CN114496597A - Preparation method and application of electron-enhanced carbon nano-net - Google Patents
Preparation method and application of electron-enhanced carbon nano-net Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003990 capacitor Substances 0.000 claims abstract description 25
- 239000002106 nanomesh Substances 0.000 claims abstract description 16
- 239000000376 reactant Substances 0.000 claims abstract description 16
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002019 doping agent Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 10
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 238000007873 sieving Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 17
- 239000011294 coal tar pitch Substances 0.000 claims description 16
- JMTCDHVHZSGGJA-UHFFFAOYSA-M potassium hydrogenoxalate Chemical compound [K+].OC(=O)C([O-])=O JMTCDHVHZSGGJA-UHFFFAOYSA-M 0.000 claims description 16
- 230000004913 activation Effects 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 11
- 229960001484 edetic acid Drugs 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 4
- 238000010000 carbonizing Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000012190 activator Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000011300 coal pitch Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000007833 carbon precursor Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002091 nanocage Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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Abstract
The invention discloses a preparation method and application of an electronic enhanced carbon nano-net, wherein the preparation method and device assembly steps are as follows: s1: preparing a nitrogen-phosphorus dopant; s2: pretreatment of three reactants; s3: transferring the reactant obtained in the step S2 to a magnetic boat of a tube furnace, heating and carbonizing the reactant in an air environment, cooling the reactant to room temperature after the reaction is finished, and stirring, filtering, drying, grinding and sieving the reactant to obtain a three-dimensional electron enhanced carbon nano-mesh; s4: preparing a three-dimensional electron-enhanced carbon nano-mesh electrode; s5: and (5) assembling the zinc ion hybrid capacitor. According to the invention, in the preparation process of the electron-enhanced carbon nano-mesh, the ethylenediamine tetraacetic acid and the dipotassium hydrogen phosphate are reacted to prepare the nitrogen-phosphorus-containing dopant, so that the volatilization of the dopant is reduced, the utilization rate of raw materials is improved, the electron conduction characteristic and the surface wettability of the carbon material are improved by introducing nitrogen-phosphorus heteroatoms, and the prepared three-dimensional electron-enhanced carbon nano-mesh has high specific surface and pore volume.
Description
Technical Field
The invention belongs to the field of carbon material preparation technology and energy storage, and particularly relates to a preparation method and application of a three-dimensional electron-enhanced carbon nano-net.
Background
The zinc ion hybrid capacitor has the advantages of high power density, long cycle life of the super capacitor and high energy density of the zinc ion battery, and becomes the focus of research in the field of energy storage devices. The zinc ion hybrid capacitor is generally composed of a zinc cathode, an anode material, a diaphragm, an electrolyte and the like, and the performance of the anode material determines the final performance of the zinc ion hybrid capacitor. Carbon materials with low price and rich raw materials become hot spots of research, such as Dong and the like which take activated carbon as a positive electrode and ZnSO4The solution is electrolyte, and the Energy density reaches 84Wh/kg (Energy Storage mater, 2018,13,96-102) under the voltage window of 0.2-1.8V; zhu et al, when PPy/PVP is used as a raw material, ZIF-8 is used as a template, KOH is used as an activator, and a carbon material prepared through activation, carbonization and acid washing is used as a positive electrode material of a zinc ion hybrid capacitor, the energy density of the carbon material reaches 107.3Wh/kg (J.Power Sources,2021,506,230224). Although the carbon materials prepared by the above methods all achieve better performance, the market demands are still difficult to meet, and especially the electronic conduction characteristics of the materials need to be further improved.
Chuaiwei et al (201910083852.4) uses sugar as raw material and adopts strong oxidant and FeSO4The carbon microsphere is prepared under the action of the catalyst, and the specific surface area can reach 1430m at most2(ii)/g; schrenergen et al (202010149840.X) prepared coal tar pitch-based carbon materials by chloride salt melting and strong base activation; luxihong et al (202110368028.0) prepared nanocage-derived carbon by adjusting the ratio of coal pitch, metal oxide template and alkali metal hydroxide, and its specific surface area was still below 1700m despite the use of strong base activator2(ii) in terms of/g. In order to further improve the active site of ion adsorption and reduce the use of a metal oxidation template and a strong base activator, the invention takes potassium hydrogen oxalate as an activator, and adopts a nitrogen-phosphorus dopant obtained by ethylenediamine tetraacetic acid and dipotassium hydrogen phosphate to fully utilize polycyclic aromatic hydrocarbons in the coal tar pitch to prepare the high specific surface area (2145.2 m)2/g) and conductivity, compared with the above patent, the invention has greatly improved specific surface area and electrochemical performance without using strong base activator.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: the method is characterized in that polycyclic aromatic hydrocarbons in chemical by-product coal tar are used as a carbon precursor, potassium hydrogen oxalate is used as an activator, and reactants of ethylene diamine tetraacetic acid and potassium hydrogen phosphate are used as nitrogen-phosphorus dopants to directly synthesize the three-dimensional electron-enhanced carbon nano-network.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of a three-dimensional electron-enhanced carbon nano-net comprises the following specific steps:
(1) preparing a nitrogen-phosphorus dopant: adding ethylenediamine tetraacetic acid into water to prepare a solution, adding dipotassium hydrogen phosphate into the solution, filtering after the reaction is finished, and drying at low temperature;
(2) pretreatment of reactants: uniformly mixing the product obtained in the step (1) with potassium hydrogen oxalate and coal tar pitch in a solid state;
(3) preparing a three-dimensional electron-enhanced carbon nano-net: and (3) transferring the reactant obtained in the step (2) to a magnetic boat of a tube furnace, heating the reactant from room temperature to the final activation temperature in an air environment, reacting for a period of time, cooling the reactant to room temperature after the reaction is finished, stirring, filtering, drying, grinding and sieving to obtain the three-dimensional electron enhanced carbon nano-mesh.
Preferably, the mass ratio of the ethylenediaminetetraacetic acid to the potassium hydrogen phosphate is 1/2.
Preferably, the coal tar pitch accounts for 1/8 of the total mass of the mixture of the potassium hydrogen oxalate, the nitrogen-phosphorus dopant and the coal tar pitch, and the mass ratio of the coal tar pitch to the potassium hydrogen oxalate is 1/6.
Preferably, the final activation temperature is 800-1000 ℃, and the reaction time is 1-3 h.
Preferably, in the step (2), the mass of the coal tar pitch is 1g, the mass of the potassium hydrogen oxalate is 6g, and the mass of the nitrogen-phosphorus dopant is 1 g.
An application of a three-dimensional electron-enhanced carbon nano-net in the preparation of a hybrid capacitor comprises the following specific steps:
(a) preparing a three-dimensional electron enhanced carbon nano-mesh electrode: mixing the three-dimensional electronic enhanced carbon nano-net with PTFE emulsion to prepare an electrode slice, drying and weighing;
(b) assembling the zinc ion hybrid capacitor: taking the electrode sheet obtained in the step (a) as a positive electrode, zinc foil as a negative electrode and 1mol/LZn (ClO)4)2The solution is electrolyte, and the paper fiber is diaphragm to assemble the zinc ion hybrid capacitor.
The invention has the following beneficial effects:
1. coal pitch is used as a carbon precursor, raw materials are cheap and easy to obtain, the three-dimensional electron-enhanced carbon nano-mesh is directly prepared by adopting an in-situ activation method, the process is simple, and high value-added utilization of chemical byproducts is realized;
2. cheap potassium hydrogen oxalate is used as an activating agent and a template, so that the corrosion to equipment in the use process of a strong alkali activating agent is avoided, no template agent is used, an acid-free process in the post-treatment process is realized, and the pollution to the environment is reduced;
3. the prepared three-dimensional electron enhanced carbon nano net material has high specific surface area reaching 2145.2m2/g；
4. When the prepared three-dimensional electron enhanced carbon nano-net is used as a positive electrode material of a zinc ion hybrid capacitor, the concentration is 1mol/LZn (ClO)4)2In the aqueous electrolyte, when the current density is 0.1A/g, the capacity is 357.1F/g, and the energy density is up to 158.9 Wh/kg; when the current density is 20A/g, the capacity reaches 256.2F/g, the energy density still reaches 62.3Wh/kg, and high capacity and energy density and excellent rate performance are shown.
Drawings
Fig. 1 is a nitrogen adsorption and desorption isotherm of the three-dimensional electron-enhanced carbon nanomesh prepared in examples 1,2 and 3 of the present invention.
Fig. 2 is a transmission electron micrograph of the three-dimensional electron-enhanced carbon nanoweb prepared in example 2 of the present invention.
FIG. 3 shows that the three-dimensional electron-enhanced carbon nanoweb electrode materials prepared in examples 1,2 and 3 of the invention are 1mol/L Zn (ClO)4)2The capacity of the zinc ion hybrid capacitor in the electrolyte is plotted as a function of current density.
FIG. 4 shows three-dimensional electron-enhanced carbon nanotubes prepared in examples 1,2 and 3 of the present inventionThe mesh electrode material is 1mol/L Zn (ClO)4)2The energy density of the zinc ion hybrid capacitor in the electrolyte is shown as a function of the power density.
Detailed Description
The following examples are included to provide further detailed description of the present invention and to provide those skilled in the art with a more complete, concise, and exact understanding of the principles and spirit of the invention.
Example 1: three-dimensional electron enhanced carbon nano-net 3DCN800The specific preparation process for assembling the zinc ion hybrid capacitor is as follows:
(1) preparing a nitrogen-phosphorus dopant: adding EDTA into water to prepare 1mol/L solution, and weighing dipotassium hydrogen phosphate (K) according to the weight ratio of EDTA substance 1/22HPO4) Adding the mixture into the solution, filtering and drying at low temperature after the reaction is finished to obtain the nitrogen-phosphorus dopant;
(2) pretreatment of reactants: uniformly mixing the nitrogen-phosphorus dopant obtained in the step (1), potassium hydrogen oxalate and coal tar pitch in a solid state; the coal tar pitch accounts for 1/8 of the total mass of the mixture of the potassium hydrogen oxalate, the nitrogen-phosphorus dopant and the coal tar pitch, and the mass ratio of the coal tar pitch to the potassium hydrogen oxalate is 1: 6.
(3) the preparation method of the three-dimensional electron-enhanced carbon nano-net comprises the following steps: and (3) transferring the reactant obtained in the step (2) to a magnetic boat of a tube furnace, heating to a final temperature of 800 ℃ at a heating rate of 2 ℃/min in an air environment, carrying out activation reaction for 2 hours, cooling to room temperature, stirring, filtering, drying, grinding and sieving to obtain the three-dimensional electron enhanced carbon nano-mesh. The obtained three-dimensional electron-enhanced carbon nano-network is named as 3DCN800The XPS test results show that the nitrogen content is 4.28% and the phosphorus content is 3.16%.
(4) Preparing a three-dimensional electron enhanced carbon nano-mesh electrode: mixing the carbon nanosheet obtained in the step (3) with the PTFE emulsion according to the mass ratio of 95:5 to prepare an electrode plate, drying and weighing;
(5) assembling the zinc ion hybrid capacitor: taking the electrode slice obtained in the step (4) as a positive electrode, zinc foil as a negative electrode and 1mol/LZn(ClO4)2The solution is electrolyte and the paper fiber is diaphragm to assemble the zinc ion hybrid capacitor. 3DCN when the current density is 0.1A/g800The capacity of the energy-saving device reaches 209.2F/g, and the energy density is 90.8 Wh/kg; 3DCN at a current density of 20A/g800The capacity of (A) is up to 68.9F/g, and the energy density is 11.2 Wh/kg.
Example 2: three-dimensional electron enhanced carbon nano-net 3DCN900The specific preparation process comprises the following steps:
the same procedures as in steps (1) to (5) in example 1 were carried out except that the final temperature of the activation reaction was 900 ℃ and the reaction time was 1 hour;
the obtained three-dimensional electron-enhanced carbon nano-network is named as 3DCN900The XPS test result shows that the nitrogen content is 6.56 percent and the phosphorus content is 4.12 percent。CNC800When the zinc ion mixed anode material is used as a positive electrode material of a zinc ion mixed capacitor, the concentration of Zn (ClO) is 1mol/L4)23DCN in the electrolyte at a current density of 0.1A/g900The capacity of (A) is 357.1F/g, and the energy density is up to 158.9 Wh/kg; 3DCN at a current density of 20A/g900The capacity of the energy-saving device reaches 256.2F/g, the energy density is 62.3Wh/kg, and the power density is up to 20.35 kW/kg.
Example 3: three-dimensional electron enhanced carbon nano-net 3DCN1000The specific preparation process comprises the following steps:
the same procedures as in steps (1) to (5) in example 1 were carried out except that the final temperature of the activation reaction was 1000 ℃ and the reaction time was 3 hours;
the obtained three-dimensional electron-enhanced carbon nano-network is named as 3DCN1000The nitrogen content was 5.78% and the phosphorus content was 3.56%. 3DCN1000When the zinc ion mixed anode material is used as a positive electrode material of a zinc ion mixed capacitor, the concentration of Zn (ClO) is 1mol/L4)23DCN in the electrolyte at a current density of 0.1A/g1000The capacity of (A) is up to 282.5F/g, and the energy density is 124.8 Wh/kg; 3DCN at a current density of 20A/g1000The capacity of (A) is up to 150.4F/g, and the energy density is 26.4 Wh/kg.
The three-dimensional electron-enhanced carbon nano-mesh prepared in examples 1 to 3 was used as a test sample to measure the pore structure parameters and the elemental composition and content, respectively. The results are shown in tables 1 and 2:
TABLE 1 pore structure parameters of three-dimensional electronically enhanced carbon nanonets
As shown in the results of Table 1 and FIG. 1, the specific surface area of the three-dimensional electron-enhanced carbon nano-network prepared by the invention is 1264.6-2145.2 m2The total pore volume is between 0.73 and 1.23cm3Between/g, a large number of net structures for electron transmission exist in the three-dimensional electron enhanced carbon nano net material, and the three-dimensional electron enhanced carbon nano net material has a high specific surface area of 2145.2m2And/g, provides abundant active sites for the adsorption of ions.
TABLE 2 elemental composition and content of three-dimensional electron-enhanced carbon nanonet
As can be seen from Table 2, the three-dimensional electron-enhanced carbon nano-mesh is directly prepared by using the chemical by-product coal pitch as a carbon source and potassium hydrogen oxalate as an activator and a confinement by using an in-situ activation method, and the method is simple in process and easy to operate. In the preparation process, potassium hydrogen oxalate is used as an activator and a template, the fused ring aromatic hydrocarbon in the coal pitch obtains a network-shaped structure in the polymerization, carbonization and cutting processes, and nitrogen and phosphorus heteroatoms are introduced to provide abundant channels for electron transmission and improve the electron conduction characteristic of the carbon nano-network.
From the experimental results shown in fig. 3 and 4, it is understood that the three-dimensional electron-enhanced carbon nanomesh prepared according to the present invention has a Zn (ClO) of 1mol/L when used as a positive electrode material for a zinc ion hybrid capacitor4)23DCN in the electrolyte at a current density of 0.1A/g900The capacity of (A) is 357.1F/g, and the energy density is up to 158.9 Wh/kg; 3DCN at a current density of 20A/g900The capacity of the material reaches 256.2mAh/g, the energy density is 62.3Wh/kg, the power density is as high as 20.35kW/kg, and the material has high energy density and power density and excellent rate capability.
In the above embodiment, the energy density and the power density of the three-dimensional electron-enhanced carbon nano-network as the positive electrode material of the zinc ion mixed capacitor are superior to those reported in the literature, for example, when the N/P co-doped graphene prepared by Zhao et al (j.power Sources,2022,521,230941) is assembled into a zinc ion mixed capacitor, the energy density and the power density are 94.6Wh/kg and 4.5kW/kg, respectively; the energy density and power density of the N/P co-doped carbon microsphere for the zinc ion hybrid capacitor prepared by Wang et al (J.Alloys Compds.,2022,901,163588) are 54.4Wh/kg and 4kW/kg respectively; yang et al (chem.eng.j.,2022,431,133250) prepared by a two-step process N/S co-doped porous carbon with an energy density and a power density of 106.7Wh/kg and 16kW/kg, respectively, in a zinc-ion hybrid capacitor; xu et al (Carbon,2022,186, 624-.
The above embodiments are only for illustrating the technical idea of the present invention, and the protection scope of the present invention cannot be limited thereby, and any modification made on the basis of the technical scheme according to the technical idea proposed by the present invention falls within the protection scope of the present invention; the technology not related to the invention can be realized by the prior art.
Claims (6)
1. A preparation method of a three-dimensional electron-enhanced carbon nano-net is characterized by comprising the following specific steps:
(1) preparing a nitrogen-phosphorus dopant: adding ethylenediamine tetraacetic acid into water to prepare a solution, adding dipotassium hydrogen phosphate into the solution, filtering after the reaction is finished, and drying at low temperature;
(2) pretreatment of reactants: uniformly mixing the product obtained in the step (1) with potassium hydrogen oxalate and coal tar pitch in a solid state;
(3) preparing a three-dimensional electron-enhanced carbon nano-net: and (3) transferring the reactant obtained in the step (2) to a magnetic boat of a tube furnace, heating the reactant from room temperature to the final activation temperature in an air environment, reacting for a period of time, cooling the reactant to room temperature after the reaction is finished, stirring, filtering, drying, grinding and sieving to obtain the three-dimensional electron enhanced carbon nano-mesh.
2. The method for preparing a three-dimensional electron-enhanced carbon nanonet according to claim 1, wherein: the mass ratio of the ethylene diamine tetraacetic acid to the potassium hydrogen phosphate is 1/2.
3. The method for preparing a three-dimensional electron-enhanced carbon nanoweb according to claim 1, wherein: the coal tar pitch accounts for 1/8 of the total mass of the mixture of the potassium hydrogen oxalate, the nitrogen-phosphorus dopant and the coal tar pitch, and the mass ratio of the coal tar pitch to the potassium hydrogen oxalate is 1/6.
4. The method for preparing a three-dimensional electron-enhanced carbon nanoweb according to claim 1, wherein: the final activation temperature is 800-1000 ℃, and the reaction time is 1-3 h.
5. The method for preparing a three-dimensional electron-enhanced carbon nanoweb according to claim 1, wherein: in the step (2), the mass of the coal tar pitch is 1g, the mass of the potassium hydrogen oxalate is 6g, and the mass of the nitrogen-phosphorus dopant is 1 g.
6. The application of the three-dimensional electron-enhanced carbon nano-net in the preparation of the hybrid capacitor is characterized by comprising the following specific steps of:
(a) preparing a three-dimensional electron enhanced carbon nano-mesh electrode: mixing the three-dimensional electron-enhanced carbon nano-mesh according to any one of claims 1 to 5 with PTFE emulsion to prepare an electrode sheet, drying and weighing;
(b) assembling the zinc ion hybrid capacitor: taking the electrode sheet obtained in the step (a) as a positive electrode, zinc foil as a negative electrode and 1mol/LZn (ClO)4)2The solution is electrolyte, and the paper fiber is diaphragm to assemble the zinc ion hybrid capacitor.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116374996A (en) * | 2023-04-14 | 2023-07-04 | 滁州学院 | Nitrogen-doped carbon quantum dot, preparation method and application thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3431206A (en) * | 1966-04-18 | 1969-03-04 | Monsanto Co | Compositions for and processes of bleaching treated textiles |
| US4675120A (en) * | 1982-12-02 | 1987-06-23 | An-Son Petrochemical, Inc. | Methods of using strong acids modified with acid solutions |
| JP2006321722A (en) * | 2005-05-17 | 2006-11-30 | Nippon Chem Ind Co Ltd | Method for producing barium titanyl oxalate and method for producing barium titanate |
| CN1909128A (en) * | 2005-08-05 | 2007-02-07 | 电源系统株式会社 | Method for conducting electric activation of electric double layer capacitors |
| JP2009167523A (en) * | 2007-12-18 | 2009-07-30 | Hitachi Chem Co Ltd | Conductive substrate for plating, method for manufacturing the same, conductive layer pattern using the same, and method for manufacturing substrate with conductive layer pattern, substrate with conductive layer pattern, and translucent electromagnetic wave shielding member |
| JP6431147B1 (en) * | 2017-08-04 | 2018-11-28 | ヤマトプロテック株式会社 | Electrochemical devices |
| CN110155981A (en) * | 2019-05-23 | 2019-08-23 | 安徽工业大学 | A kind of preparation method of the supercapacitor porous charcoal nanometer sheet of nitrogen sulphur codope |
| WO2019172119A1 (en) * | 2018-03-05 | 2019-09-12 | 株式会社ジェイテクト | Electricity storage device |
| WO2019227169A1 (en) * | 2018-05-31 | 2019-12-05 | The University Of Queensland | Core-shell polymer nanoparticle |
| KR20200092039A (en) * | 2019-01-24 | 2020-08-03 | 한국원자력연구원 | Silver coating particle for removing radioactive iodine and method for removing radioactive iodine using the same |
| CN112374485A (en) * | 2020-11-12 | 2021-02-19 | 滁州学院 | Preparation method of nitrogen-phosphorus double-doped foamy carbon for zinc ion hybrid capacitor |
| CN113948316A (en) * | 2021-05-12 | 2022-01-18 | 滁州学院 | Preparation method and application of three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon |
-
2022
- 2022-02-23 CN CN202210168018.7A patent/CN114496597B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3431206A (en) * | 1966-04-18 | 1969-03-04 | Monsanto Co | Compositions for and processes of bleaching treated textiles |
| US4675120A (en) * | 1982-12-02 | 1987-06-23 | An-Son Petrochemical, Inc. | Methods of using strong acids modified with acid solutions |
| JP2006321722A (en) * | 2005-05-17 | 2006-11-30 | Nippon Chem Ind Co Ltd | Method for producing barium titanyl oxalate and method for producing barium titanate |
| CN1909128A (en) * | 2005-08-05 | 2007-02-07 | 电源系统株式会社 | Method for conducting electric activation of electric double layer capacitors |
| JP2009167523A (en) * | 2007-12-18 | 2009-07-30 | Hitachi Chem Co Ltd | Conductive substrate for plating, method for manufacturing the same, conductive layer pattern using the same, and method for manufacturing substrate with conductive layer pattern, substrate with conductive layer pattern, and translucent electromagnetic wave shielding member |
| JP6431147B1 (en) * | 2017-08-04 | 2018-11-28 | ヤマトプロテック株式会社 | Electrochemical devices |
| WO2019172119A1 (en) * | 2018-03-05 | 2019-09-12 | 株式会社ジェイテクト | Electricity storage device |
| WO2019227169A1 (en) * | 2018-05-31 | 2019-12-05 | The University Of Queensland | Core-shell polymer nanoparticle |
| KR20200092039A (en) * | 2019-01-24 | 2020-08-03 | 한국원자력연구원 | Silver coating particle for removing radioactive iodine and method for removing radioactive iodine using the same |
| CN110155981A (en) * | 2019-05-23 | 2019-08-23 | 安徽工业大学 | A kind of preparation method of the supercapacitor porous charcoal nanometer sheet of nitrogen sulphur codope |
| CN112374485A (en) * | 2020-11-12 | 2021-02-19 | 滁州学院 | Preparation method of nitrogen-phosphorus double-doped foamy carbon for zinc ion hybrid capacitor |
| CN113948316A (en) * | 2021-05-12 | 2022-01-18 | 滁州学院 | Preparation method and application of three-dimensional nitrogen-phosphorus-sulfur-doped honeycomb carbon |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116374996A (en) * | 2023-04-14 | 2023-07-04 | 滁州学院 | Nitrogen-doped carbon quantum dot, preparation method and application thereof |
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