CN113206229B - Preparation method of quinone@nitrogen doped microporous carbon composite material - Google Patents
Preparation method of quinone@nitrogen doped microporous carbon composite material Download PDFInfo
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- CN113206229B CN113206229B CN202110432968.1A CN202110432968A CN113206229B CN 113206229 B CN113206229 B CN 113206229B CN 202110432968 A CN202110432968 A CN 202110432968A CN 113206229 B CN113206229 B CN 113206229B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 101
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 29
- 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 29
- 239000000843 powder Substances 0.000 claims abstract description 25
- 238000002844 melting Methods 0.000 claims abstract description 17
- 230000008018 melting Effects 0.000 claims abstract description 12
- 238000000859 sublimation Methods 0.000 claims abstract description 12
- 230000008022 sublimation Effects 0.000 claims abstract description 12
- 238000011068 loading method Methods 0.000 claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 31
- 150000004056 anthraquinones Chemical class 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 16
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 13
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 12
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 claims description 10
- 238000003763 carbonization Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000003837 high-temperature calcination Methods 0.000 claims 1
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 13
- 238000004090 dissolution Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- 239000005486 organic electrolyte Substances 0.000 abstract description 5
- 239000010405 anode material Substances 0.000 abstract description 3
- 238000010000 carbonizing Methods 0.000 abstract 2
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000007774 positive electrode material Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- DVVGIUUJYPYENY-UHFFFAOYSA-N 1-methylpyridin-2-one Chemical compound CN1C=CC=CC1=O DVVGIUUJYPYENY-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 235000012431 wafers Nutrition 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 150000004053 quinones Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of carbon composite materials, in particular to a preparation method of a quinone@nitrogen doped microporous carbon composite material, which comprises the steps of preparing ZIF-8 powder, carbonizing at high temperature, synthesizing the quinone@nitrogen doped microporous carbon composite material by adopting a sublimation melting method, and preparing the organic active molecule composite material by taking nitrogen doped microporous carbon obtained by carbonizing ZIF-8 as a carrier and adsorbing organic active molecules into carbonized nitrogen doped microporous carbon holes through sublimation-melting, thereby improving loading and binding effects, inhibiting dissolution of the organic active molecules, effectively improving conductivity of the composite material, solving the problems of weak conductivity of an organic active molecule anode material, dissolution in an organic electrolyte and the like, effectively improving cycle performance and multiplying power performance of a lithium ion battery, and having wide application prospect in the field of new energy.
Description
Technical Field
The invention relates to the technical field of carbon composite materials, in particular to a preparation method of a quinone@nitrogen doped microporous carbon composite material.
Background
In recent years, the demand for Lithium Ion Batteries (LIBs) has grown dramatically from portable batteries to large energy storage systems, and the LIBs currently rely mainly on traditional inorganic cathode materials, however, inorganic cathode materials achieve a bottleneck capacity (< 170 mAh g-1), are expensive in extraction and preparation technology, and are harmful to the environment. Compared with inorganic positive electrode materials, the organic quinone compounds used as the positive electrode materials of the lithium battery have the advantages of high theoretical specific capacity, rich raw materials, strong structural designability and the like, and in addition, certain quinone substances can be directly extracted from plants, so that the quinone compounds are energy storage substances with wide application prospects. Anthraquinone (AQ), an important chemical raw material, has abundant raw materials and low cost, has a conjugated carbonyl structure with a planar structure, and has two reactive carbonyl groups (C=O), and can be used as a lithium ion battery anode material with a theoretical gram capacity of as high as 257 mAh/g. However, the lithium ion battery of the organic positive electrode material still has some problems in practical application, and the organic active molecule serving as the positive electrode material has the defects of weak conductivity, easy dissolution in electrolyte and the like, so that the problems of difficult electron and ion transmission, poor cycle performance and the like are caused.
Therefore, it is important to explore a preparation method of a lithium ion battery anode material which effectively binds organic active molecules and improves the electron and ion transmission capacity of the organic active molecules.
Disclosure of Invention
In order to overcome the defects, the invention provides a preparation method of a quinone@nitrogen doped microporous carbon composite material. The design thought of this application lies in: starting from the microstructure design of the electrode material, a novel method is designed to solve the problems of weak conductivity, dissolution in organic electrolyte and the like of the organic active molecular positive electrode material. The porous carbon skeleton material obtained by carbonization is used as a carrier, organic active molecules are adsorbed into the holes of the carbonized organic skeleton material through sublimation-melting action to prepare the organic active molecule composite material, so that the loading and binding effects are improved, the dissolution of the organic active molecules is inhibited, and the conductivity of the composite material is effectively improved.
The technical scheme adopted for solving the technical problems is as follows: a preparation method of a quinone@nitrogen doped microporous carbon composite material comprises the following steps:
step (1), preparing ZIF-8 powder: dispersing 2-methylimidazole in methanol, dripping Zn (NO 3) 2.6H2O solution, standing at room temperature, centrifugally washing the methanol for multiple times, and drying to obtain ZIF-8 powder;
step (2), high-temperature carbonization treatment: carrying out high-temperature carbonization treatment on the ZIF-8 powder prepared in the step (1) in an inert gas atmosphere to obtain nitrogen-doped microporous carbon;
and (3) ball milling the nitrogen-doped microporous carbon and sublimable carbonyl organic active molecules prepared in the step (2), then adding the mixture into a reaction kettle for high-temperature treatment, and synthesizing the quinone@nitrogen-doped microporous carbon composite material by adopting a sublimation melting method.
According to another embodiment of the present invention, the specific method of the step (1) further includes dispersing 2-methylimidazole in methanol through ultrasonic dispersion, dripping a Zn (NO 3) 2.6h2o solution, standing at room temperature for 24-72 h, centrifuging methanol at 60-100 ℃ under vacuum condition of 1000-4000 Pa, washing for multiple times, and drying to obtain ZIF-8 powder. Specifically, the ultrasonic dispersion time is 10-30 min, the standing time at room temperature is 24-72 h, and finally, the materials are dried in a vacuum drying oven for 12-48 h.
According to another embodiment of the present invention, the mass ratio of 2-methylimidazole to Zn (NO 3) 2.6h2o in the step (1) is 2:1 to 4:1.
according to another embodiment of the present invention, the specific method of the step (2) further includes: under inert gas atmosphere, ZIF-8 powder is placed in a tube furnace for 5-20 ℃ min -1 And (3) heating to 900-1000 ℃ and calcining for 1-3 hours at high temperature to obtain the nitrogen-doped microporous carbon. Preferably, the diameter of the furnace tube in the tube furnace is larger than 5 cm.
Preferably, the nitrogen doping amount of the nitrogen doped microporous carbon is 5.5-8.5 wt%.
According to another embodiment of the invention, the method in the step (3) further comprises the specific steps of ball milling nitrogen-doped microporous carbon and sublimable carbonyl organic active molecules for 1-3 hours at 300-800 r/min, adding the ball milled organic active molecules into a reaction kettle after drying, and preparing the quinone@nitrogen-doped microporous carbon composite material by adopting a sublimation melting method.
According to another embodiment of the present invention, the method further comprises, in the step (3), a mass ratio of nitrogen doped microporous carbon to sublimable carbonyl-type organic active molecules is 7: 3-3: 7. preferably, the mass ratio of the nitrogen doped microporous carbon to the sublimable carbonyl organic active molecules is 2:3.
according to another embodiment of the present invention, further comprising, the step (3) of sublimable carbonyl-type organic active molecule is anthraquinone or phenanthrenequinone. Anthraquinone or phenanthrenequinone is added, and the main effect is that the sublimation and melting reaction conditions are different. When anthraquinone is selected, the reaction kettle is kept at 295-310 ℃ for 3-12 hours, preferably 300 ℃ and 6 hours. When phenanthrenequinone is selected, the reaction kettle is kept at 210-250 ℃ for 3-12 hours, preferably 220 ℃ and 6 hours.
Preferably, the step (3) uses ethanol as a solvent for the ball milling process. Specifically, ball milling is carried out for 1-3 hours at the speed of 300-800 r/min.
The invention also provides a quinone@nitrogen doped microporous carbon composite material, which is characterized in that the quinone@nitrogen doped microporous carbon composite material is prepared by the method, and the quinone@nitrogen doped microporous carbon composite material is black powder, and has the density of less than 1.42g cm -3 The loading of the organic active molecules is 30% -70%, and the dodecahedron cubic structure of the ZIF-8 is maintained.
The invention also provides application of the quinone@nitrogen doped microporous carbon composite material in the field of new energy.
Specifically, the quinone@nitrogen doped microporous carbon composite material is prepared into slurry by taking N-methyl-2-pyridone (NMP) as a solvent, wherein the slurry comprises 80 wt% of prepared composite material, 10 wt% of conductive carbon and 10 wt% of polyvinylidene fluoride (PVDF), uniformly dispersed and then roll-coated on an aluminum foil, dried overnight in a vacuum drying oven at 80 ℃ and cut into wafers with the diameter of 1.3 cm, and the wafers are used as the positive electrode of the quinone@nitrogen doped microporous carbon composite material.
Further, assembling a button battery on the prepared composite material anode in an argon-filled glove box, wherein the anode is a lithium sheet, the diaphragm is a Celgard 2325 membrane, the electrolyte is LiPF6 (ethyl carbonate/diethyl carbonate (EC: DEC=1:1 v/v)), and assembling to obtain the quinone@nitrogen doped microporous carbon composite material anode lithium ion battery.
According to the scheme, the nitrogen-doped and microporous carbon framework is utilized to bind the organic active micromolecules, so that the cycle life and the rate capability of the lithium ion battery of the organic positive electrode material are greatly improved, and the material with excellent performance has a wide application prospect in the field of new energy.
The invention has the beneficial effects that the nitrogen-doped microporous carbon obtained by ZIF-8 carbonization is used as a carrier, organic active molecules are adsorbed into carbonized nitrogen-doped microporous carbon holes through sublimation-melting to prepare the organic active molecule composite material, the loading and binding effects are improved, the dissolution of the organic active molecules is inhibited, the conductivity of the composite material is effectively improved, the problems of weak conductivity of an organic active molecule positive electrode material, dissolution in an organic electrolyte and the like are solved, and the cycle performance and the multiplying power performance of the lithium ion battery are effectively improved. The application obtains the quinone@nitrogen doped microporous carbon composite material, wherein the nitrogen doped microporous carbon plays roles of binding organic active molecules and improving conductivity.
Drawings
The invention will be further described with reference to the drawings and examples.
FIG. 1 is a transmission electron microscopic image of the anthraquinone @ nitrogen-doped microporous carbon composite material prepared as described above in examples 1 to 3 of the present invention;
fig. 2 is a graph of the cycling stability performance of the anthraquinone @ nitrogen doped microporous carbon anodes prepared as described above in examples 1 through 3 of the present invention and the anthraquinone anode prepared in comparative example 1 assembled between 1.5 and 3.5V at 0.1C for the first three hundred times.
Detailed Description
A preparation method of a quinone@nitrogen doped microporous carbon composite material comprises the following steps:
step (1), preparing ZIF-8 powder: dispersing 2-methylimidazole in methanol, dripping Zn (NO 3) 2.6H2O solution, standing at room temperature, centrifugally washing the methanol for multiple times, and drying to obtain ZIF-8 powder;
step (2), high-temperature carbonization treatment: carrying out high-temperature carbonization treatment on the ZIF-8 powder prepared in the step (1) in an inert gas atmosphere to obtain nitrogen-doped microporous carbon;
and (3) ball milling the nitrogen-doped microporous carbon and sublimable carbonyl organic active molecules prepared in the step (2), then adding the mixture into a reaction kettle for high-temperature treatment, and synthesizing the quinone@nitrogen-doped microporous carbon composite material by adopting a sublimation melting method.
According to the preparation method, nitrogen-doped microporous carbon obtained by ZIF-8 carbonization is used as a carrier, organic active molecules are adsorbed into carbonized nitrogen-doped microporous carbon holes through sublimation-melting, so that the loading and binding effects are improved, the dissolution of the organic active molecules is inhibited, the conductivity of the composite is effectively improved, the problems that an organic active molecule positive electrode material is weak in conductivity and is dissolved in an organic electrolyte are solved, and the cycle performance and the multiplying power performance of a lithium ion battery are effectively improved. The application obtains the quinone@nitrogen doped microporous carbon composite material, wherein the nitrogen doped microporous carbon plays roles of binding organic active molecules and improving conductivity.
According to another embodiment of the present invention, the specific method of the step (1) further includes dispersing 2-methylimidazole in methanol through ultrasonic dispersion, dripping a Zn (NO 3) 2.6h2o solution, standing at room temperature for 24-72 h, centrifuging methanol at 60-100 ℃ under vacuum condition of 1000-4000 Pa, washing for multiple times, and drying to obtain ZIF-8 powder.
Specifically, the ultrasonic dispersion time is 10-30 min, the standing time at room temperature is 24-72 h, and finally, the materials are dried in a vacuum drying oven for 12-48 h.
According to another embodiment of the present invention, the mass ratio of 2-methylimidazole to Zn (NO 3) 2.6h2o in the step (1) is 2:1 to 4:1.
according to another embodiment of the present invention, the specific method of the step (2) further includes: under inert gas atmosphere, ZIF-8 powder is placed in a tube furnace for 5-20 ℃ min -1 And (3) heating to 900-1000 ℃ and calcining for 1-3 hours at high temperature to obtain the nitrogen-doped microporous carbon. Preferably, the diameter of the furnace tube in the tube furnace is larger than 5 cm.
Preferably, the nitrogen doping amount of the nitrogen doped microporous carbon is 5.5-8.5 wt%.
According to another embodiment of the invention, the method in the step (3) further comprises the specific steps of ball milling nitrogen-doped microporous carbon and sublimable carbonyl organic active molecules for 1-3 hours at 300-800 r/min, adding the ball milled organic active molecules into a reaction kettle after drying, and preparing the quinone@nitrogen-doped microporous carbon composite material by adopting a sublimation melting method.
According to another embodiment of the present invention, the method further comprises, in the step (3), a mass ratio of nitrogen doped microporous carbon to sublimable carbonyl-type organic active molecules is 7: 3-3: 7. preferably, the mass ratio of the nitrogen doped microporous carbon to the sublimable carbonyl organic active molecules is 2:3.
according to another embodiment of the present invention, further comprising, the step (3) of sublimable carbonyl-type organic active molecule is anthraquinone or phenanthrenequinone. Anthraquinone or phenanthrenequinone is added, and the main effect is that the sublimation and melting reaction conditions are different. When anthraquinone is selected, the reaction kettle is kept at 295-310 ℃ for 3-12 hours, preferably 300 ℃ and 6 hours. When phenanthrenequinone is selected, the reaction kettle is kept at 210-250 ℃ for 3-12 hours, preferably 220 ℃ and 6 hours.
Preferably, the step (3) uses ethanol as a solvent for the ball milling process. Specifically, ball milling is carried out for 1-3 hours at the speed of 300-800 r/min.
The invention also provides a quinone@nitrogen doped microporous carbon composite material, which is characterized in that the quinone@nitrogen doped microporous carbon composite material is prepared by the method, and the quinone@nitrogen doped microporous carbon composite material is black powder, and has the density of less than 1.42g cm -3 The loading of the organic active molecules is 30% -70%, and the dodecahedron cubic structure of the ZIF-8 is maintained.
The invention also provides application of the quinone@nitrogen doped microporous carbon composite material in the field of new energy.
Specifically, the quinone@nitrogen doped microporous carbon composite material is prepared into slurry by taking N-methyl-2-pyridone (NMP) as a solvent, wherein the slurry comprises 80 wt% of prepared composite material, 10 wt% of conductive carbon and 10 wt% of polyvinylidene fluoride (PVDF), uniformly dispersed and then roll-coated on an aluminum foil, dried overnight in a vacuum drying oven at 80 ℃ and cut into wafers with the diameter of 1.3 cm, and the wafers are used as the positive electrode of the quinone@nitrogen doped microporous carbon composite material.
Further, assembling a button battery on the prepared composite material anode in an argon-filled glove box, wherein the anode is a lithium sheet, the diaphragm is a Celgard 2325 membrane, the electrolyte is LiPF6 (ethyl carbonate/diethyl carbonate (EC: DEC=1:1 v/v)), and assembling to obtain the quinone@nitrogen doped microporous carbon composite material anode lithium ion battery.
According to the scheme, the nitrogen-doped and microporous carbon framework is utilized to bind the organic active micromolecules, so that the cycle life and the rate capability of the lithium ion battery of the organic positive electrode material are greatly improved, and the material with excellent performance has a wide application prospect in the field of new energy.
The technical scheme of the present invention will be further described in detail below with reference to several preferred embodiments and the accompanying drawings, but the present invention includes but is not limited to the following embodiments.
Example 1
The preparation method of the anthraquinone @ nitrogen doped microporous carbon composite material comprises the following steps:
(1) Weighing 0.616 g of 2-methylimidazole and 0.558 g of Zn (NO 3) 2.6H2O, respectively adding into 15 mL methanol, performing ultrasonic dispersion for 30 min, dropwise adding the 2-methylimidazole dispersion into the Zn (NO 3) 2.6H2O dispersion under continuous stirring, standing at room temperature for 24 h, performing centrifugal washing with methanol for three times, and drying in a vacuum drying oven at 2000 Pa and 60 ℃ for 24 h to obtain ZIF-8 white powder;
(2) Placing the dried ZIF-8 white powder in a tube furnace under argon atmosphere, heating to 1000 ℃ at a rate of 5 ℃ min < -1 > and maintaining the temperature at 3h to obtain nitrogen-doped microporous carbon;
(3) The method comprises the steps of weighing nitrogen doped microporous carbon after 0.4 and g calcination and 0.6 g anthraquinone respectively, mixing and adding the mixture into 10 mL ethanol solvent, ball milling the mixture at a rotating speed of 600 r/min for 2h, drying the mixture in a vacuum drying oven at 60 ℃ for 24 h, adding the mixture into a reaction kettle, preserving heat at 300 ℃ for 3h, and preparing the anthraquinone@nitrogen doped microporous carbon composite material by adopting a sublimation melting method.
Example 2
Preparation of an anthraquinone @ nitrogen doped microporous carbon composite material, wherein the anthraquinone loading is 40%, and the preparation method comprises the following steps of:
(1) Weighing 0.616 g of 2-methylimidazole and 0.558 g of Zn (NO 3) 2.6H2O, respectively adding into 15 mL methanol, performing ultrasonic dispersion for 30 min, dropwise adding the 2-methylimidazole dispersion into the Zn (NO 3) 2.6H2O dispersion under continuous stirring, standing at room temperature for 24 h, performing centrifugal washing with methanol for three times, and drying in a vacuum drying oven at 2000 Pa and 60 ℃ for 24 h to obtain ZIF-8 white powder;
(2) Placing the dried ZIF-8 white powder in a tube furnace under argon atmosphere, heating to 1000 ℃ at a rate of 5 ℃ min < -1 > and maintaining the temperature at 3h to obtain nitrogen-doped microporous carbon;
(3) The method comprises the steps of weighing nitrogen doped microporous carbon after 0.6 g calcination and 0.4 g anthraquinone respectively, mixing and adding the mixture into 10 mL ethanol solvent, ball milling the mixture at a rotating speed of 600 r/min for 2h, drying the mixture in a vacuum drying oven at 60 ℃ for 24 h, adding the mixture into a reaction kettle, preserving heat at 300 ℃ for 3h, and preparing the anthraquinone@nitrogen doped microporous carbon composite material by adopting a sublimation melting method.
Example 3
The preparation method of the phenanthrenequinone@nitrogen doped microporous carbon composite material comprises the following steps:
(1) Weighing 0.616 g of 2-methylimidazole and 0.558 g of Zn (NO 3) 2.6H2O, respectively adding into 15 mL methanol, performing ultrasonic dispersion for 30 min, dropwise adding the 2-methylimidazole dispersion into the Zn (NO 3) 2.6H2O dispersion under continuous stirring, standing at room temperature for 24 h, performing centrifugal washing with methanol for three times, and drying in a vacuum drying oven at 2000 Pa and 60 ℃ for 24 h to obtain ZIF-8 white powder;
(2) Placing the dried ZIF-8 white powder in a tube furnace under argon atmosphere, heating to 1000 ℃ at a rate of 5 ℃ min < -1 > and maintaining the temperature at 3h to obtain nitrogen-doped microporous carbon;
(3) And respectively weighing the nitrogen-doped microporous carbon calcined by 0.4 g and 0.6 g phenanthrenequinone, mixing and adding the mixture into a 10 mL ethanol solvent, ball-milling the mixture at a rotation speed of 600 r/min for 2h, drying the mixture in a vacuum drying oven at 60 ℃ for 24 h, adding the mixture into a reaction kettle, preserving heat at 210-250 ℃ for 3h, and preparing the phenanthrenequinone@nitrogen-doped microporous carbon composite material by adopting a sublimation melting method.
Comparative example
Preparation of anthraquinone material.
This control is substantially identical to example 1, except that the mass ratio of nitrogen doped microporous carbon to anthraquinone is 0:1, the steps are as follows:
weighing 0.6 g anthraquinone, adding into 6 mL ethanol solvent, ball milling at 600 r/min for 2h, drying in vacuum drying oven at 60deg.C for 24 h, adding into reaction kettle, and maintaining at 300 deg.C for 3h to obtain anthraquinone material.
The materials prepared in examples 1 to 3 and the comparative examples were fabricated into positive electrode sheets according to the following procedures, and the batteries were assembled and tested:
(1) Manufacturing of positive plate
Uniformly dispersing the materials prepared in the examples 1-3 and the comparative examples, conductive carbon and polyvinylidene fluoride (PVDF) in a mass ratio of 8:1:1 in N-methyl-2-pyridone (NMP), stirring for 6h to obtain positive electrode slurry, then roll-coating the slurry on aluminum foil, drying overnight in a vacuum drying oven at 80 ℃, and cutting into wafers with diameters of 1.3 cm to obtain positive electrode plates.
(2) Battery assembly
And (3) assembling the button cell on the prepared positive plate, wherein in an argon-filled glove box, the lithium plate is used as a negative electrode, a Celgard 2325 film is used as a diaphragm, liPF6 (ethyl carbonate/diethyl carbonate (EC: DEC=1:1 v/v)) is used as electrolyte, and the lithium ion cell is assembled.
(3) Battery testing
The assembled battery is subjected to electrochemical performance test, and the specific steps are as follows:
after the assembled battery is kept stand at room temperature for 12 h, the battery is tested by using an electrochemical workstation, CV is measured within a voltage range of 1.5-3.5V at a scanning rate of 0.1 mV s < -1 >, the battery is subjected to charge and discharge testing by using an electrochemical tester, the charge and discharge testing is performed under a test condition of 0.1C between 1.5-3.5V, a charge and discharge curve and a cycling stability curve of the first three hundred times are obtained, and the rate performance under the conditions of 0.1C, 0.2C, 0.5C and 1C are tested, wherein the discharge specific capacity of the battery is calculated by using organic active substances. The battery is disassembled at different stages of charge and discharge to measure the ex-situ XPS local spectrum of the Li 1s region, so as to explore the charge and discharge mechanism.
Further, the inventors of the present application have characterized and studied the anthraquinone @ nitrogen-doped microporous carbon composite material, anthraquinone material and nitrogen-doped microporous carbon material prepared by the processes described in examples 1 to 3 and comparative examples, and specifically as follows:
FIG. 1 is a transmission electron microscopic image of the anthraquinone @ nitrogen-doped microporous carbon composite material prepared as described above in examples 1 to 3 of the present invention.
Fig. 2 is a graph of the cycling stability performance of the anthraquinone @ nitrogen doped microporous carbon anodes prepared as described above in examples 1 through 3 of the present invention and the anthraquinone anode prepared in comparative example 1 assembled between 1.5 and 3.5V at 0.1C for the first three hundred times.
In summary, the comparative analysis shows that the anthraquinone@nitrogen doped microporous carbon composite materials prepared in examples 1 to 3 have excellent electrochemical properties, and have the best cycle performance and the best rate performance. Specifically, the reversible capacities of the positive electrode prepared from the anthraquinone@nitrogen doped microporous carbon composite material in the embodiment 1 at 0.1, 0.2, 0.5 and 1.0C multiplying powers are 240 mAh g-1, 226 mAh g-202 and 173 mAh g-1 respectively, and the multiplying power performance is remarkably improved compared with the comparison example; and, the positive electrode prepared by the anthraquinone@nitrogen doped microporous carbon composite material in the above examples 1 to 3 has a first week discharge specific capacity up to 240 mAh/g, and after 300 times of circulation, the discharge specific capacity is kept at 216 mAh/g, the capacity retention rate is up to 90%, and compared with the comparative example, the cycle life is remarkably prolonged. According to the technical scheme of the embodiment 1-3, the nitrogen-doped microporous carbon obtained by ZIF-8 carbonization is used as a carrier, organic active molecular quinone is adsorbed into carbonized nitrogen-doped microporous carbon holes through sublimation-melting to prepare the organic active molecular composite material, the nitrogen-doped microporous carbon and the quinone are organically combined, the loading and binding effects are improved, the dissolution of organic active molecules is inhibited, the conductivity of the composite material is effectively improved, the problems of weak conductivity, dissolution in organic electrolyte and the like of an organic active molecular positive electrode material are solved, the cycle performance and the multiplying power performance of a lithium ion battery are effectively improved, and the lithium ion battery has wide application prospect in the field of new energy.
The above description is illustrative of the invention and is not to be construed as limiting, and it will be understood by those skilled in the art that many modifications, changes or equivalents may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (9)
1. The preparation method of the quinone@nitrogen doped microporous carbon composite material is characterized by comprising the following steps of:
step (1), preparing ZIF-8 powder: dispersing 2-methylimidazole in methanol, dripping Zn (NO 3) 2.6H2O solution, standing at room temperature, centrifugally washing with methanol for multiple times, and drying to obtain ZIF-8 powder;
step (2), high-temperature carbonization treatment: carrying out high-temperature carbonization treatment on the ZIF-8 powder prepared in the step (1) in an inert gas atmosphere to obtain nitrogen-doped microporous carbon;
step (3), ball milling the nitrogen doped microporous carbon and sublimable carbonyl organic active molecules prepared in the step (2), then adding the mixture into a reaction kettle for high-temperature treatment, synthesizing the quinone@nitrogen doped microporous carbon composite material by adopting a sublimation melting method,
the carbonyl organic active molecules easy to sublimate in the step (3) are anthraquinone or phenanthrenequinone.
2. The preparation method of the quinone@nitrogen doped microporous carbon composite material according to claim 1, wherein the specific method of the step (1) is that 2-methylimidazole is dispersed in methanol through ultrasonic dispersion, zn (NO 3) 2.6H2O solution is dripped, standing time is 24-72H at room temperature, and the ZIF-8 powder is obtained through centrifugal washing and drying of methanol for multiple times under the vacuum condition of 1000-4000 Pa at 60-100 ℃.
3. The preparation method of the quinone@nitrogen doped microporous carbon composite material according to claim 1, wherein the mass ratio of 2-methylimidazole to Zn (NO 3) 2.6H2O in the step (1) is 2:1 to 4:1.
4. the preparation method of the quinone@nitrogen doped microporous carbon composite material according to claim 1, wherein the specific method of the step (2) is as follows: under inert gas atmosphere, ZIF-8 powder is placed in a tube furnace for 5-20 ℃ min -1 The temperature is raised to 900-1000 ℃, and the nitrogen doped microporous carbon is obtained after high-temperature calcination for 1-3 hours.
5. The method for preparing a quinone @ nitrogen-doped microporous carbon composite material according to claim 4, wherein the nitrogen doping amount of the nitrogen-doped microporous carbon is 5.5-8.5 wt%.
6. The preparation method of the quinone@nitrogen doped microporous carbon composite material is characterized in that the specific method in the step (3) is that nitrogen doped microporous carbon and sublimable carbonyl organic active molecules are ball-milled for 1-3 hours at the speed of 300-800 r/min, and the quinone@nitrogen doped microporous carbon composite material is prepared by adding the dried organic active molecules into a reaction kettle and adopting a sublimation melting method.
7. The preparation method of the quinone@nitrogen doped microporous carbon composite material according to claim 1, wherein the mass ratio of the nitrogen doped microporous carbon to the sublimable carbonyl organic active molecules in the step (3) is 7: 3-3: 7.
8. a quinone-nitrogen-doped microporous carbon composite material is characterized in that the quinone-nitrogen-doped microporous carbon composite material is prepared by the method of any one of claims 1-7, and the quinone-nitrogen-doped microporous carbon composite material is black powder with the density of less than 1.42g cm -3 The loading of the organic active molecules is 30-70%, and the dodecahedron cubic structure of ZIF-8 is maintained.
9. Use of the quinone @ nitrogen doped microporous carbon composite material of claim 8, wherein the quinone @ nitrogen doped microporous carbon composite material is used in the field of new energy.
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