CN115881445A - Preparation method and application of N/P co-doped carbon nanocage - Google Patents
Preparation method and application of N/P co-doped carbon nanocage Download PDFInfo
- Publication number
- CN115881445A CN115881445A CN202310032804.9A CN202310032804A CN115881445A CN 115881445 A CN115881445 A CN 115881445A CN 202310032804 A CN202310032804 A CN 202310032804A CN 115881445 A CN115881445 A CN 115881445A
- Authority
- CN
- China
- Prior art keywords
- doped carbon
- basic copper
- copper carbonate
- carbonate
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 51
- 239000002091 nanocage Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229940116318 copper carbonate Drugs 0.000 claims abstract description 39
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims abstract description 39
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 24
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 17
- 239000002608 ionic liquid Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000376 reactant Substances 0.000 claims abstract description 14
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000010000 carbonizing Methods 0.000 claims abstract description 5
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 24
- 239000003990 capacitor Substances 0.000 claims description 22
- 239000011148 porous material Substances 0.000 claims description 11
- -1 1-ethyl-3-methylimidazolium hexafluorophosphate Chemical compound 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 14
- 239000003575 carbonaceous material Substances 0.000 abstract description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 10
- 239000012190 activator Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000004146 energy storage Methods 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 6
- 238000001994 activation Methods 0.000 abstract description 5
- 239000001569 carbon dioxide Substances 0.000 abstract description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 5
- 230000004913 activation Effects 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract description 3
- 239000005751 Copper oxide Substances 0.000 abstract description 3
- 229910000431 copper oxide Inorganic materials 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 3
- 150000004706 metal oxides Chemical class 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000010405 anode material Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000007833 carbon precursor Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a preparation method and application of an N/P co-doped carbon nanocage, and relates to the technical field of carbon material preparation and energy storage. The method comprises the following steps: uniformly mixing a copper chloride solution and a potassium carbonate solution, heating, filtering and drying to obtain the basic copper carbonate; mixing anthracene oil, the basic copper carbonate, ionic liquid and N, N-dimethylformamide uniformly to obtain a reactant; and carbonizing the reactant to obtain the N/P co-doped carbon nanocage. According to the method, cheap copper chloride and potassium carbonate are used as raw materials to prepare the basic copper carbonate, an expensive metal oxide template and an alkaline activator are replaced, corrosion to equipment in the using process of the alkaline activator is avoided, carbon dioxide generated by decomposition of the basic copper carbonate can be used as the activator to carry out physical activation, and copper oxide is used as the template to form a cage-shaped structure, so that storage and transmission of electrolyte ions are facilitated.
Description
Technical Field
The invention relates to the technical field of carbon material preparation and energy storage, in particular to a preparation method and application of an N/P co-doped carbon nanocage.
Background
With the consumption of fossil fuels, carbon dioxide is discharged, a greenhouse effect is formed, glaciers are melted, the sea level rises, and the phenomenon prompts people to develop new energy sources and further reduce the emission of carbon dioxide. However, the development of new energy needs energy storage and conversion devices, which are lithium ion batteries, and the price of lithium sources is rising and the storage capacity is low, so that the development of cheap energy storage devices is urgently needed. As one of the most promising energy storage devices, the zinc-ion hybrid capacitor organically combines the advantages of high energy density of zinc-ion battery and long cycle life and high power density of super capacitor, however, the performance of the positive electrode material (such as carbon material, metal material, conductive polymer) limits its application area. As a cheap anode material, the precursor for preparing the carbon material comprises chemical byproducts, biomass, polymers and the like, and the chemical byproducts are used as carbon sources, so that the pollution to the environment can be reduced, and the high-added-value utilization of the carbon material can be realized. However, the use of a nano metal oxide template in the preparation of the carbon material results in high material cost, and the use of a strong base as an activator causes corrosion of equipment. In addition, the porous carbon material has lower conductivity than the graphene material.
Disclosure of Invention
The invention aims to provide a preparation method and application of an N/P co-doped carbon nanocage, wherein cheap copper chloride and potassium carbonate are used as raw materials to prepare basic copper carbonate which is used as a domain-limited template and an activating agent, anthracene oil is used as a carbon precursor, ionic liquid (1-ethyl-3-methylimidazolium hexafluorophosphate) is used as an N and P doping agent, and the N/P co-doped carbon nanocage is prepared through high-temperature carbonization and activation processes; as the positive electrode material of the zinc ion mixed capacitor, excellent zinc ion storage performance is obtained.
In order to achieve the purpose, the invention provides the following scheme:
according to one technical scheme of the invention, the N/P co-doped carbon nanocage has the N content of 2.6-4.2 at%, the P content of 1.7-2.1 at%, the average pore diameter of 2.5-3.1 nm and the specific surface area of 1200-2400 m 2 Per g, total pore volume of 0.9-1.6 cm 3 Per g, the pore volume of the micropores is 0.3-0.7 cm 3 /g。
According to the second technical scheme, the preparation method of the N/P co-doped carbon nanocage comprises the following steps:
step 1, preparing basic copper carbonate: uniformly mixing a copper chloride solution and a potassium carbonate solution, heating, filtering and drying to obtain the basic copper carbonate;
step 2, pretreatment of reactants: mixing anthracene oil, the basic copper carbonate, ionic liquid and N, N-dimethylformamide uniformly to obtain a reactant;
step 3, preparation of N/P co-doped carbon nanocages: and carbonizing the reactant to obtain the N/P co-doped carbon nanocage.
Further, in the step 1, the concentrations of the copper chloride solution and the potassium carbonate solution are both 0.1-0.5 mol/L; the mass ratio of the copper chloride to the potassium carbonate is 1; the heating temperature is 40-80 ℃ and the time is 12h.
Further, in the step 2, the mass ratio of the anthracene oil to the basic copper carbonate is 1; the basic copper carbonate accounts for 4/7-8/11 of the total mass of the anthracene oil, the basic copper carbonate and the ionic liquid; the N, N-dimethylformamide is used in such a way that anthracene oil, basic copper carbonate and the ionic liquid can be uniformly mixed in a liquid state.
Further, in step 2, the ionic liquid is 1-ethyl-3-methylimidazole hexafluorophosphate.
Further, in step 3, the carbonization treatment specifically comprises: heating from room temperature to 200 deg.C at a heating rate of 2 deg.C/min, maintaining for 1h, heating to 850-1050 deg.C at a heating rate of 5 deg.C/min, and maintaining for 1h.
The reason why the present invention is limited to heating from room temperature to 200 ℃ at a heating rate of 2 ℃/min for 1 hour is that: the decomposition temperature of the basic copper carbonate is 200 ℃, decomposition can occur beyond the temperature, and the temperature is mainly kept to uniformly mix the raw materials.
The reason why the invention limits the heating to 850-1050 ℃ at the heating rate of 5 ℃/min and keeping the temperature for 1h is that: outside this temperature range, the pore structure is affected, as well as changes in the thermostatting time. In a preferred embodiment of the invention, the heating is carried out at a heating rate of 5 ℃/min to 950 ℃ and the temperature is kept constant for 1h.
Further, the step 3 of carbonizing also comprises the steps of acid washing, drying, grinding and sieving.
In the third technical scheme of the invention, the N/P co-doped carbon nanocage is applied to a zinc ion hybrid capacitor.
In the fourth technical scheme of the invention, the anode material of the zinc ion hybrid capacitor comprises the N/P co-doped carbon nanocage.
According to the method, cheap copper chloride and potassium carbonate are used as raw materials to prepare basic copper carbonate as a limited-domain template and an activating agent, anthracene oil is used as a raw material (carbon precursor), ionic liquid (1-ethyl-3-methylimidazole hexafluorophosphate) is used as N and P doping agents, aromatic hydrocarbon in the anthracene oil is coated on the surface of a self-made basic copper carbonate template along with the rise of temperature, carbon dioxide and water vapor generated by the decomposition of the basic copper carbonate play a role in activating, cutting and pore-forming (play a role in physical activation) along with the rise of temperature to form a hierarchical pore structure, and a cage-shaped structure is formed under the effect of a copper oxide template; in addition, the ionic liquid (1-ethyl-3-methylimidazolium hexafluorophosphate) is decomposed to generate N and P dopants, carbon atoms in a carbon matrix are replaced, N/P heteroatoms are introduced, and after acid washing and drying, N/P co-doped carbon nanocages are obtained and applied to zinc ion hybrid capacitors to study the structure-activity relationship.
The invention discloses the following technical effects:
1. according to the method, cheap copper chloride and potassium carbonate are used as raw materials to prepare the basic copper carbonate, an expensive metal oxide template and an alkaline activator are replaced, corrosion to equipment in the using process of the alkaline activator is avoided, carbon dioxide generated by decomposition of the basic copper carbonate can be used as the activator to carry out physical activation, and copper oxide is used as the template to form a cage-shaped structure, so that storage and transmission of electrolyte ions are facilitated.
2. According to the invention, anthracene oil rich in polycyclic aromatic hydrocarbon is used as a carbon source, the raw material is cheap and easy to obtain, the N/P co-doped carbon nanosheets for the zinc ion hybrid capacitor are directly prepared by adopting a simple one-step carbonization and activation method, the process is simple, and the high added value utilization of the anthracene oil which is a chemical byproduct is realized.
3. The N/P co-doped carbon nanocage prepared by the method has high specific surface area which can reach 2317.6m 2 (iv) g. When the N/P co-doped carbon nanocage prepared by the invention is used as the anode material of a zinc ion hybrid capacitor, the concentration of Zn (ClO) is 1mol/L 4 ) 2 In the water-based electrolyte, when the current density is 0.5A/g, the capacity can reach 149.8mAh/g; when the current density is 20A/g, the capacity can reach 83.9mAh/g; at a current density of 3A/g, the capacity retention rate after 15000 cycles can be 96.4%, the coulombic efficiency is 99.7%, and high specific volume and excellent cycle life are shown.
4. The N/P co-doped carbon nanocage prepared by the invention has the advantages of low cost and easy operation, in addition, the cage-shaped structure can be used as an electrolyte tank to store electrolyte ions, the transmission of electrons is accelerated, and the introduction of N and P heteroatoms enhances the adsorption capacity of the electrolyte ions, thereby improving the electrochemical performance of the zinc ion hybrid capacitor.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required in the embodiments will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a nitrogen adsorption and desorption isotherm of the N/P co-doped carbon nanocages prepared in examples 1 to 3 of the present invention.
Fig. 2 is a transmission electron micrograph of the N/P co-doped carbon nanocage prepared in example 2 of the present invention.
FIG. 3 shows that the N/P co-doped carbon nanocage electrode material prepared in examples 1-3 of the present invention is 1mol/L Zn (ClO) 4 ) 2 The capacity of the zinc ion hybrid capacitor in the electrolyte is plotted as a function of current density.
Fig. 4 is a cycle stability test of a zinc ion hybrid capacitor assembled by N/P co-doped carbon nanocages prepared in example 2 of the present invention.
Fig. 5 is a field emission scanning electron microscope image of basic copper carbonate prepared in step 1 of example 2 of the present invention.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but rather as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the documents are cited. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including but not limited to.
In the present invention, "%" is in terms of atomic percent unless otherwise specified.
The "room temperature" in the present invention means 20 to 30 ℃ unless otherwise specified.
The ionic liquid used in the examples of the present invention is 1-ethyl-3-methylimidazolium hexafluorophosphate.
Example 1N/P Co-doped carbon nanocage NP-CN 850 The specific preparation process comprises the following steps:
(1) Preparation of basic copper carbonate: respectively preparing copper chloride and potassium carbonate into 0.1mol/L solution, then mixing according to the mass ratio of the copper chloride to the potassium carbonate of 0.5; obtaining basic copper carbonate;
(2) Pretreatment of reactants: weighing anthracene oil, basic copper carbonate and ionic liquid according to a mass ratio of 1;
(3) Preparing an N/P co-doped carbon nanocage: and (3) putting the reactant obtained in the step (2) into a magnetic boat, then putting the magnetic boat in the center of a tube furnace, heating to 200 ℃ from room temperature at the heating rate of 2 ℃/min, keeping for 1h, then heating to 850 ℃ at the heating rate of 5 ℃/min, keeping for 1h, cooling to room temperature, and then carrying out acid washing, drying, grinding and sieving on the product to obtain the carbon material. I.e., N/P co-doped carbon nanocagesIs named NP-CN 850 The XPS test results show that the N content is 2.68% and the P content is 1.78%. NP-CN 850 When the zinc ion mixed capacitor anode material is used as a zinc ion mixed capacitor anode material, the concentration of Zn (ClO) is 1mol/L 4 ) 2 NP-CN at a current density of 0.5A/g in the electrolyte 850 The capacity of the energy-saving material reaches 74.9mAh/g, and the energy density is 66.7Wh/kg; NP-CN at a current density of 20A/g 850 The capacity of the composite material reaches 35.5mAh/g, and the energy density is 66.7Wh/kg.
Example 2: N/P co-doped carbon nanocage NP-CN 950 The specific preparation process comprises the following steps:
(1) Preparation of basic copper carbonate: respectively preparing 0.3mol/L solution of copper chloride and potassium carbonate, mixing according to the mass ratio of the copper chloride to the potassium carbonate being 1, heating in a water bath at 60 ℃ for 12 hours, and filtering and drying after the reaction is finished; obtaining basic copper carbonate;
(2) Pretreatment of reactants: weighing anthracene oil, basic copper carbonate and ionic liquid according to the mass ratio of 1;
(3) Preparing an N/P co-doped carbon nanocage: and (3) putting the reactant obtained in the step (2) into a magnetic boat, then putting the magnetic boat in the center of a tube furnace, heating the magnetic boat from room temperature to 200 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 1h, then heating the magnetic boat to 950 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 1h, cooling the heated magnetic boat to room temperature, and then carrying out acid washing, drying, grinding and sieving on the product to obtain the carbon material. Namely, N/P co-doped carbon nano cage is named as NP-CN 950 The XPS test result shows that the N content is 4.18 percent and the P content is 2.01 percent. NP-CN 950 When the zinc ion mixed capacitor anode material is used as a zinc ion mixed capacitor anode material, the concentration of Zn (ClO) is 1mol/L 4 ) 2 In the aqueous electrolyte, when the current density is 0.5A/g, the capacity is 149.8mAh/g, and the energy density is 133.3Wh/kg; when the current density is 20A/g, the capacity reaches 83.9mAh/g, and the energy density is 47.1Wh/kg; under the current density of 3A/g, the capacity retention rate is 96.4 percent and the coulombic efficiency is 99.7 percent after 15000 cycles.
Example 3: N/P codoped carbon nanocage NP-CN 1050 The specific preparation process comprises the following steps:
(1) Preparation of basic copper carbonate: respectively preparing 0.5mol/L solution of copper chloride and potassium carbonate, mixing according to the mass ratio of the copper chloride to the potassium carbonate being 1; obtaining basic copper carbonate;
(2) Pretreatment of reactants: weighing anthracene oil, basic copper carbonate and ionic liquid according to the mass ratio of 1;
(3) Preparing an N/P co-doped carbon nanocage: and (3) putting the reactant obtained in the step (2) into a magnetic boat, then putting the magnetic boat in the center of a tube furnace, heating the magnetic boat from room temperature to 200 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 1h, then heating the magnetic boat to 1050 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 1h, cooling the heated magnetic boat to room temperature, and then carrying out acid washing, drying, grinding and sieving on the product to obtain the carbon material. Namely, N/P co-doped carbon nano cage is named as NP-CN 1050 The XPS test result shows that the N content is 3.25 percent and the P content is 1.87 percent. NP-CN 1050 When the zinc oxide is used as a positive electrode material of a zinc ion hybrid capacitor, the concentration of Zn (ClO) is 1mol/L 4 ) 2 NP-CN at a current density of 0.5A/g in the electrolyte 850 The capacity of the energy-saving device reaches 99.2mAh/g, and the energy density is 99.3Wh/kg; NP-CN at a current density of 20A/g 850 The capacity of the energy storage battery reaches 50.1mAh/g, and the energy density is 28.2Wh/kg.
The N/P co-doped carbon nanocages prepared in examples 1 to 3 were used as test samples to determine pore structure parameters, respectively. The results are shown in fig. 1 (nitrogen adsorption and desorption isotherms of the N/P co-doped carbon nanocages prepared in examples 1 to 3) and table 1:
TABLE 1 parameters of pore structure of N/P co-doped carbon nanocages
As shown in Table 1 and the results of FIG. 1, the specific surface area of the N/P co-doped carbon nanocage prepared by the method is 1278.8-2317.6m 2 Per gram, the total pore volume is between 0.95 and 1.54cm 3 Between/g, has high specific surface area (up to 2317.6m 2 /g), a rich multiple pore structure for ion adsorption and transport.
Fig. 2 is a transmission electron micrograph of the N/P co-doped carbon nanocages prepared in example 2. As can be seen from fig. 2, the N/P co-doped carbon nanocage prepared in example 2 is a cage-like structure, the cage-like structure is conducive to storage and rapid transmission of electrolyte ions, and the cages are connected to each other to achieve rapid conduction of electrons.
FIG. 3 shows that the N/P co-doped carbon nanocage electrode material prepared in examples 1-3 of the present invention is 1mol/L Zn (ClO) 4 ) 2 The capacity of the zinc ion hybrid capacitor in the electrolyte is plotted as a function of current density. As can be seen from fig. 3, the N/P co-doped carbon nanocage electrode material prepared in embodiments 1 to 3 of the present invention has a high specific volume when used as an anode material of a zinc ion hybrid capacitor.
Fig. 4 is a cycle stability test of a zinc ion hybrid capacitor assembled by the N/P co-doped carbon nanocages prepared in example 2 of the present invention. As shown in the experimental results of FIG. 4, it is understood that the N/P co-doped carbon nanocage prepared in example 2 of the present invention is 1mol/LZn (ClO) when it is used as a positive electrode material of a zinc ion hybrid capacitor 4 ) 2 In the aqueous electrolyte, the capacity retention ratio was 96.4% and the coulombic efficiency was 99.7% after 15000 cycles at a current density of 3A/g, indicating an excellent cycle life.
Fig. 5 is a field emission scanning electron microscope image of basic copper carbonate prepared in step 1 of example 2 of the present invention. As can be seen from fig. 5, basic copper carbonate prepared in example 2 of the present invention is a nano-scale capsule structure.
Comparative example 1
The only difference from example 2 is that step 1 is omitted and the basic copper carbonate in step 2 is replaced by basic copper carbonate obtained commercially (green amorphous powder, insoluble in water and ethanol, soluble in dilute acid and aqueous ammonia).
The N/P co-doped carbon material prepared by the comparative example is of a sheet structure, and is 1mol/L when used as a positive electrode material of a zinc ion hybrid capacitorZn(ClO 4 ) 2 In the aqueous electrolyte, when the current density is 0.5A/g, the capacity is 95.3mAh/g, and the energy density is 84.9Wh/kg; when the current density is 20A/g, the capacity is 42.1mAh/g, and the energy density is 23.7Wh/kg; under the current density of 3A/g, the capacity retention rate is 88.9 percent and the coulombic efficiency is 95.3 percent after 15000 cycles.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (9)
1. The N/P co-doped carbon nanocage is characterized in that the N content in the N/P co-doped carbon nanocage is 2.6-4.2 at%, the P content is 1.7-2.1 at%, the average pore diameter is 2.5-3.1 nm, and the specific surface area is 1200-2400 m 2 Per g, total pore volume of 0.9-1.6 cm 3 Per g, the pore volume of the micropores is 0.3-0.7 cm 3 /g。
2. The preparation method of the N/P co-doped carbon nanocage according to claim 1, which comprises the following steps:
step 1, preparing basic copper carbonate: uniformly mixing a copper chloride solution and a potassium carbonate solution, heating, filtering and drying to obtain the basic copper carbonate;
step 2, pretreatment of reactants: mixing anthracene oil, the basic copper carbonate, ionic liquid and N, N-dimethylformamide uniformly to obtain a reactant;
step 3, preparation of N/P codoped carbon nanocages: and carbonizing the reactant to obtain the N/P co-doped carbon nanocage.
3. The preparation method according to claim 2, wherein in step 1, the concentrations of the copper chloride solution and the potassium carbonate solution are both 0.1-0.5 mol/L; the mass ratio of the copper chloride to the potassium carbonate is 1; the heating temperature is 40-80 ℃ and the time is 12h.
4. The preparation method according to claim 2, wherein in the step 2, the mass ratio of the anthracene oil to the basic copper carbonate is 1; the basic copper carbonate accounts for 4/7-8/11 of the total mass of the anthracene oil, the basic copper carbonate and the ionic liquid; the dosage of the N, N-dimethylformamide is that the anthracene oil, the basic copper carbonate and the ionic liquid can be uniformly mixed in a liquid state.
5. The method according to claim 2, wherein in step 2, the ionic liquid is 1-ethyl-3-methylimidazolium hexafluorophosphate.
6. The method according to claim 2, wherein in step 3, the carbonization treatment is specifically: heating from room temperature to 200 deg.C at a heating rate of 2 deg.C/min, maintaining for 1h, heating to 850-1050 deg.C at a heating rate of 5 deg.C/min, and maintaining for 1h.
7. The method according to claim 2, wherein the carbonizing step in step 3 further comprises pickling, drying, grinding, and sieving.
8. The use of the N/P co-doped carbon nanocage of claim 1 in a zinc ion hybrid capacitor.
9. A zinc ion hybrid capacitor, wherein the positive electrode material comprises the N/P co-doped carbon nanocage according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310032804.9A CN115881445A (en) | 2023-01-10 | 2023-01-10 | Preparation method and application of N/P co-doped carbon nanocage |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310032804.9A CN115881445A (en) | 2023-01-10 | 2023-01-10 | Preparation method and application of N/P co-doped carbon nanocage |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115881445A true CN115881445A (en) | 2023-03-31 |
Family
ID=85758370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310032804.9A Withdrawn CN115881445A (en) | 2023-01-10 | 2023-01-10 | Preparation method and application of N/P co-doped carbon nanocage |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115881445A (en) |
-
2023
- 2023-01-10 CN CN202310032804.9A patent/CN115881445A/en not_active Withdrawn
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109243853B (en) | Method for preparing high-specific-capacity nano composite material by adopting double templates | |
| CN110467182B (en) | Reaction template-based hierarchical porous carbon-based material and preparation method and application thereof | |
| CN109921041B (en) | Preparation and application of non-noble metal nitrogen-doped hollow carbon nanotube electrocatalyst | |
| CN113054183A (en) | Preparation method of CoNi bimetal organic framework derived carbon-sulfur composite material | |
| Peng et al. | Hierarchically nitrogen-doped mesoporous carbon nanospheres with dual ion adsorption capability for superior rate and ultra-stable zinc ion hybrid supercapacitors | |
| CN112850708A (en) | Preparation method and application of nitrogen-doped porous carbon material with high specific surface area | |
| CN110600713A (en) | Porous carbon doped anode material, preparation method thereof and alkali metal ion battery | |
| CN113707868B (en) | Ternary composite electrode material, preparation method thereof and zinc ion battery | |
| CN109360961B (en) | Hollow composite microsphere for lithium-sulfur battery positive electrode material and preparation method thereof | |
| CN115036516A (en) | Cobalt and nitrogen co-doped hollow tubular porous carbon composite material and preparation method and application thereof | |
| CN113851703A (en) | Polyhydroxy nano material composite solid polymer electrolyte | |
| CN113809286B (en) | Metal Organic Framework (MOF) catalyzed growth carbon nanotube coated nickel-tin alloy electrode material and preparation method and application thereof | |
| CN112320792A (en) | Preparation method of negative electrode material for lithium ion battery and product thereof | |
| CN110482523A (en) | A kind of application in the classifying porous carbon material of N doping and its supercapacitor preparation | |
| CN115881445A (en) | Preparation method and application of N/P co-doped carbon nanocage | |
| CN115224291A (en) | Hollow spherical Fe and N co-doped porous carbon-based catalyst and preparation method and application thereof | |
| CN110589818B (en) | Preparation method and application of nitrogen-doped mesoporous carbon material | |
| CN114105141A (en) | Preparation method and application of oxygen-rich functional group carbon material | |
| CN113072056A (en) | Preparation method of metal organic framework derived carbon with high specific surface area | |
| CN112420401A (en) | Bismuth oxide/manganese oxide composite supercapacitor and preparation method thereof | |
| CN112053858A (en) | Method for preparing zinc ion hybrid capacitor by using acid activated carbon electrode material | |
| CN111653793A (en) | Sea urchin-shaped Ag-doped α -MnO2Catalyst material, preparation method thereof and lithium-air battery | |
| CN114664570B (en) | Preparation method of nitrogen-phosphorus-sulfur co-doped biomass-based porous carbon for zinc ion hybrid capacitor | |
| CN114990565B (en) | Preparation method and application of ruthenium-doped rod-shaped lithium manganese spinel electrocatalyst | |
| CN114188549B (en) | Preparation and application of nitrogen-sulfur-doped cellulose as flexible zinc-air battery electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20230331 |