBETAC, but their electrochemical capacitor It is still poor with high rate performance.In our case, we have discovered optimal super capacitor performance to be not from Sample with highest face temperature product.This is seemingly because be unfavorable for the more irregular pore structure of mass transport.However, we Synthetic schemes can obtain high structure controllability to realize unprecedented chemical property.For carbon black, in carbon particle Portion does not have hole, and therefore, total surface area is not enough to be used for supercapacitor applications.In addition, its granularity it is very small (<100nm) so that It is very big in contact resistance, especially for thick electrode.This is excessively poor in Li-S batteries, wherein being deposited on particle surface On insulation polysulfide can easily block charge transfer path.By comparison, HPG carbon skeletons include the 3D of small graphene film Porous web, therefore high surface area, small carbon granules degree, open-celled structure and good electric conductivity are obtained simultaneously.It therefore meets high property The important requirement of energy motor：I) big electrode/electrolyte interface to be to provide a large amount of avtive spots for redox reaction, by This obtains high charge storage capacity；Ii) effective transmission of ion and minimum electrolyte transport resistance；And iii) ensure to be used to have Imitate the graphitized carbon skeleton of the high electron conduction and high chemical stability of electric charge transmission.These features realize fast quick-action together Mechanics and low ESR, high rate capability is provided for electrode.Therefore, such porous graphitic carbon, which has, is used for ultracapacitor and tool There is the huge prospect of high-energy and the Li-S batteries of high power density.
It should be noted that in the recent period it has been reported that some other 3D porous graphenes structures.For example, graphene network can be by Templated chemistry vapour deposition (CVD) technique, then etching is manufactured, but still has challenge using CVD large-scale production. Although the support graphite alkene grown by sugared blow moulding (sugar blowing process) can potentially be given birth on a large scale Production, but its superelevation porosity (99.85%) and extremely-low density (~3mg cm-3) cause manufacture that there is reasonable volume energy density Device problem be present.3D porous graphenes, but low surface area (S are manufactured using commercial polymer induced with laserBET~340m2 g-1) limit it and be used for the application of high-energy electrochemical appliance.By comparing, our scheme and the existing big rule for AC Mould production method is compatible, and HPG carbon provides ultra-high surface area and the density (~0.47g cm similar to commercially available AC-3)。 For the low cost of raw material (the HPG carbon produced<7-11 $/kg, Figure 23), our HPG carbon is easily with extensive, inexpensive Manufactured.
In a word, we, which have developed, can expand synthetic schemes, with by one-step synthesis since inexpensive raw material by being conjugated Polymer molecule skeleton manufactures 3D porous graphitic carbons.Specifically, this method can be produced with ultra-high surface area and big hole body The high graphitic carbon of product and the graphene-like network structure being connected with each other.These performances cause outstanding electro-chemical activity and height steady It is qualitative, and the unprecedented performance in ultracapacitor and Li-S batteries.Manufacture monomer, the crosslinking agent of precursor polymer Can be easily changed with oxidant, in the form of for final carbon, surface area and chemical composition larger controllability is provided. Our synthetic method can also be by adding the salt containing metal or using the salt work containing metal during polymer process For the oxidant of polymer so that metal, metal oxide, nitride or carbide are readily inserted into carbon skeleton.Therefore, make The new way for making 3D porous graphitic carbons goes for carbon material of the manufacture with performance needed for wide range of applications.
B4) auxiliary information
B4a) experimental section
B4a1) the synthesis of 3D HPG carbon skeletons：
In experiment synthesizes, ammonium persulfate (0.572g) is dissolved in 1ml deionized water (solution A).Pass through mixing The phytic acid (50%, wt/wt, in water) of 0.458ml aniline, 2mL deionized water and 0.921mL prepares solution B.By solution A and B is together cooled to 4 DEG C, then quick mixing.In order to remove the accessory substance of excessive acid and polymerization, the PANi obtained leads to Cross to submerge 24 hours in deionized water and purified.PANi aeroges are manufactured by being freeze-dried to hydrogel.Most Eventually, the carbonization of sample is carried out in nitrogen at 400~900 DEG C, heating rate during less than 600 DEG C is 2 DEG C of min-1, and it is high Heating rate when 600 DEG C is 5 DEG C of min-1.The polymer of carbonization mixes well with 2mL 7M KOH, (KOH/ carbonizations Polymer) weight rate be 3.After the vacuum drying oven processing of 4 hours evaporates the water at by 60 DEG C, the water of KOH/ carbonizations Gel mixture is with 5 DEG C of min-1Heating rate heated at 800 DEG C, and in 75sccm nitrogen stream and~500 support The temperature is kept under operating pressure 1 hour.After the cooling period, sample carries out repeated washing with deionized water, until pH value reaches 7. Then, they are dried in vacuo 2 hours at 65 DEG C, to produce final 3D HPG carbon dusts.The gross production rate being computed is~30%.
B4a2) physics and chemical characterization
Electron microscopic (SEM) is scanned using FEI Magellan 400XHR microscopes to be imaged.Using equipped with figure Form the spherical aberration (C of (object lens) lenss) adjuster and monochromator FEI Titan microscopes carried out under 80kV TEM into Picture.CsCoefficient is set as about -10 μm.Image is obtained using the CCD cameras of Ultrascan 1000.Using identical microscope with And the EEL spectrometers of Gatan Quantum 966 carry out Electron Energy Loss spectrum (EELS).By using formula (1) to each carbon material The peak area of π * and σ * components of proximal edge structural energy loss spectra integrated to compare π * and (π *+σ *) ratio：
Wherein, fπ* it is the ratio between two π * peaks, Iπ* it is the integration of 1s → π * transition, and △ E are for standardization Integral counting (1s → π * of energy window:283.2-287.2eV and 1s → σ *:292.5-312.5eV).Subscript s and u distinguish Represent standard spectrum and unknown spectrum.At least three diverse locations are checked to obtain average result on each carbon sample.Surface Element composition is measured by XPS (PHI 5000 Versaprobe, Al KR sources).Using equipped with 532nmNiYAG laser The confocal Raman microscopes of WiTech obtain Raman spectrum.Nitrogen and CO2Adsorption experiment uses AutoSorb iQ2(quart gram Rom instrument company (Quantachrome Instruments)) progress of low-pressure gas Sorption Analyzer.Nitrogen adsorption is under 77K Use 99.999% N2Carry out.Pore-size distribution (PSD) is close using quenching solid-state by slit, spherical and cylindrical hole carbon model Functional Theory (quenched solid-state density functional theory, QSDFT) is spent to calculate.Pass through BET Method is in pressure limit P/PoSurface area test is realized within=0.05--0.25.CO2Absorption is carried out under 273K, and temperature is led to Circulation bath is crossed to be controlled.CO2Adsorption isotherm is also by using extra-pure grade CO2Autosorb iQ2 analyzers collect.Micropore Footpath distribution is based on CO by Nonlocal D FT (NLDFT) using AS1Win softwares2Adsorption isotherm is calculated.
B4a3) the manufacture and test of ultracapacitor：
In order to manufacture interdigital (interdigital) ultracapacitor, by by HPG carbon (90wt%) and poly- (3,4- Ethene dioxythiophene) PSS (10wt%, as electroconductive binder) is scattered manufactures ink in ethanol.In order to make Typical ultracapacitor is made, by the mixing HPG carbon (90wt%) in the 1-METHYLPYRROLIDONE (NMP) and poly- (vinylidene fluoride) (PVDF, 10wt%) manufactures slurries.By the way that slurries are coated coated in titanium foil or carbon 2 are dried on aluminium foil and under vacuo at 80 DEG C Hour manufactures electrode.The electrode formed is rolled and is further dried 5 hours at 100 DEG C under vacuo.Electrolyte is molten Liquid is the 0.5M H for aqueous batteries2SO4With the 1M ttraethylammonium tetrafluoroborates in the propene carbonate for organic battery (NEt4BF4) solution.The specific capacitance C of electrode materials(F g-1) according to C=I/ (dV/dt) ≈ I/, (Δ V/ Δ t) are by constant current The discharge curve of circulation calculates, wherein I constant discharge currents density, and E is cell voltage, and dV/dt is the oblique of discharge curve Rate.EIS tests are operated with 10mHz-100kHz frequencies and 10mV AC amplitudes.
B4a4) the manufacture and test of lithium-polysulfide electrode：
In order to manufacture carbon/polysulfide battery electrode, using in DOX (DOL)/1,2- dimethoxy-ethanes (DME) (1 in volume:1) the 5M Li in2S8Solution uses 5wt% LiNO as active sulfur materials3As active sulfur materials. Using freshly prepared 1M containing containing LiNO3The 1 of (1wt%):Double (- trimethyl fluoride sulfonyls in 1v/v DOL/DME Base) imide li solution is as electrolyte.By mixing different carbon activity materials (80wt%) and PVDF (20wt%) in NMP Form carbon slurries.In order to manufacture working electrode and barrier film, carbon slurries are coated on aluminium foil or the barrier films of Celgard 2400, then Carry out being dried in vacuo for 10 hours at 60 DEG C.By 5M Li2S8Solution instills carbon coating foil electrode, and then exists at room temperature DOL/DME solvents are evaporated in glove box full of Ar.For 3.2mg cm-2Sulphur quality load, by 20 μ L 5M Li2S8It is molten Liquid is added in carbon electrode, then adds electrolyte.The quality ratio of active sulfur species and HPG carbon in whole electrode is 3:2.Apply The barrier film for applying HPG carbon is placed at the top of the working electrode with the carbon side contacted with electrode.Lithium metal disk is used as to electrode, And button cell is assembled in glove box.
B4b) cost analysis
Cost analysis is carried out on HPC samples, and compared with other commercially available carbon.Figure 23 shows all kinds The cost of activated carbon.HPC price estimated using the prices of raw materials of aniline, phytic acid, potassium hydroxide and ammonium persulfate, and And calculate the yield of thermal annealing technique.$ 15/kg processing cost is added into yield, so as to adjust the prices of raw materials to calculate The totle drilling cost of HPC carbon production.
C) from the porous carbon for rationally designing polypyrrole
C1) introduce
The CO2 emissions relevant with global annual energy reach the new highest record in history of 31.2 hundred million tons (Gt) within 20121, And the energy demand in view of increasing and the energy infrastructure of lasting dependence fossil fuel, it is contemplated that will also be continuously increased. CO2Emission reduction has been considered as vital necessary condition, because CO2It is to cause global warming and rising for associated consequences mainly to be made Greenhouse gases, the associated consequences include that sea level rise, the great change of synoptic model and to human health and open country The threat of raw biological habitat.Due to because the high heat capacity of the water for regenerating causes sizable energy loss, for two Carbonoxide capture, the state-of-the-art technology of water-based amine washing are not yet proved in scale be feasible.Unlike, it is porous solid Body adsorbent has many advantages, such as relatively low regeneration energy, pore geometry and controllability in the size of hole, And the flexibility of Heteroatom doping or functionalisation of surfaces.Therefore, it is used for CO to a variety of2The porosu solid of capture is carried out Many researchs, such as zeolite, metal-organic framework (MOF), porous carbon, porous silica and porous polymer.It is however, real The expansible adsorbent for now meeting to be required still has challenge.Exist generally between required property and accept or reject, i.e. big suction Attached capacity, quick adsorption and desorption kinetic, gentle regeneration condition and multi-cycle stability.For example, although chemosorbent (such as porosu solid support type amine) can by with CO2Chemical reaction reach outstanding equilibrium adsorption capacities and CO2/N2Selection Property, but they usually require to carry out regeneration heating by relatively long absorption/de-adsorption cycle conversion time.On the other hand, often Rule physical absorbent (such as activated carbon and MOF) can minimum energy input regenerated, but it has under after-combustion environment There is relatively low capacity, because CO2- attached dose weaker and other smoke components (N that interact2And H2O competitive Adsorption) etc..
In this study, we are reported with hierarchical porous structure and high activity CO2The N doping porous carbon of adsorption site The easy synthesis of material.Our result of study shows that the carbon material balances above-mentioned choice, has under after-combustion environment The CO of prospect2The new highest record in history CO in adsorption capacity, i.e. porous carbon materials2/N2Selectivity, to the relatively low energy demand and height of regeneration Multi-cycle stability.Our porous carbon is soft by being applied in combination altogether for the pyrrole monomer of rational design and triblock copolymer Template method is synthesized, and compared with hard template scheme, its is easy, more cost-effective and more rapidly.The nitrogen function of pyrroles's precursor Group is provided for strengthening CO2The adsorption site of-adsorbent interaction；It therefore, there is no need to extra nitrogen source or surface function Change.The hole that rigid polypyrrole conjugated polymer structure additionally aids during preventing combination of polymers carbonization caves in, and aromatic polymerization Thing structure advantageously forms Graphitic carbon structure.
Carbon structure is classified by the inspiration of natural system (such as lung and leaf), it passes through with hierarchical porous structure and aperture model Enclose the gas diffusion for showing enhancing.Natural imitation is desirable, but challenging to provide the synthesis of hierarchy.This is Unite substantially usually using supramolecular chemistry to produce hybrid material.We can be assembled jointly by soft template in novel synthesis Scheme manufactures the hierarchy of simulated lung alveolitoid structure.
Robert Brenner-Emmett-Teller (BET) specific surface area for the porous carbon (SU-MC1) that we synthesize is 805m2 g-1, And micropore (d<2nm) volume is 0.17cm3 g-1, it is respectively 1.0 and 3.1mmol g to show under 0.1 and 1 bar-1Height CO2Adsorption capacity (298K) and 51:1 outstanding CO2/N2Selectivity.Produced with the carbonized polymers of 500 DEG C of cryochemistry activation Raw BET specific surface area is 759m2 g-1Nitrogen-dopped activated carbon (SU-MAC1).It shows micro pore volume (0.34cm3 g-1) and CO under 298K2It (is respectively 1.4 and 4.5mmol g under 0.1 and 1 bar that adsorption capacity, which dramatically increases,-1, equal to than described two 40%) highest record value under pressure increases, and the new highest record in history CO2/N2Selectivity (331：1, than the N- doping reported in the past High an order of magnitude of peak of carbon adsorbent).Be important to note that selectivity be to determine VSA unit economy it is main because One of element.The advantage is extremely important, because high selectivity improves CO2Purity, so as to being reduced by reducing energy resource consumption The operating cost of factory.Porous carbon can only be carried out complete by inert gas purge rather than pressure-variable adsorption/desorption process heating Regeneration.It is stable for multiple absorption/de-adsorption cycle (10 circulations), is declined without any carbon dioxide capacity.In addition, Compared with drying capacity, it maintains 78% CO in wet condition2Capacity.Coal combustion rear pass is typically found in addition Acid impurities (SO in gas2、NO、NO2And HCl) in the case of, it maintains the 53% pure CO of drying2Capacity.Our nitrogen is mixed Miscellaneous graded porous carbon has many preferable properties, becomes for CO after burning2The promising material of capture.
C2) result and discussion
Our graded porous carbon is expressed as SU-MC1, have macropore (~1 μm), mesoporous (~5.6nm) and micropore (< Combination 2nm), this is realized by the rational design of polymerized monomer precursor and building-up process.SU-MC1 is shown in Figure 24 A The synthesis technique of material and schematically showing for graded porous structure.Classification form is advantageous to CO2The application of capture, because macroscopical Network is by using being advantageous to CO2The ultramicropore of absorption makes resistance to mass tranfer decline to promote CO2Diffusion.First, monomer needs to be hydrophilic Property, so that it, preferentially with the hydrophilic segments of triblock copolymer surfactant templates group altogether, but not is excessively hydrophily , to cause it to rest in aqueous phase.In addition, it can not be excessively hydrophobic, to cause it to be more preferably assembled into three block In the hydrophobic core of copolymer micelle.For example, will be assembled into without the pyrrole monomer of any modification in hydrophobic core, and produce solid Body polypyrrole nanosphere replaces hollow particle.We devise a kind of 4- (pyrroles -1- bases) butyric acid (Py-COOH) monomer, its The performance needed for preferable monomer is showed in assembling process.The fence that its hydrophily tail makes it be partially soluble in water and enters micella Region, but avoid whole molecule from being assembled into hydrophobic core.During porous polymer network is formed, pass through electrostatic interaction Macroporous structure in our samples is formed with microphase-separated.Meso-hole structure passes through monomer and structure guided bone triblock copolymer Packaging technology produces altogether.Finally, microcellular structure is to be entered by removing IPN block copolymer afterbody in polymer substrate to produce Raw, and may partly be cracked and produced by butyric acid group.
The scanning electron microscopy (SEM) (Figure 24 B) of SU-MC1 materials shows the big of the carbon skeleton synthesized under pH=2 Hole characteristic.The structure is similar to the appearance height of alveolar, has thin-walled and the void space interconnected.It is interesting that macropore Structure can be simply adjusted by protonation.By the way that pH is maintained at into 1 or 3.5, foam-like knot is observed respectively Structure (Figure 27) or filamentary structure (Figure 24 C).This is probably due to influenceing the intramolecular of the spatial distribution of polymer precursor and dividing The change of electrostatic interaction between son.Before, Stejskal et al. illustrates the different journeys due to hydrogen bond and ionic interaction Stability is spent, oligomer of phenylamine is polymerize the different shape to obtain under different acidity and oxidant size.Liao et al. Also illustrate protonation pyrrole monomer and form cation, the cation and other anion and oxidant self assembly are to form Different polypyrrole nano structures.
Transmission electron microscopy (TEM) image and corresponding Fourier's diffraction pattern (Figure 24 D-E) disclose from [110] and [100] periodicity for the height that direction is observed, two-dimentional six side's mesoscopic structures be further demonstrate.Spread out using low-angle X ray (XRD) further characterization SU-MC1 periodicity is penetrated, as shown in figure 28.The presence at (100) and (200) peak is clearly observed, This further supports the presence of two-dimentional six square arrays.It is noted that temperature is reduced during oxidation polymerization for slowing down The polymerization of pyrrole monomer has very big advantage, therefore remains meso-hole structure and avoid Polymer-Polymer classification.
The chemical composition of SU-MC1 materials by determination of elemental analysis, to find it be 3.8 weight %N and 93.3 weight % C.The property of nitrogen material is further study by x-ray photoelectron spectroscopy (XPS).N 1s core stage spectrum are as shown in figure 25, 398.0,39.5 and 400.8eV, tri- secondary peaks can wherein be identified, correspond respectively to pyridine nitrogen (N-6), pyrroles's nitrogen (N-5) and Quaternary nitrogen (N-Q).Quaternary nitrogen is most stable of nitrogen material under pyrolytical condition, and it represents 69% of all nitrogen materials in carbonized polymers.
The loose structure of SU-MC1 samples is further analyzed by gas absorption/desorption technology.Nitrogen adsorption and Desorption is carried out under 77K, and carbon dioxide adsorption is carried out under 273K.The combination of nitrogen and carbon dioxide adsorption data provides From mesoporous (2nm<d<50nm) arrive ultramicropore (d<Hole characteristic 0.8nm).Nitrogen adsorption isotherm (Figure 25 B) can be built according to IUPAC View is categorized as IV type thermoisopleths.The absorption to be risen sharply under relatively low relative pressure discloses pore characteristics (d<2nm), relative pressure >Hysteresis when 0.4 then shows to exist mesoporous.The apparent specific surface area of mesoporous carbon is 805m2 g-1, it uses Robert Brenner-Ethylmercurichlorendimide Spy-Teller (BET) method is calculated based on the Nitrogen adsorption isotherm that relative pressure is 0.05-0.3.By under relative pressure 0.995 Nitrogen absorb estimation total pore volume be 0.88cm3 g-1.It can be seen that accumulation pore volume and pore-size distribution (PSD) at 5.6nm Main peak (Figure 25 C insertion figure) in scanning, corresponding to from the mesoporous passage for removing block copolymer template.Furthermore, it is possible to From CO2PSD observes pore characteristics, wherein three main peaks are at 0.35,0.48 and 0.79nm.Accumulate ultramicropore (d<0.8nm) Volume is 0.12cm3 g-1.It is worth noting that, ultramicropore is in CO2Played an important role in capture, because they are largely CO in upper and carbon material2Adsorption capacity is consistent.
In view of the specific characteristic of SU-MC1 materials, including be largely connected with each other macro network, high-sequential it is mesoporous, A great deal of micropore and a large amount of nitrogen functional groups, SU-MC1 materials are in CO2/N2There are very big potentiality in separation application.Separating property is led to Cross including CO2And N2The component balanced absorption of pure gas and CO2And N2The dynamic post separation of mixed gas assessed.This Outside, other important properties, such as isosteric heat of adsorption, selectivity and recyclability are investigated.In 298K, SU-MC1 materials 3.1mmol g are showed in 1 Ba Chu-1High CO2Capacity (Figure 25 D).As a comparison, there are 1150-3150m2 g-1Higher table The conventional commercially available activated carbon of area shows 1.2 to 2.0mmol g under the same conditions-1Relatively low CO2Range of capacity.It is worth note Meaning, this high power capacity have surmounted the soft template mesoporous carbon being previously reported by and hard template CMK-3, and have been N doping mesoporous carbons One of optimum capacity.In addition, in the case where carbon dioxide partial pressure (being to capture to apply more relevant pressure with after-combustion) is 0.1 bar, SU-MC1 materials show 1.0mmol g-1Have prospect volume, exceeded document record nitrogen doped micropore and mesoporous carbon.It is logical Often, CO2Capacity reduces with the rise of temperature, shows CO2The exothermal nature of adsorption process.By contrast, find in 298K and N under 1 bar2Adsorbance is 0.46mmol g-1(Figure 25 D), the far smaller than CO under the same terms2Absorption.CO2/N2Selectivity is logical Cross Henry's law calculating.First, CO under 298K is calculated2And N2The initial slope of adsorption isotherm, for CO2And N2For 33.4 With 0.65mmol g-1Bar-1(Figure 29 A-B).Then 51 are obtained using the ratio of these slopes:1 CO2/N2Selectivity.According to work The knowledge of person, it is highest in micropore and mesoporous carbon that the selectivity is previously reported by the literature.High CO2Initial slope is probably The CO provided is cooperateed with by microporosity and nitrogen functional group2The result of Adsorption thermodynamics driving force.CO2Phase between SU-MC1 materials Interaction intensity can further be assessed by isosteric heat of adsorption, and the isosteric heat of adsorption passes through based on 273,298 and 323K CO2The Clausius of adsorption isotherm-carat amber dragon equation calculates.Isosteric heat of adsorption scope is 37.2kJ mol-1Extremely 24.0kJ mol-1, corresponding to 0.01-2mmol g-1CO2Adsorption range (Figure 30).Low CO2High isosteric heat of adsorption under load From CO2Strong pole-pole interaction between the quadrupole and polarity nitrogen groups of molecule.With CO2The increase of load, institute The CO of absorption2Molecule occupies active surface site, so as to weaken surface site and gas phase CO2Between interaction.Cause This, isosteric heat of adsorption is with CO2Load increases and reduced, and finally in~24kJ mol-1Become flat.
In order to further improve CO2Acquisition performance, employ the chemical activating process using KOH.Synthesized poly- (4- (pyrroles -1- bases) butyric acid) compound progress low-temperature carbonization, weak chemical activation is then carried out, is situated between with producing obtained N doping Mesoporous activated carbon, it is expressed as SU-MAC1.Show that nitrogen load is 5.8 weight % using the elementary analysis of combustion method.XPS shows： Pyrroles's nitrogen (N-5) is main nitrogen material (69.0%), and pyridine nitrogen (N-6) is 13.2% and nitrogen oxides (N- oxides) For 17.8% (Figure 26 A).With and the similar combination of pyrroles's nitrogen can pyridone nitrogen (Pyridonic nitrogen, N-5') It may be produced by the weak oxide activation process.Pass through the N under 77K2Absorption is analyzed hole characteristic, and thermoisopleth is painted Make in Figure 31.SU-MAC1 shows 759m2 g-1Apparent BET specific surface area, slightly below SU-MC1.This may be attributed to polymerization The incomplete carbonization of thing compound and block copolymer template and butyric acid group are partly removed in low-temperature carbonization and activation process. This is by N2Lag (Figure 31) reduction and N2Demonstrate,proved at 5.6nm in PSD in the absence of very big volume peak (Figure 26 B illustrations) It is real.However, low-temperature activation causes the narrower bore for having grown significant quantity, while the further size increase of narrower bore is minimized. From PSD (Figure 26 B insertion figure) as can be seen that and hole width scope<1nm SU-MC1 is compared, SU-MAC1 different pore volumes Dramatically increase.SU-MAC1 has 0.34 and 0.30cm respectively3 g-1Micro pore volume and ultra-micropore volume (Figure 26 B and Figure 40), Represent its total pore volume (0.47cm3 g-1) 72% and 64%.They are higher than SU-MC1 by 100% and 150% respectively.
In 298K, SU-MAC1 CO2Balancing capacity (Figure 26 C) (4.5mmol g-1, 1 bar；1.4mmol g-1, 0.1 bar) Show than SU-MC1 (3.1mmol g-1, 1 bar；1.0mmol g-1, bar) increase 40-45%.In addition, art heretofore taught pyridine Ketone nitrogen (B.E.399.8eV) is advantageous to CO2Absorption.CO2The vast improvement of absorption is the amount increasing of ultra-micropore volume and preferred nitrogen material The result added.It was found that pass through CO2And N2The ratio (Figure 29 C-D) of isothermal initial slope, SU-MAC1 Henry's law CO2/ N2Selectivity will be up to 331:1.Two kinds of commercially available carbon of selection are compared, including CMK-3 and Maxsorb.Their gas absorption Phenomenon is described in Figure 32 A-B, and their texture attribute is listed in Figure 40.SU-MAC1 CO2Capacity (298K, 1 bar) is respectively 158% and 102% (Figure 33) higher than commercially available CMK-3 and Maxsorb.In addition, SU-MAC1 CO2/N2Selectivity also apparently higher than CMK-3(19：And Maxsorb (9 1)：1).SU-MAC1 outstanding CO2Capacity have also exceeded previous research than under environment There is the new highest record in history CO2/N2The mesoporous carbon of selectivity.The table provided in Figure 39 summarizes and the mesoporous carbon phase described in document The SU-MC1 and SU-MAC1 of ratio texture attribute and CO2Acquisition performance.In 0.01-2mmol g-1CO2SU-MAC1 under load CO2Isosteric heat of adsorption scope is 46~28kJ mol-1(Figure 30).The SU-MAC1 higher than SU-MC1 CO2Heat of adsorption shows Go out stronger adsorbent-CO2Interaction.
In addition to based on the isothermal absorption property of pure gas, in order to assess in actual process using the latent of adsorbent Power, it is necessary to reality environment, i.e., in a dynamic system with N2Competitive CO2Absorption.In addition, repeatedly circulation in reproducibility and Stability is also vital in actual applications.Therefore, dynamic column breakthrough experiment has been carried out.In this experiment, by 10% (v/v)CO2+ 90% (v/v) N2Mixed airflow be used for approximate simulation after-combustion flue gas (referring to Figure 34 experimental provision).It is dynamic State CO2Capacity passes through CO2Mass balance, subtracting the CO of blank assay2Calculated on the basis of breakthrough curve integration. During 298K, the SU-MC1 and SU-MAC1 CO that are obtained2Capacity is respectively 0.98 and 1.45mmol g-1.It is worth noting that, CO from the experiment of binary Kinetic penetration2Capacity under 298K and 0.1 bar with using pure CO2Balancing a survey result (that is, for SU-MC1 and SU-MAC1 is respectively 1.0 and 1.4mmol g-1) matched well.This means CO2Compare N2It is preferentially adsorbed to adsorbent On material, this further demonstrates that the high CO of material2/N2Selectivity.
In addition, CO is tested by dynamic column through transmission technique2The invertibity of absorption.For with CO2The sample of saturation, by pure N2 Purged under 298K, until not detecting CO in effluent after 30 minutes2.For SU-MC1 and SU-MAC1, subsequent CO2 Absorption shows CO2Capacity recovers completely.It is important to note that CO2This temperate condition of release is favourable, because with The adsorbent (such as amine functionalised materials) for needing quite a lot of heat energy input for regeneration is compared, and it applies and adsorbent reactivation phase The minimal energy losses of pass.In addition, carry out 10 absorption and de-adsorption cycle.As can be seen that except caused by experimental error Change, after 10 circulations, maintain the CO of SU-MC1 (Figure 35) and SU-MAC1 (Figure 36 D) material2Capacity.Therefore, deposit herein SU-MC1 and SU-MAC1 materials easily and can be completely carried out regenerating under multiple circulation, reduce CO without obvious2 Absorption property.In addition, under 298K and 0.1 bars partial pressure, SU-MC1 and SU-MAC1 are under wet environment (~3 volume % water) Dynamic CO2Capacity is respectively 0.51 and 1.13mmol g-1, equal to than dry CO2Capacity reduces by 48% and 22% (Figure 36 A-C). These suppression ratio Typical physical adsorbents (such as zeolite 13X) reduce a lot, and when introducing vapor, capacity declines>90%, with this Study and~0.03mmol g are left under suitable wet condition-1Capacity.SU-MAC1 CO2Capacity Ratio SU-MC1 is reduced can be with It is attributed to stronger adsorbent-CO2Interact (such as CO2Shown in isosteric heat of adsorption) and carbon skeleton in more pyrroles and Pyridone type nitrogen quantity.The CO of humidity is repeated 10 times on SU-MAC12Absorption/desorption, the SU-MAC1 is in subsequent circulation Between there is the CO that regenerates completely2Capacity (Figure 26 D), what this showed in the moisture material goes out color stability.Although moist ring CO can be obtained under border on porous carbon2The finite data of physical absorption, but even in slightly higher CO2Under partial pressure (0.14 bar), SU- MAC1 moist CO2Capacity is also above the nitrogenous mesoporous carbon being previously reported by, i.e. 0.91mmol g-1.In addition, 10%/90% CO2/N2The acid impurities of trace, i.e. 300ppm SO are introduced in mixture2, 100ppm NO, 5ppm NO2With 10ppm's HCl, to study the effect of the acid impurities in the case of the ub-bituminous coal that burns, as shown in figure 37.It was found that SU-MAC1 CO2Capacity For 0.74mmol g-1, equal to pure CO2Capacity, which is compared, reduces 47%.Need further to study physical absorbent moist and CO is improved under sour environment2Capacity；However, all these promising performances all show its CO2/N2The extraordinary potential of separation.
C3) conclusion
In a word, we have demonstrated that passing through soft template scheme by using the nitrogen containing monomer of rational design makes doping nitrogen The synthesis strategy of mesoporous carbon.Carbon derived from porous conjugated polymer have high-specific surface area, larger pore volume and from macropore, be situated between Hierarchy of the hole to micropore.Our graded porous carbon shows promising CO2Adsorption capacity (298K, 0.1 and 1 bar CO2Under, respectively 1.0and 3.1mmol g-1), outstanding CO2/N2Selectivity (51：1), it is easy to regeneration and multi-cycle. In addition, have 331 with what is be previously reported by:The mesoporous carbon of 1 the new highest record in history carbon dioxide/nitrogen selectivity is compared, chemism charcoal Realize highest CO2 Specific adsorptions capacity (in 298K, 0.1 and 1 bar of CO2Under, respectively 1.4 and 4.5mmol g-1).Material can With regeneration completely in a mild condition.It appear that high-performance in humid conditions and going out color stability under moisture. Design concept in the research can further be developed, for being synthesized by well-designed polymer with nitrogen precursor for two The graded porous carbon of carbonoxide capture, causes common group between the precursor based on conjugated polymer and surfactant soft template Dress.
C4) material and method
C4a) material.Two kinds of commercially available porous carbon materials, i.e. Maxsorb and CMK-3 are limited from Northwest coke chemical respectively Company (Kansai Coke and Chemicals Co., Ltd.) and ACS Materials Co., Ltd (ACS Material, LLC) purchase Buy.All other chemicals and solvent are purchased from the strange company in SIGMA-Ai Er Delhis (Sigma Aldrich), and need not enter The purifying of one step can be used.
C4b) the synthesis of 4- (pyrroles -1- bases) butyric acid.The synthetic route of 4- (pyrroles -1- bases) butyric acid is changed from Gracia etc. The previous research of people is carried out.In exemplary synthesis, by 4-Aminobutanoicacid (10.0g, 97mmol), H2O (144ml), sodium acetate (NaOAc, 8.0g, 97.5mmol), acetic acid (AcOH, 48ml) and 1,2- dichloroethanes (144 milliliters) are together in N2In in 90 DEG C Lower heating.2,5- dimethoxy-tetrahydrofurans (12.6ml, 97.2mmol) are added into the mixture, 16 are stirred energetically at 90 DEG C Hour.Mixture is cooled down, removes organic layer.Water layer extracts (CH three times with dichloromethane2Cl2, 3 × 20ml).What is merged is organic Extract is washed with water (2 × 200ml), with anhydrous magnesium sulfate (MgSO4) dry, filtering, and depressurized using Rotovapor Lower removal solvent.Crude product is dissolved in CH2Cl2In (20ml), and with saturation NaHCO3The aqueous solution extracts repeatedly.By the alkali of merging Property extract is acidified with HCl/water solution, and uses CH again2Cl2(3 × 20ml) is extracted.Organic phase is set to dry (MgSO4), Decompression is lower to remove solvent, and 4- (pyrroles -1- bases) butyric acid is obtained with yield 64%.1H NMR(400MHz,CDCl3,δ,ppm)6.64 (t, J=2.1Hz, ArH, 2H), 6.15 (t, J=2.1Hz, ArH, 2H), 3.95 (t, J=6.8Hz, NCH2-,2H),2.32(d, J=7.3Hz ,-CH2COOH, 2H), 2.08 (q, J=6.9Hz ,-CH2CH2CH2-,2H)。1H H NMR spectroscopies are as shown in figure 38.
C4c) the synthesis of N doping mesoporous polymer/mesoporous carbon (SU-MC1).Triblock copolymerP-123 Soft template in being synthesized as mesoporous polypyrrole.Respectively using hydrochloric acid and the pH and temperature of ice-water bath control solution.By iron chloride (FeCl3) be added in the aqueous solution, to cause 4- (pyrroles -1- bases) controlled ways of butyric acid as described below and soft mode plate surface Activating agent assembles altogether.
, will in exemplary synthesisP-123 (0.598g, purchased from aldrich company (Aldrich) and directly Connect use) and iron chloride (1.14g) be added to ice-water bath cool down ultra-pure water (Millipore Water) (15ml) and 12M In HCl (2.5ml) mixture.Solution is mixed energetically 2 hours, then 4- (pyrroles -1- bases) butyric acid be added dropwise above-mentioned In solution.After stirring 20 minutes energetically with magnetic stirring bar in atmosphere, the solution is set to be stood in ice-water bath (without stirring) 20 hours, then hydro-thermal be heated to 100 DEG C, to complete the polymerization of 4- (pyrroles -1- bases) butyric acid monomer.Then hydrothermal product is entered Row filtering, and washed repeatedly with deionized water.In horizontal tube furnace (25mm diameters), in 75sccm N2(99.999%) peace treaty is flowed It is carbonized under the operating pressure of 520 supports.Polymer composites are heated to 350 DEG C with 1 DEG C/min of heating rate first And kept for 3 hours slowly to decompose triblock copolymer surfactant, then it is heated to 600 with 1 DEG C/min of heating rate DEG C, finally it is heated to 800 DEG C with 5 DEG C/min and is kept for 2 hours, produces final porous carbon (SU-MC1).
C4d) the synthesis of N doping mesoporous activated carbon (SU-MC1).Cryogenic carbon using potassium hydroxide (KOH) to SU-MC1 Change sample and implement oxidation chemistry activation to produce SU-MAC1.In illustrative methods, by synthesized poly- (4- (pyrroles -1- bases) Butyric acid) compound in horizontal tube furnace in N2Flow down and be heated to 350 DEG C with 1 DEG C/min heating rate, and kept for 3 hours, to enter Row carbonization, is denoted herein as SU-MC1-350 DEG C.Powder is collected, and uses 3:Mass ratioes of 1 KOH with respect to SU-MC1-350 DEG C Be dispersed in the 7M KOH aqueous solution.Stir the mixture for 2 hours, and it is dry 4 hours at 65 DEG C in vacuum drying oven, so Afterwards in N2Under be heated to 500 DEG C of (heating rates：5℃·min-1, the retention time：1 hour).Then it is activated sample is molten with HCl Liquid (10 weight %) thoroughly three times to remove the inorganic salts of any residual, then with deionized water fully washed until measure by washing Go out neutral pH.Finally, activated carbon is dried all night in 65 DEG C, vacuum in an oven.Thus the N doping synthesized is mesoporous activated Charcoal is expressed as SU-MAC1.
C4e) characterize.Entered using the XHR microscopes of FEI Magellan 400 with 5kV accelerating potentials and 25pA electric currents Row scanning electron microscopy (SEM).Transmission electron microscope is carried out using 200kV TEM FEI Tecnai T20 instruments (TEM) study.The element composition on surface is measured by XPS (PHI 5000 Versaprobe, Al KR sources).Elementary analysis makes Carried out with the analyzers of Carlo-Erba NA 1500, to determine the total nitrogen of bulk sample and carbon content.1H H NMR spectroscopies are at 293k Recorded in deuterochloroform using Varian Inova 500.N2And CO2Adsorption experiment uses AutoSorb iQ2(quart Crow nurse instrument company (Quantachrome)) progress of low-pressure gas Sorption Analyzer.Sample takes off at 0.001 support and 200 DEG C Gas 12 hours, is then measured.N2Physical absorption analysis uses 99.999% N under 77K2Carry out.N2Pore-size distribution (PSD) obtained by the carbon model with slit and cylindrical geometries using non local solid state density Functional Theory (NLDFT) .Specific surface area is in relative pressure range p/p0Obtained in=0.05-0.35 by Robert Brenner-Emmett-Teller (BET) method. For CO2Absorption measurement, using identical outgassing routine.CO2Absorption is using circulation bath control temperature under 273,298 and 323K Carry out.CO2PSD uses CO of the NLDFT carbon model based on 273K2Adsorption isotherm is calculated.
C4f) dynamic column breakthrough experiment.Dynamic CO2Capacity is assessed using the dynamic gas penetrating system of customization.90 bodies Product %N2With 10 volume %CO2Mixed gas the flow velocity of every kind of gas adjusted by using mass flow controller obtain.Gaseous mixture The overall flow rate of body is maintained at 30cm3min-1.Filling column (packed-bed column) is that internal diameter is the vertical stainless of 0.40cm Steel pipe.Sample of sorbent is fixed on porous stainless steel filter, the sample of sorbent is cut closely to install In stainless steel tube.Sample size is generally in the range of 15-30mg.Post is added using controlled Thermolyne heating tapes Heat.Sample of sorbent is heat-treated at least 6 hours at 130 DEG C in helium stream, is then measured.It is regenerated by subsequent Circulation between purge N at 25 DEG C2Carry out within 30 minutes.Gas is discharged to carry out using Extrel Max300-LG mass spectrographs Analysis.In testing in wet condition, N2Air-flow bubbling by the stainless steel column with water, then with CO2Mixing.Before analysis, So that sparging process balances at least 20 minutes.Under 298K water saturation vapour pressure (100% humidity), the water concentration in air-flow is about For 3 volume %.

Claims (17)

1. a kind of method for forming porous carbon, methods described include：
The first precursor is provided, first precursor includes one or more aromatic monomers；
Second precursor is provided；
3D polymer networks are formed by first precursor and the second precursor, wherein, second precursor is from the first precursor One or more polymer provide crosslinking；
The 3D polymer networks are dried to provide drying structure；And
Drying structure is carbonized to provide porous carbon structure, wherein, the carbon of the porous carbon structure is at least partly by first The carbonization of precursor is provided, and wherein the hole of porous carbon structure is at least partly provided by the volatilization of the second precursor, and before wherein second The volatilization of body at least partially in drying structure it is partially carbonized when occur.
2. the method as described in claim 1, it is characterised in that methods described further comprises：Porous carbon structure is lived Change further to improve the porosity of the porous carbon structure.
3. method as claimed in claim 2, it is characterised in that the temperature at 1000 DEG C or lower is activated to porous carbon structure Degree is lower to be carried out.
4. the method as described in claim 1, it is characterised in that the aromatic monomer includes one or more hetero atoms to provide Functional group in porous carbon structure.
5. the method as described in claim 1, it is characterised in that the aromatic monomer forms one or more conjugated polymers.
6. the method as described in claim 1, it is characterised in that the porous carbon structure is at least partly graphite.
7. the method as described in claim 1, it is characterised in that the 3D polymer networks pass through the first precursor and the second precursor Between noncovalent interaction formed.
8. method as claimed in claim 7, it is characterised in that the noncovalent interaction include one kind for being selected from the group or A variety of interactions：Hydrogen bond, metal-ligand key and ionic bond.
9. the method as described in claim 1, it is characterised in that second precursor is selected from the group：Phytic acid, phytic acid derivative, Inositol monophosphate, inositol monophosphate derivative, four [phenyl -4- boryls (dihydroxy)] methane and metal or H, H- phthalocyanine tetrasulfonic acid.
10. a kind of method for forming porous carbon, methods described include：
The first precursor is provided, first precursor has the A-B structures that one or more B groups are attached on A skeletons；
Wherein, A is the chemical combination of hydrophobic aromatic monomer or the aromatic monomer being selected from the group：Pyrroles, thiazole, pyridine, aniline, Thiophene, furans and their derivative；And
Wherein B is the functional group being selected from the group：Hydroxy-acid group (- COOH), oh group (- OH), amino group (- NH2), itrile group Group (- CN), sulfonic acid group (- SO3H), phosphonyl group (- PO4H), amide group (- C (=O)-NH-), boric acid (- BO2H2) and Amino acid group (- CH (NH2)-COOH)；
Second precursor is provided；
Structuring polymer is formed by the first precursor and the second precursor, the wherein structure of structuring polymer is formed by the second precursor Micellar structure determine, and wherein, set what the first polymer formed by the first precursor was formed to apply by the second precursor Micellar structure；
Structuring polymer is carbonized to provide porous carbon structure, wherein, the carbon of porous carbon structure is at least partly by first The carbonization of precursor is provided, and wherein the hole of porous carbon structure is at least partly provided by the volatilization of the second precursor.
11. method as claimed in claim 10, it is characterised in that B group is hydrophilic, also, is wherein used to form the The solvent of the micellar structure of two precursors is hydrophilic.
12. method as claimed in claim 10, it is characterised in that B group is hydrophobic, also, is wherein used to form the The solvent of the micellar structure of two precursors is hydrophobic.
13. method as claimed in claim 10, it is characterised in that methods described further comprises：Porous carbon structure is carried out Activate further to improve the porosity of porous carbon structure.
14. method as claimed in claim 13, it is characterised in that activated to porous carbon structure at 1000 DEG C or lower At a temperature of carry out.
15. method as claimed in claim 10, it is characterised in that the aromatic monomer includes one or more hetero atoms to carry For the functional group in porous carbon structure.
16. method as claimed in claim 10, it is characterised in that the aromatic monomer forms conjugated polymer.
17. method as claimed in claim 10, it is characterised in that the loose structure is at least partly graphite.
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