CN116525317A - Boron-nitrogen co-doped dodecahedron layered porous carbon, preparation method thereof and layered porous carbon electrode - Google Patents
Boron-nitrogen co-doped dodecahedron layered porous carbon, preparation method thereof and layered porous carbon electrode Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 64
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 21
- 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 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000003763 carbonization Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 14
- BXYRXXQUTQUQJF-UHFFFAOYSA-N OB(O)O.N.N.N.O.O.O.O Chemical compound OB(O)O.N.N.N.O.O.O.O BXYRXXQUTQUQJF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010000 carbonizing Methods 0.000 claims abstract description 7
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 239000003990 capacitor Substances 0.000 abstract description 29
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 28
- 239000011148 porous material Substances 0.000 abstract description 10
- 239000003575 carbonaceous material Substances 0.000 abstract description 9
- 125000002883 imidazolyl group Chemical group 0.000 abstract description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052796 boron Inorganic materials 0.000 abstract description 7
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 abstract description 3
- 230000003044 adaptive effect Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 description 13
- GKRYSUZXCCOHLM-UHFFFAOYSA-N methyl 2,4-dimethyl-5-oxo-6h-benzo[c][2,7]naphthyridine-1-carboxylate Chemical compound C12=CC=CC=C2NC(=O)C2=C1C(C(=O)OC)=C(C)N=C2C GKRYSUZXCCOHLM-UHFFFAOYSA-N 0.000 description 9
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 239000004246 zinc acetate Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 239000012621 metal-organic framework Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- NTBYNMBEYCCFPS-UHFFFAOYSA-N azane boric acid Chemical group N.N.N.OB(O)O NTBYNMBEYCCFPS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000013183 functionalized metal-organic framework Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention belongs to the technical field of zinc ion mixed capacitors. The invention provides boron-nitrogen co-doped dodecahedron layered porous carbon, a preparation method thereof and a layered porous carbon electrode. According to the invention, 2-methylimidazole, zinc acetate dihydrate and water are mixed and then aged to obtain a zeolite-like imidazole framework material ZIF-8; and (3) mixing ZIF-8 and ammonium borate tetrahydrate, and carbonizing to obtain the boron-nitrogen co-doped dodecahedron layered porous carbon. According to the invention, the zeolite-like imidazole skeleton material ZIF-8 is used as a carbon source, the porous carbon is co-doped with boron and nitrogen by using ammonium borate, a dodecahedron layered porous structure is formed by one-step carbonization, the specific surface area is large, the pore size is adaptive to a zinc ion mixed capacitor, the boron and nitrogen co-doping effect is utilized, the reactive site is increased, and the specific capacity and the cycle performance of the porous carbon material are improved. The layered porous carbon electrode is used as the positive electrode, so that the specific capacity and the cycle performance of the zinc ion mixed capacitor are improved.
Description
Technical Field
The invention relates to the technical field of zinc ion mixed capacitors, in particular to boron-nitrogen co-doped dodecahedron layered porous carbon, a preparation method thereof and a layered porous carbon electrode.
Background
The super capacitor has the characteristics of high power density, good cycling stability, wide temperature adaptability and the like, and is widely applied to the fields of civil electronic equipment, electric vehicles, military and the like, but the super capacitor has low energy density and cannot meet the actual living needs. The zinc ion mixed super capacitor has high theoretical capacity (823 mA.h.g) -1 ) Low oxidation-reduction voltage (-0.76V), abundant zinc source, low cost, safety and no pollution compared with lithium ion, sodium ion and potassium ion.
In the zinc ion hybrid capacitor construction, a porous carbon material is generally used as the positive electrode material. The porous carbon material prepared by taking the metal organic framework material as a template has high specific surface area, porosity and stability, and is considered to be an effective energy storage material. At present, two methods exist for preparing the porous carbon material by taking the metal organic framework as a template, wherein the first method is to calcine the organic carbon source and the metal organic framework together as the template, and the method needs to additionally mix the organic carbon source, and has complex operation and higher cost. The second method is to directly calcine the metal-organic framework as the sole carbon source.
In order to further improve the electrochemical performance of the zinc ion hybrid capacitor, researchers carbonize the functionalized metal-organic framework material to obtain a porous carbon material, but the following problems still exist: 1) The porous carbon material has unsuitable pore size distribution and low zinc ion storage capacity, so that the electrochemical performance of the zinc ion capacitor is not ideal; 2) In order to enhance the porosity of the positive electrode material, a large amount of strong acid and strong alkali are used in the preparation process, and the process is complex and is not friendly to the environment; 3) The electrochemical performance of the assembled zinc ion hybrid capacitor needs to be improved.
Therefore, the boron-nitrogen co-doped dodecahedron layered porous carbon which has stable structure, large specific surface area and pore size distribution and is suitable for zinc ion storage is researched and developed, the electrochemical performance of the zinc ion mixed capacitor is improved, and the boron-nitrogen co-doped dodecahedron layered porous carbon has good prospect.
Disclosure of Invention
The invention aims to provide boron-nitrogen co-doped dodecahedron layered porous carbon, a preparation method thereof and a layered porous carbon electrode.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of boron-nitrogen co-doped dodecahedron layered porous carbon, which comprises the following steps:
1) Mixing 2-methylimidazole, zinc acetate dihydrate and water, and aging to obtain a zeolite-like imidazole framework material ZIF-8;
2) And mixing the zeolite-like imidazole framework material ZIF-8 and ammonium borate tetrahydrate, and carbonizing to obtain the boron-nitrogen co-doped dodecahedron layered porous carbon.
Preferably, the mass ratio of the 2-methylimidazole to the zinc acetate dihydrate in the step 1) is 2-5:1, and the mass volume ratio of the 2-methylimidazole to the water is 10.5-12 g:200mL.
Preferably, the mixing time in the step 1) is 8-12 min; the aging temperature is 20-30 ℃, and the aging time is 20-30 h.
Preferably, the aged product in step 1) is washed and dried sequentially, the washed reagent is water, the washing times are 2-4 times, the single washing time is 2-3 min, the drying temperature is 50-70 ℃, and the drying time is 6-10 h.
Preferably, the mass ratio of the zeolite-like imidazole framework material ZIF-8 to the ammonium borate tetrahydrate in the step 2) is 1:2-6.
Preferably, the carbonization in the step 2) is performed under a protective atmosphere, wherein the protective atmosphere is argon and/or nitrogen; the carbonization temperature is 800-1000 ℃, the rate of heating to the carbonization temperature is 3-5 ℃/min, and the carbonization time is 1-3 h.
The invention also provides the boron-nitrogen co-doped dodecahedron layered porous carbon prepared by the preparation method.
The invention also provides a layered porous carbon electrode containing the boron-nitrogen co-doped dodecahedron layered porous carbon, which comprises the boron-nitrogen co-doped dodecahedron layered porous carbon, a conductive agent and a binder, wherein the mass ratio of the boron-nitrogen co-doped dodecahedron layered porous carbon to the conductive agent to the binder is 6-8:1-2:1-2.
The beneficial effects of the invention include the following points:
1) According to the invention, the zeolite-like imidazole framework material ZIF-8 is used as a carbon source, and metal Zn is evaporated at high temperature in the carbonization process to form a rich micropore structure, so that the specific surface area of the carbon material is increased, and the subsequent step of acid washing and Zn removal is omitted. Ammonium borate is used as a doping agent and a pore-forming agent simultaneously, ammonia gas is released in the high-temperature carbonization process to form a layered porous structure, and the Zn of micropores is eliminated 2+ Transmission restriction, acceleration of Zn 2+ To promote Zn transmission 2+ And the energy density of the zinc ion hybrid capacitor is improved. The boron and nitrogen co-doped porous carbon plays the advantages of the boron and nitrogen co-doping porous carbon, and simultaneously plays the mutual synergistic effect, and the active site of the reaction is increased by utilizing the boron and nitrogen co-doping effect, so that the specific capacity and the cycle performance of the porous carbon material are improved.
2) The invention takes the zeolite-like imidazole framework material ZIF-8 as a carbon source, uses ammonium borate to carry out boron and nitrogen co-doping on porous carbon, prepares the boron and nitrogen co-doped dodecahedron layered porous carbon through one-step carbonization, and has the specific surface area reaching 2670m 2 ·g -1 The microporosity is 45.6%, the mesopore and macroporosity is 54.4%, and the pore size is adapted to the zinc ion mixed capacitor.
3) The boron-nitrogen co-doped layered porous carbon is used as a positive electrode material, and the zinc ion mixed capacitor with zinc foil as a negative electrode has excellent multiplying power performance and cycle performance, and is in a voltage range of 0.2-1.8V and 0.2 A.g -1 The specific capacity is 148.8mAh/g under the current density, and is 20 A.g -1 The specific capacity still can reach 91.8mAh/g under the current density. At 5 A.g -1 Has a capacitance retention of 98.2% after 100000 cycles at a current density of (C) and a reservoirThe efficiency of the solution is kept at 100%, and the solution has excellent cycling stability.
4) According to the invention, the zeolite-like imidazole skeleton material ZIF-8 is obtained through coordination reaction, and water is used for cleaning in the preparation process to replace toxic methanol solution. When boron-nitrogen co-doping is carried out, no additional activator is added, and the carbonized sample is washed by water, so that the pickling and purifying process is omitted. The preparation process is safe, simple to operate and environment-friendly.
Drawings
FIG. 1 is a scanning electron microscope image of boron-nitrogen co-doped dodecahedron layered porous carbon prepared in example 1;
FIG. 2 is an X-ray photoelectron spectrum of boron-nitrogen co-doped dodecahedron layered porous carbon prepared in example 1;
FIG. 3 shows that the zinc ion mixed capacitor prepared in example 1 has a voltage in the range of 0.2 to 1.8V, and 0.2 A.g -1 、0.5A·g -1 、1A·g -1 、2A·g -1 、5A·g -1 、10A·g -1 And 20 A.g -1 A rate performance curve under constant current, wherein I is 0.2 A.g -1 II is 0.5 A.g -1 III is 1A g -1 IV is 2A.g -1 V is 5 A.g -1 VI is 10A.g -1 VII is 20A.g -1 ；
FIG. 4 shows the zinc ion mixed capacitor prepared in example 1 at 5 A.g -1 Cycling performance curve at current density.
Detailed Description
The invention provides a preparation method of boron-nitrogen co-doped dodecahedron layered porous carbon, which comprises the following steps:
1) Mixing 2-methylimidazole, zinc acetate dihydrate and water, and aging to obtain a zeolite-like imidazole framework material ZIF-8;
2) And mixing the zeolite-like imidazole framework material ZIF-8 and ammonium borate tetrahydrate, and carbonizing to obtain the boron-nitrogen co-doped dodecahedron layered porous carbon.
The mass ratio of the 2-methylimidazole to the zinc acetate dihydrate in the step 1) is preferably 2-5:1, more preferably 3-4:1, even more preferably 3.73:1, and the mass volume ratio of the 2-methylimidazole to the water is preferably 10.5-12 g:200mL, more preferably 10.8 to 11.5g:200mL, more preferably 11 to 11.2g:200mL.
The mixing time in step 1) of the present invention is preferably 8 to 12min, more preferably 9 to 11min, and still more preferably 10min; the aging temperature is preferably 20 to 30 ℃, more preferably 22 to 28 ℃, and even more preferably 23 to 25 ℃; the aging time is preferably 20 to 30 hours, more preferably 22 to 28 hours, and still more preferably 24 to 26 hours.
Washing, centrifuging and drying the aged product in step 1) in sequence, wherein the washed reagent is preferably water, the washing times are preferably 2-4 times, more preferably 3 times, the time of single washing is preferably 2-3 min, and the rotating speed of the centrifuging is preferably 6500-7500 rpm, more preferably 6800-7200 rpm, more preferably 7000rpm; the drying temperature is preferably 50 to 70 ℃, more preferably 55 to 65 ℃, still more preferably 60 ℃, and the drying time is preferably 6 to 10 hours, more preferably 7 to 9 hours, still more preferably 8 hours.
The mass ratio of the zeolite-like imidazole framework material ZIF-8 to the ammonium borate tetrahydrate in the step 2) is preferably 1:2-6, more preferably 1:3-5, and even more preferably 1:4.
The carbonization in step 2) is carried out in a protective atmosphere, and the protective atmosphere is preferably argon and/or nitrogen; the carbonization temperature is preferably 800-1000 ℃, more preferably 850-950 ℃, more preferably 900 ℃, the rate of heating to the carbonization temperature is preferably 3-5 ℃/min, more preferably 4 ℃/min, the carbonization time is preferably 1-3 h, more preferably 2h;
the invention also provides the boron-nitrogen co-doped dodecahedron layered porous carbon prepared by the preparation method.
The invention also provides a layered porous carbon electrode containing the boron-nitrogen co-doped dodecahedron layered porous carbon, which comprises the boron-nitrogen co-doped dodecahedron layered porous carbon, a conductive agent and a binder, wherein the mass ratio of the boron-nitrogen co-doped dodecahedron layered porous carbon to the conductive agent to the binder is preferably 6-8:1-2:1-2, and is further preferably 7:2:1.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
11.2g of 2-methylimidazole and 100mL of water were mixed to obtain a 2-methylimidazole aqueous solution, 3g of zinc acetate dihydrate and 100mL of water were mixed to obtain a zinc acetate aqueous solution, and the 2-methylimidazole aqueous solution and the zinc acetate aqueous solution were mixed for 10 minutes to obtain a mixed solution. Aging the mixed solution at 25 ℃ for 24 hours, washing the aged product with water for 3 times, washing for 2 minutes each time, centrifuging for 5 minutes at a rotating speed of 7000rpm, and drying for 8 hours at 60 ℃ to obtain the zeolite-like imidazole skeleton material ZIF-8. Mixing a zeolite-like imidazole skeleton material ZIF-8 and ammonium borate tetrahydrate according to a mass ratio of 1:4, carbonizing for 2 hours in an argon atmosphere at 900 ℃, and heating to the temperature of 900 ℃ at a heating rate of 3 ℃/min to obtain boron-nitrogen co-doped dodecahedron layered porous carbon BNC-1.
70mg of BNC-1, 20mg of acetylene black and 10mg of polyvinylidene fluoride are mixed, 800 mu L of N-methyl pyrrolidone is added, electrode slurry is obtained after uniform mixing, the slurry is uniformly coated on titanium foil, drying is carried out for 24 hours at 60 ℃, and a circular electrode plate with the diameter of 12mm is cut into the layered porous carbon electrode.
A layered porous carbon electrode with a diameter of 12mm was used as a positive electrode, a zinc foil with a thickness of 0.1mm and a diameter of 12mm was used as a negative electrode, and a Whatman GF/C glass fiber filter paper filter membrane with a diameter of 14mm was used as a separator. Impregnating a filter paper membrane to 0.2mol/L ZnSO 4 ·7H 2 And in the O aqueous solution, sequentially superposing the negative plate, the diaphragm, the positive plate, the gasket and the elastic sheet (the elastic sheet and the gasket are C2025 adaptive elastic sheets and gaskets), putting the mixture into a CR2025 buckle type shell, and assembling the mixture into the zinc ion hybrid capacitor through a packaging machine.
The structure of the boron-nitrogen co-doped dodecahedron layered porous carbon BNC-1 prepared in the embodiment is analyzed by a scanning electron microscope, the result is shown in figure 1, it can be seen from the figure that BNC-1 presents a dodecahedron structure with rough and porous surface, the particle size is uniform, and the pore structure parameters are shown in table 1.
TABLE 1 pore structure parameters of boron-nitrogen co-doped dodecahedron layered porous carbon BNC-1
The specific surface area of the boron-nitrogen co-doped dodecahedron layered porous carbon BNC-1 of the embodiment reaches 2670m 2 ·g -1 The microporosity is 45.6%, the mesopore and macroporosity is 54.4%, and the pore size is suitable for the zinc ion mixed capacitor.
The boron-nitrogen co-doped dodecahedron layered porous carbon BNC-1 prepared in the embodiment is characterized by using an X-ray photoelectron spectroscopy technology, and the result is shown in figure 2. As can be seen from FIG. 2, two characteristic peaks around 24℃and 43℃represent (002) and (100) plane diffraction peaks of graphite, respectively, and broad and weak 002 and 100 diffraction peaks show low graphitization degree of BNC-1, and defects and disordered structures are generated due to doping.
The zinc ion mixed capacitor prepared in this example was subjected to constant current charge and discharge test using the LAND battery test system, and the zinc ion mixed capacitor was in the voltage range of 0.2 to 1.8V, respectively 0.2 A.g -1 、0.5A·g -1 、1A·g -1 、2A·g -1 、5A·g -1 、10A·g -1 And 20 A.g -1 As shown in FIG. 3, the zinc ion mixed capacitor prepared in the embodiment has a voltage of 0.2-1.8V and a voltage of 0.2A.g -1 The specific capacity is 148.8mA.h/g at a current density of 20A.g -1 The specific capacity still can reach 91.8mA.h/g under the current density.
The zinc ion mixed capacitor prepared in the embodiment is 5 A.g -1 The cycle performance test was conducted at the current density of (2) and the results are shown in FIG. 4, and it can be seen from the graph that the cycle performance test was conducted at 5 A.g -1 Is (1) the current of the (a)After 100000 times of circulation under the density, the capacitor retention rate is 98.2%, the coulombic efficiency is kept at 100%, and the circulation stability is excellent. The zinc ion mixed capacitor taking the boron-nitrogen co-doped dodecahedron layered porous carbon as the positive electrode has excellent multiplying power performance and cycle performance as shown in the figures 3 and 4.
Comparative example 1
The ammonium borate tetrahydrate in example 1 was omitted, and the conditions were the same as in example 1 to obtain porous carbon CC.
The porous carbon CC was substituted for BNC-1 in example 1, and the other conditions were the same as in example 1, to obtain a porous carbon electrode, and a zinc ion mixed capacitor was assembled with reference to the sequence of example 1.
The porous carbon CC prepared in this comparative example had a specific surface area of 1273m 2 ·g -1 The method comprises the steps of carrying out a first treatment on the surface of the The total pore volume is 0.584cm 3 ·g -1 The method comprises the steps of carrying out a first treatment on the surface of the The micropore volume is 0.377cm 3 ·g -1 The method comprises the steps of carrying out a first treatment on the surface of the Mesoporous and macroporous pore volume of 0.207cm 3 ·g -1 . From example 1 and comparative example 1, it is known that ammonium borate forms macropores during carbonization, and that these macropores form a large number of centers and channels, resulting in more effective micropores and mesopores.
The voltage of the zinc ion mixed capacitor prepared in the comparative example is 0.2 A.g in the range of 0.2-1.8V -1 The specific capacity at current density was 76.8mA.h/g, at 5 A.g -1 Has a capacitance retention of 48.2% after 100000 cycles at current density.
Comparing example 1 with comparative example 1, it is apparent that the zinc ion mixed capacitor prepared in example 1 has superior performance to comparative example 1, and the layered porous structure eliminates pore size limitation during zinc ion transport, accelerates electrolyte permeation, and enhances electrode transfer kinetics. B. The N co-doping not only can significantly adjust the active sites of the interaction, but also improves the wettability of the carbon-based material, so that the capacitor has an ultra-long cycle life.
Example 2
10.8g of 2-methylimidazole and 100mL of water were mixed to obtain a 2-methylimidazole aqueous solution, 5g of zinc acetate dihydrate and 100mL of water were mixed to obtain a zinc acetate aqueous solution, and the 2-methylimidazole aqueous solution and the zinc acetate aqueous solution were mixed for 8 minutes to obtain a mixed solution. Aging the mixed solution at 30 ℃ for 20 hours, washing the aged product with water for 4 times, washing for 3 minutes each time, centrifuging for 5 minutes at a rotating speed of 6800rpm, and drying for 10 hours at 70 ℃ to obtain the zeolite-like imidazole skeleton material ZIF-8. Mixing a zeolite-like imidazole skeleton material ZIF-8 and ammonium borate tetrahydrate according to a mass ratio of 1:3, carbonizing for 3 hours in a nitrogen atmosphere at a temperature of 1000 ℃, and heating to a temperature of 1000 ℃ at a heating rate of 4 ℃/min to obtain boron-nitrogen co-doped dodecahedron layered porous carbon BNC-2.
Example 3
11.6g of 2-methylimidazole and 100mL of water were mixed to obtain a 2-methylimidazole aqueous solution, 4g of zinc acetate dihydrate and 100mL of water were mixed to obtain a zinc acetate aqueous solution, and the 2-methylimidazole aqueous solution and the zinc acetate aqueous solution were mixed for 12 minutes to obtain a mixed solution. Aging the mixed solution at 22 ℃ for 28 hours, washing the aged product with water for 2 times, washing for 2 minutes each time, centrifuging for 5 minutes at the rotating speed of 7200rpm, and drying for 7 hours at 50 ℃ to obtain the zeolite-like imidazole skeleton material ZIF-8. Mixing a zeolite-like imidazole skeleton material ZIF-8 and ammonium borate tetrahydrate according to a mass ratio of 1:5, carbonizing for 1h under an argon atmosphere at 800 ℃, and heating to the temperature of 800 ℃ at a heating rate of 5 ℃/min to obtain boron-nitrogen co-doped dodecahedron layered porous carbon BNC-3.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. The preparation method of the boron-nitrogen co-doped dodecahedron layered porous carbon is characterized by comprising the following steps of:
1) Mixing 2-methylimidazole, zinc acetate dihydrate and water, and aging to obtain a zeolite-like imidazole framework material ZIF-8;
2) And mixing the zeolite-like imidazole framework material ZIF-8 and ammonium borate tetrahydrate, and carbonizing to obtain the boron-nitrogen co-doped dodecahedron layered porous carbon.
2. The preparation method according to claim 1, wherein the mass ratio of the 2-methylimidazole to the zinc acetate dihydrate in the step 1) is 2-5:1, and the mass volume ratio of the 2-methylimidazole to the water is 10.5-12 g:200mL.
3. The method of claim 1 or 2, wherein the mixing time of step 1) is 8 to 12 minutes; the aging temperature is 20-30 ℃, and the aging time is 20-30 h.
4. The method according to claim 3, wherein the aged product of step 1) is washed and dried sequentially, the washed reagent is water, the number of times of washing is 2-4 times, the time of single washing is 2-3 min, the drying temperature is 50-70 ℃, and the drying time is 6-10 h.
5. The preparation method of claim 4, wherein the mass ratio of the zeolite-like imidazole framework material ZIF-8 to the ammonium borate tetrahydrate in the step 2) is 1:2-6.
6. The method according to claim 4 or 5, wherein the carbonization in step 2) is performed under a protective atmosphere of argon and/or nitrogen; the carbonization temperature is 800-1000 ℃, the rate of heating to the carbonization temperature is 3-5 ℃/min, and the carbonization time is 1-3 h.
7. The boron-nitrogen co-doped dodecahedron layered porous carbon prepared by the preparation method of any one of claims 1 to 6.
8. A layered porous carbon electrode comprising the boron-nitrogen co-doped dodecahedron layered porous carbon of claim 7, wherein the layered porous carbon electrode comprises the boron-nitrogen co-doped dodecahedron layered porous carbon, a conductive agent, and a binder, and the mass ratio of the boron-nitrogen co-doped dodecahedron layered porous carbon, the conductive agent, and the binder is 6-8:1-2:1-2.
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