CN115403041B - Hemicellulose-based hollow porous carbon, preparation method thereof and application thereof in zinc ion energy storage device - Google Patents
Hemicellulose-based hollow porous carbon, preparation method thereof and application thereof in zinc ion energy storage device Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 69
- 229920002488 Hemicellulose Polymers 0.000 title claims abstract description 67
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000004146 energy storage Methods 0.000 title abstract description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 128
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 64
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 48
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 28
- 239000000661 sodium alginate Substances 0.000 claims abstract description 28
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 28
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 24
- 239000011148 porous material Substances 0.000 claims abstract description 16
- 239000003990 capacitor Substances 0.000 claims abstract description 14
- 238000003763 carbonization Methods 0.000 claims abstract description 11
- 238000010000 carbonizing Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 68
- 238000003756 stirring Methods 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000006185 dispersion Substances 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 15
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004005 microsphere Substances 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims 1
- 239000003575 carbonaceous material Substances 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 8
- 238000001354 calcination Methods 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 2
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 229940072056 alginate Drugs 0.000 description 4
- 235000010443 alginic acid Nutrition 0.000 description 4
- 229920000615 alginic acid Polymers 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 235000012431 wafers Nutrition 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The application provides hemicellulose-based hollow porous carbon, a preparation method thereof and application thereof in a zinc ion energy storage device, and relates to the technical field of hemicellulose-based materials. The hemicellulose-based hollow porous carbon is prepared by taking nano cubic calcium carbonate as a template, taking hemicellulose coated on the surface of the calcium carbonate as a carbon source and carbonizing at a high temperature; the length, width and height of the cubic calcium carbonate are 200-600nm; the hollow porous carbon has an average pore diameter of 7-17nm and a specific surface area of 500-900m 2 g ‑1 The total pore volume is 0.8-4.0cm 3 g ‑1 . According to the application, the mass ratio of sodium carbonate to sodium alginate is changed to synthesize specific cubic calcium carbonate, and a cubic structure is utilized to self-stack during calcination to provide a sphere-like morphology, so that a hollow porous carbon structure is obtained; porous carbon materials with different microcosmic morphologies are obtained by adjusting the proportion of the precursor and the calcium carbonate and proper carbonization conditions, so that the electrochemical performance of the zinc ion mixed capacitor prepared by taking the porous carbon materials as raw materials is improved.
Description
Technical Field
The application belongs to the technical field of hemicellulose-based materials, and particularly relates to a hemicellulose-based hollow porous carbon, a preparation method thereof and application thereof in a zinc ion energy storage device.
Background
Porous carbon is the most widely used electrode material at present. The porous carbon material has the advantages of relatively low cost, easy preparation, environmental protection and the like. In particular, carbon materials with developed pore structures, high specific surface area and good conductivity are widely researched and applied in the energy storage field. The preparation of the porous carbon comprises a hard template method, a soft template method, a pyrolysis combined activation method, a hydrothermal method, a molten salt synthesis method and the like. The preparation process is an important factor in the construction of porous carbon materials.
Among the synthetic methods, the template method is the most effective method for controlling the microcosmic morphology and pore structure characteristics of the synthesized carbon material. In China patent (CN 112897499A), a method for preparing a double-hetero-element doped porous carbon material by a salt template method is disclosed, wherein a carbon source, a hetero-element doped source and a salt template are mixed and freeze-dried, and the double-hetero-element doped porous carbon material is obtained through simple carbonization treatment. The preparation process is complex, the carbonization temperature is high, and the prepared material has non-uniform microscopic morphology. In addition, in chinese patent (CN 110734047 a), porous carbon materials were prepared using a nano zinc oxide template. The porous carbon material is obtained by taking nano zinc oxide as a template, furfuryl alcohol as a carbon source and reducing the furfuryl alcohol with high-temperature hydrogen. The preparation process involves the use of dangerous gases, and the morphology of the prepared product cannot be effectively controlled. In China patent (CN 109835880A), alginate is used as a carbon source, an in-situ template method is adopted, and an alginate and carbonate ions react with calcium ions to generate a porous carbon precursor, so that the porous carbon material is prepared by carbonization and decalcification. The method needs to use higher amount of alginate, the process of dissolving the alginate in water to form a uniform solution is time-consuming and energy-consuming, and the microstructure of the formed porous carbon material is difficult to form a hollow nano structure by effectively regulating and controlling the ratio of a carbon source to a template.
Therefore, the design of the method with low energy consumption and simple preparation can effectively control the microscopic morphology and the pore structure of the carbon material, thereby obtaining the porous carbon with a hollow structure and remarkably improving the electrochemical performance of the zinc ion hybrid capacitor, and the method is a problem to be solved by the technicians in the field.
Disclosure of Invention
The application aims to provide hemicellulose-based hollow porous carbon, which is characterized in that cubic calcium carbonate is designed and synthesized by changing the mass ratio of sodium carbonate to sodium alginate, the obtained nano three-dimensional calcium carbonate is used as a template, hemicellulose coated on the surface of the nano three-dimensional calcium carbonate is used as a carbon source, and porous carbon materials with different microcosmic morphologies are obtained by the proportion of a precursor (hemicellulose) to the calcium carbonate and proper carbonization conditions.
In order to achieve the above purpose, the application provides a hemicellulose-based hollow porous carbon, which is prepared by taking nano cubic calcium carbonate as a template, taking hemicellulose coated on the surface of the calcium carbonate as a carbon source, and carbonizing at high temperature; the length, width and height of the cubic calcium carbonate are 200-600nm; the hollow porous carbon has an average pore diameter of 7-17nm and a specific surface area of 500-900m 2 g -1 The total pore volume is 0.8-4.0cm 3 g -1 。
The application further aims to provide a preparation method of the hemicellulose-based hollow porous carbon, which comprises the steps of firstly preparing a template with a three-dimensional structure, forming a sphere-like morphology by self-stacking nano cubic calcium carbonate mixed with hemicellulose in a calcining process, and endowing the hollow porous microsphere morphology of the material after removal. At the same time CaCO 3 CO is generated during pyrolysis 2 The material is physically activated to produce a rich pore structure. Thus obtaining the hollow porous calcium carbonate microsphere, the whole preparation method is simple, the nano three-dimensional calcium carbonate is prepared by stirring at normal temperature, the time is short, and the energy consumption is low.
In order to achieve the above object, the present application provides a method for preparing hemicellulose-based hollow porous carbon, comprising the following steps:
s1, preparing nano cubic calcium carbonate at normal temperature: respectively dissolving sodium alginate and sodium carbonate in water, mixing the obtained sodium alginate solution and sodium carbonate solution, and uniformly stirring to obtain a clear water solution;
adding a calcium chloride solution into the clear water solution under stirring, and stirring to obtain a mixed solution;
filtering the mixed solution, collecting filter residues and drying to obtain cubic calcium carbonate;
s2, coating calcium carbonate with hemicellulose: completely dissolving hemicellulose and stereoscopic calcium carbonate in water respectively to obtain hemicellulose solution and stereoscopic calcium carbonate dispersion;
slowly injecting the hemicellulose solution into the stereoscopic calcium carbonate dispersion liquid, stirring and heating the mixed liquid, and evaporating to constant weight to obtain powder;
and S3, carbonizing and activating the powder to obtain the hemicellulose-based hollow porous carbon.
In a preferred embodiment, in step S1, the concentration of the sodium alginate solution is 0.0025-0.01g/ml; the concentration of the sodium carbonate solution is 0.02-0.11g/ml; the concentration of the calcium chloride solution is 0.03-0.14g/ml.
In a preferred embodiment, in step S1, the volume ratio of the sodium alginate solution, the sodium carbonate solution and the calcium chloride solution is 1: (2-8): (1-10).
In a preferred embodiment, in step S1, the mixing of the sodium alginate solution and the sodium carbonate solution is performed by: slowly dripping sodium carbonate solution into sodium alginate solution at a rate of 1.25mL/min, wherein after dripping, the stirring temperature is 20-25 ℃, the stirring time is 5-20min, and the clear water solution is obtained, preferably, the stirring temperature is 20 ℃, and the stirring time is 5min.
In a preferred embodiment, in step S2, the hemicellulose solution has a concentration of 0.05-0.2g/ml; the concentration of the stereoscopic calcium carbonate dispersion liquid is 0.2-0.6g/ml.
In a preferred embodiment, in step S2, the volume ratio of hemicellulose solution to stereoscopic calcium carbonate dispersion is 1: (0.2-5).
In a preferred embodiment, in step S2, the slow injection operation is: injecting the hemicellulose solution into the stereoscopic calcium carbonate dispersion liquid in a stirring state at a rate of 2 mL/min; the operation of stirring and heating the mixed liquid is as follows: heating the mixed liquid to 70-90 ℃, keeping the temperature, stirring and evaporating to dryness.
In a preferred embodiment, in step S3, the inert atmosphere is nitrogen or argon; the carbonization conditions are as follows: heating at a heating rate of 2-8deg.C/min, carbonizing at a final temperature of 800-900deg.C, and standing for 0-1 hr.
Another object of the present application is to provide an electrode, comprising the steps of:
the hemicellulose-based hollow porous carbon prepared by the method is taken as a raw material, 60 weight percent of polytetrafluoroethylene dispersion and a proper amount of distilled water are added, the mixture is uniformly mixed, a carbon film is prepared by rolling, the carbon film is pressed on foam nickel by a certain pressure and dried in vacuum, and the dried sheet is cut into wafers, thus obtaining the hemicellulose-based hollow porous carbon.
In a preferred embodiment, the mass ratio of hemicellulose-based hollow porous carbon to 60wt% polytetrafluoroethylene dispersion is (80-90): (10-20), wherein the drying temperature is 100-120 ℃, the tabletting pressure is 20-30MPa, and the diameter of the wafer is 12mm.
Another object of the present application is to provide an electrode, wherein the electrode made of hemicellulose-based hollow porous carbon is used as a negative electrode, and the zinc ion hybrid capacitor is assembled to operate at 0.5. 0.5A g -1 The current density can reach 89.4Wh kg -1 And at 10A g -1 Can reach 6.9kW kg under the current density -1 Shows high energy density and power density.
To achieve the above object, the present application provides a zinc ion mixed capacitor comprising a zinc foil positive electrode, a glass fiber separator and 0.1-3M ZnSO impregnated therewith 4 ·7H 2 The electrolyte of O, the carbon electrode negative electrode, the gasket and the elastic sheet of claim 7 are stacked together, and are put into a CR2032 button battery shell to be assembled into the zinc ion hybrid capacitor through a packaging machine.
Compared with the prior art, the technical scheme of the application has the following advantages:
1. according to the application, nano three-dimensional calcium carbonate is used as a template, and the nano three-dimensional calcium carbonate is self-stacked during calcination to provide a sphere-like morphology, so that a hollow porous carbon structure is obtained; hemicellulose is used as a carbon source, the raw material is low in cost and easy to purchase, porous carbon is prepared after activation and carbonization, a large specific surface area can be obtained, and a large number of active sites are provided for ion transmission.
2. According to the application, the morphology of the calcium carbonate is obtained by designing the mass ratio of the sodium carbonate to the sodium alginate and regulating and controlling the reaction conditions, and the sodium alginate is less in dosage, so that the reaction time is shortened, the reaction energy consumption is reduced, and the three-dimensional calcium carbonate can be prepared in a normal temperature environment.
3. The method has the advantages of simple integral operation steps, environment-friendly process, low raw material and energy consumption cost, and is particularly suitable for large-scale industrial production and preparation.
Drawings
These and/or other aspects and advantages of the present application will become more apparent and more readily appreciated from the following detailed description of the embodiments of the application, taken in conjunction with the accompanying drawings, wherein:
fig. 1 is an SEM image of the stereoscopic calcium carbonate prepared in example 1 of the present application at different magnifications.
Fig. 2 is an SEM image of MC4 prepared in example 1 of the present application at different magnifications.
FIG. 3 is an SEM image of MCs prepared in example 2 and example 3 of the application.
FIG. 4 shows the energy density versus power density results for MCs prepared in examples 1-3 of the application.
Detailed Description
For a better understanding of the present application, those skilled in the art will now make further details with reference to the drawings and the detailed description, but it should be understood that the scope of the application is not limited by the detailed description.
The embodiment of the application solves the technical problems that the micro morphology and pore structure of a carbon material cannot be effectively controlled in the prior art, so that porous carbon microspheres with hollow structures and high specific surface areas are difficult to prepare, and the electrochemical performance of an electrode prepared from the material is poor.
The technical scheme of the application aims to solve the problems, and the general idea is as follows:
the application provides a hemicellulose-based hollow porous carbon, which is prepared by taking nano cubic calcium carbonate as a template, taking hemicellulose coated on the surface of the calcium carbonate as a carbon source and carbonizing at a high temperature; the length, width and height of the cubic calcium carbonate are 200-600nm; the hollow porous carbon has an average pore diameter of 7-17nm and a specific surface area of 500-900m 2 g -1 The total pore volume is 0.8-4.0cm 3 g -1 。
Another object of the present application is to provide a method for preparing hemicellulose-based hollow porous carbon, specifically comprising the steps of:
s1, preparing nano cubic calcium carbonate at normal temperature: respectively dissolving sodium alginate and sodium carbonate in water, mixing the obtained sodium alginate solution and sodium carbonate solution, and uniformly stirring to obtain a clear water solution;
adding a calcium chloride solution into the clear water solution under stirring, and stirring to obtain a mixed solution;
filtering the mixed solution, collecting filter residues and drying to obtain cubic calcium carbonate;
s2, coating calcium carbonate with hemicellulose: completely dissolving hemicellulose and stereoscopic calcium carbonate in water respectively to obtain hemicellulose solution and stereoscopic calcium carbonate dispersion;
slowly injecting the hemicellulose solution into the stereoscopic calcium carbonate dispersion liquid, stirring and heating the mixed liquid, and evaporating to constant weight to obtain powder;
and S3, carbonizing and activating the powder to obtain the hemicellulose-based hollow porous carbon.
In a preferred embodiment, in step S1, the concentration of the sodium alginate solution is 0.0025-0.01g/ml; the concentration of the sodium carbonate solution is 0.02-0.11g/ml; the concentration of the calcium chloride solution is 0.03-0.14g/ml; preferably, the concentration of the sodium alginate solution is 0.005g/ml; the concentration of the sodium carbonate solution is 0.053g/ml; the concentration of the calcium chloride solution was 0.066g/ml.
The volume ratio of the sodium alginate solution to the sodium carbonate solution to the calcium chloride solution is 1: (2-8): (1-10); preferably, the volume ratio of the sodium alginate solution to the sodium carbonate solution to the calcium chloride solution is 1:4:4.
in a preferred embodiment, in step S1, the mixing of the sodium alginate solution and the sodium carbonate solution is performed by: slowly dripping sodium carbonate solution into sodium alginate solution at a rate of 1.25mL/min, and stirring at 20-25deg.C for 5-20min to obtain clear water solution; preferably, the stirring temperature is 20 ℃ and the stirring time is 20min.
According to the application, the addition amount of sodium alginate is reduced by optimizing the ratio and the dripping mode of the sodium alginate aqueous solution and the sodium carbonate aqueous solution, so that a clarified aqueous solution can be quickly obtained under the normal temperature condition, the reaction energy consumption and the synthesis time are reduced, and a foundation is laid for obtaining the three-dimensional calcium carbonate in the later stage and improving the electrical property of the material.
In a preferred embodiment, in step S1, the rotational speed in the stirring state is 100 to 200rpm; after the calcium chloride solution is added, stirring the mixture for 10 to 30 minutes at the temperature of 20 to 25 ℃; preferably, the stirring temperature is 20 ℃ and the stirring time is 30min.
In a preferred embodiment, in step S1, the condition for drying the collected filter residues may be any condition known to those skilled in the art, and the preferred drying condition is that: the drying temperature is 70-90 ℃ and the drying time is 2-8h.
In a preferred embodiment, in step S2, the hemicellulose solution has a concentration of 0.05-0.2g/ml; the concentration of the stereoscopic calcium carbonate dispersion liquid is 0.2-0.6g/ml, and the volume ratio of the hemicellulose solution to the stereoscopic calcium carbonate dispersion liquid is 1: (0.2-5); preferably, the hemicellulose solution has a concentration of 0.1g/ml; the concentration of the stereoscopic calcium carbonate dispersion liquid is 0.4g/ml, and the volume ratio of the hemicellulose solution to the stereoscopic calcium carbonate dispersion liquid is 1:1.
in a preferred embodiment, in step S2, the slow injection operation is: injecting the hemicellulose solution into the stereoscopic calcium carbonate dispersion liquid in a stirring state at a rate of 2 mL/min; the operation of stirring and heating the mixed liquid is as follows: heating the mixed liquid to 70-90 ℃, keeping the temperature, stirring and evaporating to dryness.
In a preferred embodiment, in step S3, the inert atmosphere is nitrogen or argon; the carbonization conditions are as follows: heating at a heating rate of 2-8deg.C/min, carbonizing at a final temperature of 800-900deg.C, and standing for 0-1 hr.
In a preferred embodiment, in step S3, in order to make the purity of the obtained hollow porous carbon better, a purification step may be further included: after carbonization, washing for 1h with an excess of 1M hydrochloric acid, and repeatedly washing with distilled water until the filtrate is neutral.
Another object of the present application is to provide an electrode, comprising the steps of:
the hemicellulose-based hollow porous carbon prepared by the method is taken as a raw material, 60 weight percent of polytetrafluoroethylene dispersion and a proper amount of distilled water are added, the mixture is uniformly mixed, a carbon film is prepared by rolling, the carbon film is pressed on foam nickel by a certain pressure and dried in vacuum, and the dried sheet is cut into wafers, thus obtaining the hemicellulose-based hollow porous carbon.
In a preferred embodiment, the mass ratio of hemicellulose-based hollow porous carbon to 60wt% polytetrafluoroethylene dispersion is (80-90): (10-20), wherein the drying temperature is 100-120 ℃, the tabletting pressure is 20-30MPa, and the diameter of the wafer is 12mm.
Another object of the application is to provide an electrode comprising a zinc foil positive electrode, a glass fiber separator and impregnated 0.1-3M ZnSO thereof 4 ·7H 2 The electrolyte of O, the carbon electrode negative electrode, the gasket and the elastic sheet of claim 7 are stacked together, and are put into a CR2032 button battery shell to be assembled into the zinc ion hybrid capacitor through a packaging machine.
The following describes the technical scheme of the application in detail through specific embodiments:
unless otherwise indicated, the technical means used in the present application are conventional means well known to those skilled in the art, and various raw materials, reagents, instruments, equipment, etc. used in the present application are commercially available or can be prepared by existing methods. The normal temperature is 20-25 ℃.
Example 1
Step one: 0.25g sodium alginate was dispersed in 50mL water and stirred until completely dissolved.
Step two: slowly dripping Na into sodium alginate solution at normal temperature under stirring at 200rpm at 1.25mL/min 2 CO 3 Solution (10.6 g Na) 2 CO 3 200 mL) was stirred for an additional 20min.
Step three: caCl is added with 2 Solution (13.31 g CaCl) 2 200 mL) was slowly added to the mixture of step two and the stirring at 200rpm was maintained throughout the process. CaCl (CaCl) 2 After the solution was completely added, the resulting mixture was stirred at room temperature for 30min.
Step four: filtering the mixed solution in the third step, washing with pure water, and drying to obtain cubic CaCO 3 。
Step five: 2g of hemicellulose was dissolved in 20mL of water and stirred at 200rpm for 1h until completely dissolved.
Step six: the 8g cubic calcium carbonate described in step four was dispersed in 20mL of water and stirred at 200rpm for 1h. Then, slowly injecting the hemicellulose solution in the fifth step into CaCO at a speed of 2mL/min under stirring 3 In the dispersion. The mixed liquid was heated to 80 ℃ and stirring was continued until evaporated to dryness.
Step seven: the powder obtained was placed in a tube furnace at 850℃and N 2 And (3) under the atmosphere, carbonizing and activating, washing the obtained solid for 1h by using excessive 1M hydrochloric acid, and repeatedly washing the solid by using distilled water until the filtrate is neutral, thereby obtaining the hollow porous carbon (MC 4).
The morphology of the three-dimensional calcium carbonate obtained in the step four is shown in figure 1, and the prepared calcium carbonate can be seen to show an obvious cube structure.
The morphology of the hollow porous carbon (MC 4) obtained in the step seven is shown in fig. 2, and it can be seen from the figure that a spherical structure is formed according to the morphology of calcium carbonate, and the interior of the hollow porous carbon (MC 4) presents a hollow morphology.
Electrochemical propertiesThe testing method comprises the following steps: mixing the prepared sample with PTFE at a mass ratio of 85/15, adding a small amount of distilled water, mixing uniformly, rolling to obtain carbon film, pressing on foam nickel, vacuum drying at 110deg.C, tabletting at 25MPa to obtain working electrode, and zinc foil as positive electrode at 1 ° 1L -1 ZnSO of (2) 4 The capacitive properties of the assembled button cell in the electrolyte were tested, and the results from FIG. 4 show that the resulting sample was at 0.5A g -1 The current density can reach 89.4Wh kg -1 And at 10A g -1 Can reach 6.9kW kg under the current density -1 Shows high energy density and power density.
Example 2
Step six: the 6g cubic calcium carbonate described in step four was dispersed in 20mL of water and stirred at 200rpm for 1h. Then, slowly injecting the hemicellulose solution in the fifth step into CaCO at a speed of 2mL/min under stirring 3 In the dispersion. The mixed liquid was heated to 80 ℃ and stirring was continued until evaporated to dryness.
The remaining reaction conditions and steps were the same as in example 1, and the obtained porous carbon was designated as a plate-like porous carbon (MC 3).
As can be seen from fig. 3 (a), the MC3 prepared in this example is a porous sheet structure. The same electrode preparation method as in example 1 showed that the obtained sample was at 0.5. 0.5A g from the results of FIG. 4 -1 The energy density decreases at the current density and the power density decreases at the same energy density, mainly due to CaCO 3 The amount is small, the template effect and the physical activation pore-forming effect cannot be fully achieved, the specific surface area is reduced, and the morphology is nonuniform.
Example 3
Step six: the 10g cubic calcium carbonate described in step four was dispersed in 20mL of water and stirred at 200rpm for 1h. Then, slowly injecting the hemicellulose solution in the fifth step into CaCO at a speed of 2mL/min under stirring 3 In the dispersion. The mixed liquid was heated to 80 ℃ and stirring was continued until evaporated to dryness.
The remaining reaction conditions and steps were the same as in example 1, and the obtained porous carbon was designated as a plate-like porous carbon (MC 5).
As can be seen from fig. 3 (b), the MC5 prepared in this example is a porous sheet structure. The same electrode preparation method as in example 1 showed that the obtained sample was at 0.5. 0.5A g from the results of FIG. 4 -1 The energy density decreases at the current density and the power density decreases at the same energy density, mainly due to CaCO 3 The use amount is large, excessive activation causes collapse of material pore canals, so that the spherical morphology is damaged, and the specific surface area is reduced.
The MCs prepared in examples 1-3 were characterized and examined for microscopic pore structure parameters, and the results are shown in Table 1:
TABLE 1
As can be seen from Table 1, the porous carbon particles prepared in examples 1-3 are mesoporous materials having particle diameters of 20nm or less, wherein the specific surface area of MC4 can reach 869.37m 2 g -1 The total pore volume is up to 3.86cm 3 g -1 The obvious hollow porous microsphere structure can be seen by combining with an SEM image, which shows that the synthesized three-dimensional calcium carbonate is effectively stacked to form a spherical morphology in the calcining process.
The foregoing descriptions of specific exemplary embodiments of the present application are presented for purposes of illustration and description. It is not intended to limit the application to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the application and its practical application to thereby enable one skilled in the art to make and utilize the application in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the application be defined by the claims and their equivalents.
Claims (8)
1. A hemicellulose-based hollow porous carbon for a zinc ion capacitor, characterized in that the hemicellulose-based hollow porous carbon is in nanocube carbonThe calcium carbonate is prepared by taking calcium carbonate as a template and hemicellulose coated on the surface of the calcium carbonate as a carbon source through high-temperature carbonization; the length, width and height of the cubic calcium carbonate are 200-600nm; the hollow porous carbon is hollow porous microsphere, has average pore diameter of 7-17-nm and specific surface area of 500-900m 2 Per gram, a total pore volume of 0.8-4.0. 4.0cm 3 /g；
The method specifically comprises the following steps:
s1, preparing nano cubic calcium carbonate at normal temperature: respectively dissolving sodium alginate and sodium carbonate in water, mixing the obtained sodium alginate solution and sodium carbonate solution, and uniformly stirring to obtain a clear water solution;
adding a calcium chloride solution into the clear water solution under stirring, and stirring to obtain a mixed solution;
filtering the mixed solution, collecting filter residues and drying to obtain cubic calcium carbonate;
s2, coating calcium carbonate with hemicellulose: completely dissolving hemicellulose and stereoscopic calcium carbonate in water respectively to obtain hemicellulose solution and stereoscopic calcium carbonate dispersion;
slowly injecting the hemicellulose solution into the stereoscopic calcium carbonate dispersion liquid, stirring and heating the mixed liquid, and evaporating to constant weight to obtain powder;
s3, carbonizing and activating the powder to obtain hemicellulose-based hollow porous carbon;
wherein in the step S2, the concentration of the hemicellulose solution is 0.1g/ml; the concentration of the stereoscopic calcium carbonate dispersion liquid is 0.4g/ml, and the volume ratio of the hemicellulose solution to the stereoscopic calcium carbonate dispersion liquid is 1:1.
2. the hemicellulose-based hollow porous carbon for zinc ion capacitor as claimed in claim 1, wherein in step S1, the concentration of said sodium alginate solution is 0.0025-0.01g/ml; the concentration of the sodium carbonate solution is 0.02-0.11g/ml; the concentration of the calcium chloride solution is 0.03-0.14g/ml;
the volume ratio of the sodium alginate solution to the sodium carbonate solution to the calcium chloride solution is 1: (2-8): (1-10).
3. The hemicellulose-based hollow porous carbon for zinc ion capacitor as claimed in claim 1, wherein in step S1, the manner of mixing the sodium alginate solution and the sodium carbonate solution is: slowly dripping sodium carbonate solution into sodium alginate solution at a rate of 1.25mL/min, and stirring at 20-25deg.C for 5-20min to obtain clear water solution.
4. The hemicellulose-based hollow porous carbon for zinc ion capacitor as claimed in claim 1, wherein in step S2, said slow injection operation is: injecting the hemicellulose solution into the stereoscopic calcium carbonate dispersion liquid in a stirring state at a rate of 2 mL/min; the operation of stirring and heating the mixed liquid is as follows: heating the mixed liquid to 70-90 ℃, keeping the temperature, stirring and evaporating to dryness.
5. The hemicellulose-based hollow porous carbon for zinc ion capacitor as claimed in claim 1, wherein in step S3, said inert atmosphere is nitrogen or argon; the carbonization conditions are as follows: heating at a heating rate of 2-8deg.C/min, carbonizing at a final temperature of 800-900deg.C, and standing for 0-1 hr.
6. An electrode is characterized in that the hemicellulose-based hollow porous carbon for a zinc ion capacitor as claimed in claim 1 is used as a raw material for preparation, and the specific method comprises the following steps: adding proper distilled water into the hemicellulose-based hollow porous carbon and 60wt% polytetrafluoroethylene dispersion, uniformly mixing, rolling to prepare a carbon film, pressing the carbon film on foam nickel with a certain pressure, vacuum drying, and cutting the sheet obtained by drying into a wafer.
7. The electrode of claim 6, wherein the mass ratio of hemicellulose-based hollow porous carbon to 60wt% polytetrafluoroethylene dispersion is (80-90): (10-20), wherein the drying temperature is 100-120 ℃, the tabletting pressure is 20-30MPa, and the diameter of the wafer is 12mm.
8. A zinc ion mixed capacitor is characterized by comprising a zinc foil positive electrode, a glass fiber diaphragm and 0.1-3M ZnSO immersed by the same 4 ·7H 2 The electrolyte of O, a carbon electrode negative electrode, a gasket and an elastic sheet, wherein the carbon electrode negative electrode is the electrode of claim 7, the above structures are overlapped together, and the electrode is put into a CR2032 button battery shell and assembled into the zinc ion mixed capacitor through a packaging machine.
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