CN113772655A - Heteroatom-doped hard carbon material and preparation method thereof - Google Patents
Heteroatom-doped hard carbon material and preparation method thereof Download PDFInfo
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 47
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 229920002749 Bacterial cellulose Polymers 0.000 claims abstract description 13
- 239000005016 bacterial cellulose Substances 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 229910052786 argon Inorganic materials 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 238000010000 carbonizing Methods 0.000 claims abstract description 4
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 10
- 239000011229 interlayer Substances 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011149 active material Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 238000002441 X-ray diffraction Methods 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 claims description 3
- 239000005539 carbonized material Substances 0.000 claims description 3
- 238000012512 characterization method Methods 0.000 claims description 3
- 238000011156 evaluation Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 238000003795 desorption Methods 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 abstract description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- -1 heating Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002390 heteroarenes Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative 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
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a heteroatom-doped hard carbon material and a preparation method thereof, belongs to the field of carbon materials, and relates to a preparation method of a heteroatom-doped hard carbon material, which comprises the following steps: stirring to prepare a strong polar organic solvent; dissolving in a second step: dissolving 2.5a-3.5a grams of bacterial cellulose into the organic solvent in the step 1 to form uniform suspension; step three, precursor preparation: stirring and dissolving a g of urea into the suspension obtained in the step two, placing the suspension in heating equipment, continuously heating and reacting under the protection of argon, circularly filtering, washing, and finally drying to obtain nitrogen-doped precursor powder; step four, carbonizing: the precursor powder in the third step is placed in a calcining device and is carbonized at high temperature under the protection of argon, so that the ion diffusion capacity can be improved, the pseudocapacitance ratio is provided, the carbon layer is distorted, the electronic arrangement is changed, and the conductivity of the carbon material is effectively improved.
Description
Technical Field
The invention relates to the field of carbon materials, in particular to a heteroatom-doped hard carbon material and a preparation method thereof.
Background
The hard carbon material is considered as the most potential commercialized negative electrode material due to the outstanding advantages of high reversible specific capacity, low voltage and the like. But still has the problems of poor rate performance, fast attenuation and the like. The rate capability can be improved to a great extent by doping heteroatoms or increasing defect sites; the biomass raw material has the characteristics of wide source and low price. Among them, bacterial cellulose is a very good carbon source, and in order to further improve electron conductivity, it is necessary to introduce hetero atoms such as nitrogen into the matrix of the carbon material. Urea is a cheap raw material and has a rich nitrogen source.
For example, the patent publication No. CN10499284B discloses a heteroatom-doped titanium composite material, a preparation method and an application thereof, wherein perhalogenated butadiene, a titanium source and heteroarene are subjected to a sealing reaction under a reaction pressure higher than atmospheric pressure; after the reaction is finished, releasing pressure to normal pressure, naturally cooling to room temperature, washing the obtained solid, and drying in vacuum to obtain a dried sample; carrying out high-temperature treatment on the dried sample under the protection of inert gas to obtain a heteroatom-doped titanium composite material with excellent electrical properties;
however, the titanium raw material is expensive, so that the preparation cost of the heteroatom-doped hard carbon material is high, and the problems of poor rate capability and rapid attenuation of the conventional heteroatom-doped hard carbon material still exist during use.
Disclosure of Invention
1. Technical problem to be solved
Aiming at the problems in the prior art, the invention aims to provide a heteroatom-doped hard carbon material and a preparation method thereof, which can improve the ion diffusion capacity, provide the pseudocapacitance ratio, distort a carbon layer, change the electronic arrangement and effectively improve the conductivity of the carbon material.
2. Technical scheme
In order to solve the above problems, the present invention adopts the following technical solutions.
A heteroatom-doped hard carbon material comprises the following raw materials: a g of urea, 2.5a-3.5a g of bacterial cellulose, 1.1a-1.6a g of resorcinol and 0.1-0.2a ml of ethylenediamine solution with the mass fraction of 60-80%.
A preparation method of a heteroatom-doped hard carbon material comprises the following steps:
step one, preparing a solvent: sequentially mixing 1.1a-1.6a g of resorcinol, 3a-3.5a ml of water and 0.1-0.2a ml of ethylenediamine solution with the mass fraction of 60-80% in a reaction vessel, and stirring to prepare a strong polar organic solvent;
dissolving in a second step: dissolving 2.5a-3.5a g of bacterial cellulose into the organic solvent in the step 1, and continuously stirring or carrying out ultrasonic treatment until the bacterial cellulose is completely dissolved to obtain uniform suspension;
step three, precursor preparation: stirring and dissolving a g of urea into the suspension obtained in the step two, placing the suspension in heating equipment, continuously heating and reacting under the protection of argon, circularly filtering, washing, and finally drying to obtain nitrogen-doped precursor powder;
step four, carbonizing: putting the precursor powder in the third step into a calcining device, and carrying out high-temperature carbonization under the protection of argon;
step five, washing: and (5) washing and filtering the carbonized material obtained in the fourth step to be neutral, and drying to obtain the heteroatom-doped hard carbon material.
And six steps of characterization observation: observing the change of the appearance of the heteroatom-doped hard carbon material, researching the change of the structure and the interlayer spacing of the carbon, and researching the distribution of the specific surface area and the pore structure and the change of the functional group.
Step seven, electrochemical evaluation: the button cell was assembled, the performance of the active material was evaluated, and then assembled into a cylindrical cell, and the practicality was explored.
Further, the stirring time in the second step is 0.5h-0.7 h.
Further, in the third step, phosphoric acid solution is adopted to soak the organic precursor, the suction filtration time is 10min to 30min, and the organic precursor after suction filtration is placed in an oven at 90 ℃ to 120 ℃ to be dried for 4h to 6 h.
Furthermore, the temperature rise rate of the calcination in the fourth step is 3-5 ℃/min, the calcination temperature is 400-800 ℃, and the calcination time is 0.5-3.5 h.
Further, the water washing liquid in the fifth step is a dilute hydrochloric acid solution with the mass fraction of 5% -8%.
Furthermore, the mass ratio of nitrogen element to carbon element in the heteroatom-doped hard carbon material in the fifth step is 1: 3.
Further, in the sixth step, a scanning electron microscope and a transmission electron microscope are adopted to observe the change of the appearance of the heteroatom-doped hard carbon material, and the change of the structure and the interlayer spacing of the carbon is researched by adopting X-ray diffraction.
Further, in the sixth step, the specific surface area and the pore structure distribution are obtained through a nitrogen adsorption and desorption experiment, and the change of the functional group is obtained through an infrared absorption spectrometer.
And further, assembling the active material and the polyvinylidene fluoride mixture to form a button cell and a cylindrical cell in the seventh step.
3. Advantageous effects
Compared with the prior art, the invention has the advantages that:
according to the scheme, the heteroatom-doped hard carbon material can be obtained by adopting bacterial cellulose and urea as raw materials and through the processes of dissolving with an organic solvent, heating, precursor preparation, carbonization and the like, and the biomass material derived carbon has larger interlayer spacing and improves the ion diffusion capacity; the carbon material has abundant functional groups, provides pseudocapacitance ratio, can be efficiently hybridized with a carbon matrix by doping nitrogen atoms, enables the carbon layer to be distorted, changes electron arrangement, effectively improves the conductivity of the carbon material, and has wide raw material sources and low manufacturing cost.
Drawings
Fig. 1 is a flow chart of a method for preparing a heteroatom-doped hard carbon material according to the present invention.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention; it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and all other embodiments obtained by those skilled in the art without any inventive work are within the scope of the present invention.
Example 1:
a heteroatom-doped hard carbon material comprises the following raw materials: a g of urea, 2.5a-3.5a g of bacterial cellulose, 1.1a-1.6a g of resorcinol and 0.1-0.2a ml of ethylenediamine solution with the mass fraction of 60-80%.
Example 2:
referring to fig. 1, a method for preparing a heteroatom-doped hard carbon material includes the following steps:
step one, preparing a solvent: sequentially mixing 1.1a-1.6a g of resorcinol, 3a-3.5a ml of water and 0.1-0.2a ml of ethylenediamine solution with the mass fraction of 60-80% in a reaction vessel, and stirring to prepare a strong polar organic solvent;
dissolving in a second step: and (2) dissolving 2.5a-3.5a g of bacterial cellulose into the organic solvent in the step (1), and continuously stirring or carrying out ultrasonic treatment until the bacterial cellulose is completely dissolved to obtain a uniform suspension, wherein the stirring time is 0.5-0.7 h.
Step three, precursor preparation: stirring and dissolving a g of urea into the suspension obtained in the step two, placing the suspension in heating equipment, continuously heating and reacting under the protection of argon, circularly filtering, washing, and finally drying to obtain nitrogen-doped precursor powder;
wherein, the organic precursor is soaked by phosphoric acid solution, the suction filtration time is 10min-30min, and the organic precursor after suction filtration is placed in an oven with the temperature of 90-120 ℃ for drying for 4h-6 h.
Step four, carbonizing: and (3) placing the precursor powder in the third step into a calcining device, and carrying out high-temperature carbonization under the protection of argon, wherein the calcining heating rate is 3-5 ℃/min, the calcining temperature is 400-800 ℃, and the calcining time is 0.5-3.5 h.
Step five, washing: washing and filtering the carbonized material obtained in the fourth step to be neutral, and drying to obtain a heteroatom-doped hard carbon material;
wherein the water washing liquid is a dilute hydrochloric acid solution with the mass fraction of 5% -8%, and the mass ratio of nitrogen elements to carbon elements in the heteroatom-doped hard carbon material is 1: 3.
And six steps of characterization observation: observing the change of the appearance of the heteroatom-doped hard carbon material, researching the change of the structure and the interlayer spacing of carbon, and researching the distribution of the specific surface area and the pore structure and the change of functional groups;
wherein, the change of the appearance of the heteroatom-doped hard carbon material is observed by adopting a scanning electron microscope and a transmission electron microscope, and the change of the structure and the interlayer spacing of the carbon is researched by adopting X-ray diffraction.
Step seven, electrochemical evaluation: assembling a button cell, evaluating the performance of an active material, assembling the button cell into a cylindrical cell, and exploring practicability;
wherein, the button cell and the cylindrical cell are formed by active materials and polyvinylidene fluoride mixed materials.
To sum up: the heteroatom-doped hard carbon material can be obtained by adopting bacterial cellulose and urea as raw materials and through the processes of dissolving with an organic solvent, heating, precursor preparation, carbonization and the like, and the derived carbon of the biomass material has larger interlayer spacing, so that the ion diffusion capacity of the wheel is improved; the carbon material has abundant functional groups, provides pseudocapacitance ratio, can be efficiently hybridized with a carbon matrix by doping nitrogen atoms, enables the carbon layer to be distorted, changes electron arrangement, effectively improves the conductivity of the carbon material, and has wide raw material sources and low manufacturing cost.
The foregoing is only a preferred embodiment of the present invention; the scope of the invention is not limited thereto. Any person skilled in the art should be able to cover the technical scope of the present invention by equivalent or modified solutions and modifications within the technical scope of the present invention.
Claims (10)
1. A heteroatom-doped hard carbon material, characterized in that: comprises the following raw materials: a g of urea, 2.5a-3.5a g of bacterial cellulose, 1.1a-1.6a g of resorcinol and 0.1-0.2a ml of ethylenediamine solution with the mass fraction of 60-80%.
2. A preparation method of a heteroatom-doped hard carbon material is characterized by comprising the following steps: the method comprises the following steps:
step one, preparing a solvent: sequentially mixing 1.1a-1.6a g of resorcinol and 0.1-0.2a ml of ethylenediamine solution with the mass fraction of 60-80% in a reaction vessel, and stirring to prepare a strong polar organic solvent;
dissolving in a second step: dissolving 2.5a-3.5a grams of bacterial cellulose into the organic solvent in the step 1, and continuously stirring or carrying out ultrasonic treatment until the bacterial cellulose is completely dissolved to form uniform suspension;
step three, precursor preparation: stirring and dissolving a g of urea into the suspension obtained in the step two, placing the suspension in heating equipment, continuously heating and reacting under the protection of argon, circularly filtering, washing, and finally drying to obtain nitrogen-doped precursor powder;
step four, carbonizing: putting the precursor powder in the third step into a calcining device, and carrying out high-temperature carbonization under the protection of argon;
step five, washing: and (5) washing and filtering the carbonized material obtained in the fourth step to be neutral, and drying to obtain the heteroatom-doped hard carbon material.
And six steps of characterization observation: observing the change of the appearance of the heteroatom-doped hard carbon material, researching the change of the structure and the interlayer spacing of the carbon, and researching the distribution of the specific surface area and the pore structure and the change of the functional group.
Step seven, electrochemical evaluation: the button cell was assembled, the performance of the active material was evaluated, and then assembled into a cylindrical cell, and the practicality was explored.
3. The method for preparing heteroatom-doped hard carbon material as claimed in claim 2, wherein the method comprises the following steps: and the stirring time in the second step is 0.5-0.7 h.
4. The method for preparing heteroatom-doped hard carbon material as claimed in claim 2, wherein the method comprises the following steps: and in the third step, the organic precursor is soaked in phosphoric acid solution, the suction filtration time is 10min-30min, and the suction-filtered organic precursor is placed in an oven at the temperature of 90-120 ℃ for drying for 4h-6 h.
5. The method for preparing heteroatom-doped hard carbon material as claimed in claim 2, wherein the method comprises the following steps: the temperature rise rate of the calcination in the fourth step is 3-5 ℃/min, the calcination temperature is 400-800 ℃, and the calcination time is 0.5-3.5 h.
6. The method for preparing heteroatom-doped hard carbon material as claimed in claim 2, wherein the method comprises the following steps: and the water washing liquid in the fifth step is a dilute hydrochloric acid solution with the mass fraction of 5% -8%.
7. The method for preparing heteroatom-doped hard carbon material as claimed in claim 2, wherein the method comprises the following steps: and the mass ratio of nitrogen elements to carbon elements in the heteroatom-doped hard carbon material in the step five is 1: 3.
8. The method for preparing heteroatom-doped hard carbon material as claimed in claim 2, wherein the method comprises the following steps: and sixthly, observing the change of the appearance of the heteroatom-doped hard carbon material by adopting a scanning electron microscope and a transmission electron microscope, and researching the change of the structure and the interlayer spacing of the carbon by adopting X-ray diffraction.
9. The method for preparing heteroatom-doped hard carbon material as claimed in claim 2, wherein the method comprises the following steps: and in the sixth step, the specific surface area and the pore structure distribution are obtained through a nitrogen adsorption and desorption experiment, and the change of the functional group is obtained through an infrared absorption spectrometer.
10. The method for preparing heteroatom-doped hard carbon material as claimed in claim 2, wherein the method comprises the following steps: and step seven, assembling the active material and the polyvinylidene fluoride mixed material to form the button cell and the cylindrical cell.
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US20090309072A1 (en) * | 2008-06-13 | 2009-12-17 | Shiaw-Min Hwang | Bacterial cellulose film and carbon nanotubes-like thin film structures developed from bacterial cellulose |
CN105390672A (en) * | 2015-10-21 | 2016-03-09 | 天津大学 | Preparation method for three-dimensional nitrogen-doped mesoporous carbon ultra-thin nanosheet material |
US20170221646A1 (en) * | 2016-02-01 | 2017-08-03 | Taiwan Carbon Nano Technology Corporation | Nitrogen-containing porous carbon material, and capacitor and manufacturing method thereof |
CN112850708A (en) * | 2021-03-05 | 2021-05-28 | 中国海洋大学 | Preparation method and application of nitrogen-doped porous carbon material with high specific surface area |
CN113206246A (en) * | 2021-04-27 | 2021-08-03 | 天津理工大学 | Biomass hard carbon negative electrode material of sodium ion battery and preparation method thereof |
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US20090309072A1 (en) * | 2008-06-13 | 2009-12-17 | Shiaw-Min Hwang | Bacterial cellulose film and carbon nanotubes-like thin film structures developed from bacterial cellulose |
CN105390672A (en) * | 2015-10-21 | 2016-03-09 | 天津大学 | Preparation method for three-dimensional nitrogen-doped mesoporous carbon ultra-thin nanosheet material |
US20170221646A1 (en) * | 2016-02-01 | 2017-08-03 | Taiwan Carbon Nano Technology Corporation | Nitrogen-containing porous carbon material, and capacitor and manufacturing method thereof |
CN107021468A (en) * | 2016-02-01 | 2017-08-08 | 台湾奈米碳素股份有限公司 | Nitrogen-containing porous carbon material, capacitor and manufacturing method thereof |
CN112850708A (en) * | 2021-03-05 | 2021-05-28 | 中国海洋大学 | Preparation method and application of nitrogen-doped porous carbon material with high specific surface area |
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Application publication date: 20211210 |