CN117410461A - Co ₂ P nanoparticle @ Cabron@CNTs composite material and preparation and application thereof - Google Patents
Co ₂ P nanoparticle @ Cabron@CNTs composite material and preparation and application thereof Download PDFInfo
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- CN117410461A CN117410461A CN202311198176.8A CN202311198176A CN117410461A CN 117410461 A CN117410461 A CN 117410461A CN 202311198176 A CN202311198176 A CN 202311198176A CN 117410461 A CN117410461 A CN 117410461A
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- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002105 nanoparticle Substances 0.000 claims abstract description 37
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 24
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000010405 anode material Substances 0.000 claims abstract description 7
- 239000002048 multi walled nanotube Substances 0.000 claims description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 5
- 230000008093 supporting effect Effects 0.000 claims description 5
- 238000011144 upstream manufacturing Methods 0.000 claims description 5
- NPUQCECELINJML-UHFFFAOYSA-N 2-ethylimidazole Chemical compound CCC1=NC=C[N]1 NPUQCECELINJML-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 2
- 238000011534 incubation Methods 0.000 claims description 2
- 239000012621 metal-organic framework Substances 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000012298 atmosphere Substances 0.000 abstract description 2
- 150000001868 cobalt Chemical class 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 230000020477 pH reduction Effects 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- 230000014759 maintenance of location Effects 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000002002 slurry Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000011530 conductive current collector Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5805—Phosphides
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
Abstract
The application relates to the technical field of composite materials and discloses a Co 2 The synthesis method of the P nano particle@carbon@CNTs composite material comprises the following steps: (1) preparing MWCNTs-COOH through acidification treatment; (2) Dispersing the prepared MWCNTs-COOH into absolute methanol, and adding a proper amount of polyvinylpyrrolidone to uniformly disperse the MWCNTs-COOH in the solution; then adding cobalt salt and 2-methylimidazole in sequence, stirring uniformly and aging to obtain a precursor solutionThe method comprises the steps of carrying out a first treatment on the surface of the (3) Filtering, washing and drying the precursor solution, and then placing the precursor solution into a tube furnace for heating in a reducing atmosphere; finally, phosphating the obtained product to obtain Co 2 P nanoparticle @ carbon@CNTs composite material. The invention can improve Co 2 The electrochemical activity and the structural stability of P obviously improve the discharge specific capacity, the cycle performance and the multiplying power performance. Co (Co) 2 The P@carbon@CNTs composite material has important application value as a lithium ion battery anode material.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a Co 2 P nano particle@Cabron@CNTs composite material and preparation and application thereof.
Background
Lithium ion batteries have become the mainstream electrochemical energy storage devices in the current market due to their high energy density, long cycle life, environmental friendliness, small volume, and other advantages. However, with the continuous development of society, the conventional lithium ion battery has problems of limited energy density, slow charge and discharge rate, fast cycle decay speed, insufficient safety and the like, and cannot meet the continuous improvement of the battery performance. Therefore, optimization and improvement of lithium ion batteries on the market are urgently needed. The positive and negative electrode materials are taken as two key components of the lithium ion battery, and the improvement and optimization of the positive and negative electrode materials become an important research direction for improving the performance of the lithium ion battery. However, research on cathode materials has approached the bottleneck, and anode materials still have great research potential. Graphite negative electrode material commonly used in commercial lithium ion batteries (theoretical capacity 372mAhg -1 ) The current demand has not been satisfied, and thus new anode materials have been developed to replace graphite. Cobalt phosphide (Co) 2 P) because of its high theoretical capacity (540 mAhg) -1 ) The preparation method has the advantages of low preparation cost, good electron conductivity, high stability and the like, and is considered as a potential negative electrode candidate material of the next-generation lithium ion battery. Although Co 2 P has high theoretical specific capacity, but is easy to generate the problems of pulverization, self-agglomeration, separation of conductive current collector and the like in the lithium intercalation and deintercalation process, so that the rate performance and the cycle performance of the P are poor, and the practical application of the P is limited.
To overcome the above problems, co is increased 2 Lithium storage Property of P Co 2 Nanocrystallization of P materials and compounding with various carbon materials has proven to be an effective strategy. However, no relevance has been found in the published patent applicationCo 2 Relevant reports of P-based lithium ion battery anode materials. Research shows that the morphology of the material and the carbon substrate structure compounded with the material are key factors influencing the performance of the lithium ion battery.
Disclosure of Invention
In view of the above-mentioned technical problems and shortcomings in the art, the present invention provides a Co 2 P nano particle@Cabron@CNTs composite material, preparation and application thereof, and Co can be improved 2 The electrochemical activity and the structural stability of P obviously improve the discharge specific capacity, the cycle performance and the multiplying power performance. Co (Co) 2 The P nano particle@carbon@CNTs composite material has important application value as a lithium ion battery anode material, and aims to solve the problems in the prior art.
In order to achieve the above purpose, the present invention provides the following technical solutions:
co (cobalt) 2 P nanoparticle @ Cabron @ CNTs composite comprising multi-walled carbon nanotubes (MWCNTs) as the primary support structure, the amorphous carbon coupled to the multi-walled carbon nanotubes, the amorphous carbon having a plurality of carbon tentacles derived therefrom, and Co, and preparation and use thereof 2 The P nanoparticles are tightly adhered in amorphous carbon.
Preferably, the amorphous carbon is formed by carbonization of a metal organic framework material (ZIF-67), co 2 The P nano particle source is oxidized by Co nano particles, and Co 2 The particle diameter of the P nanometer particles is 20-80nm, the diameter of the multi-wall carbon nano tube is 50nm, the length of the multi-wall carbon nano tube is 1.5 mu m, the thickness of the amorphous carbon is 70nm, and the diameter of the derived carbon tentacle is 10nm.
The invention also provides a Co 2 The preparation method of the P nano particle@carbon@CNTs composite material comprises the following steps:
(1) Dispersing multiwall carbon nanotubes (MWCNTs) in concentrated nitric acid (mass fraction 68%) and concentrated sulfuric acid (mass fraction 98%), performing ultrasonic dispersion for 30 minutes, heating and stirring in an oil bath, washing for several times to neutrality, collecting, and finally drying the obtained product in a blast drying oven at 60 ℃ to obtain MWCNTs-COOH;
(2) Will beDispersing MWCNTs-COOH into anhydrous methanol, adding into polyvinylpyrrolidone to uniformly disperse MWCNTs-COOH in the solution, and sequentially adding CoCl 2 And 2-methylimidazole, stirring uniformly and aging to obtain a precursor solution, and finally, washing and collecting a product by using methanol, and drying at 60 ℃ to obtain a precursor;
(3) Placing the precursor in a tube furnace, introducing 5% hydrogen/argon mixed gas at 700 ℃, preserving heat for 2 hours, and performing phosphating reaction on the obtained product to obtain Co 2 P nanoparticle @ carbon@CNTs composite material.
The preparation method principle of the application is as follows: firstly, adsorbing polyvinylpyrrolidone by enabling the surface of a carbon nano tube to be provided with hydroxyl groups; then adsorb Co by electrostatic interaction force 2+ And coordinates with 2-methylimidazole to form ZIF-67@CNTs composite material; then heating in a reducing atmosphere to cool Co 2+ Reducing into Co nano particles, carbonizing organic matters in ZIF-67 into amorphous carbon and deriving carbon tentacles; finally, co nano-particles are phosphated into Co 2 P gives the final product. Wherein CNTs play a role in reaction supporting conduction, and carbon tentacles provide larger specific surface area and conduction.
Preferably, in the step (1), the volume ratio of the concentrated nitric acid to the concentrated sulfuric acid in the reaction is 1:2. The molar mass ratio of the multiwall carbon nanotubes to the concentrated nitric acid to the concentrated sulfuric acid in the reaction is 2:15:37. The oil bath heating reaction condition was 90℃for 3 hours.
Preferably, in step (2), the ratio of MWCNTs-COOH to anhydrous methanol is 2 mg/7.5 ml. MWCNTs-COOH, polyvinylpyrrolidone and CoCl 2 And 2-methylimidazole at a mass ratio of 1:16:10:33, aging conditions of 25℃for 12 hours.
Preferably, in the step (3), the phosphating reaction conditions are: in a tube furnace, 0.1g of the obtained product was placed downstream and 1.5g of sodium hypophosphite was placed upstream, followed by argon and incubation at 300℃for 2 hours.
The invention also provides a Co 2 The application of the P nano particle@carbon@CNTs composite material in the field of lithium ion battery anode materials.
The specific steps for manufacturing the lithium ion battery cathode by adopting the composite material of the invention are as follows:
firstly, co with the mass ratio of 8:1:1 is respectively taken 2 The composite material comprises a P nano particle@carbon@CNTs composite material, an acetylene black conductive agent and a polyvinylidene fluoride (PVDF) binder.
PVDF was dissolved in an appropriate amount of 1-methyl-2-pyrrolidone (NMP), and stirred until PVDF was completely dissolved, to prepare a binder solution.
Co to be ground uniformly 2 The P nanoparticle @ carbon @ cnts composite and the acetylene black conductive agent were gradually added to the PVDF solution described above and stirring was continued to ensure uniform slurry mixing. This step is intended to prepare an active material slurry for the electrode.
The prepared slurry is uniformly coated on a copper foil wafer, and the diameter of the copper foil wafer is usually 12mm.
And (3) placing the coated electrode slice in a vacuum oven, baking at 90 ℃, and then annealing at 150 ℃ to obtain the electrode slice. This step aims to remove residual solvent and enhance the binding and conductive properties of the electrode material.
And finally, assembling the prepared electrode plate, a metal lithium plate and a Celgard2500 diaphragm into the CR2025 button-type lithium ion battery. As the electrolyte, a mixed solvent of dimethyl carbonate (DMC) -Ethylene Carbonate (EC) containing 1.0ml ipf6 was used.
The prepared lithium ion battery was subjected to a test of charge-discharge performance and cycle performance using a new battery test system to evaluate its performance.
The invention has the technical effects and advantages that:
1、Co 2 the composite material of P nano particle @ carbon@CNTs takes a multi-wall carbon nano tube as a supporting main body, and ZIF-67 is Co 2 The preparation method adopts the processes of precipitation, carbonization and oxidation synthesis of the precursors of P and amorphous carbon, and is based on the precursors of the multiwall carbon nanotube and ZIF-67, so that the preparation process is simpler and more efficient. This reduces the cost of preparation and improves the scalability of preparation.
2、Co 2 The carbon nano tube in the P nano particle@carbon@CNTs composite material has excellent propertiesThe conductivity has excellent mechanical strength, which is not only beneficial to the transmission of electrons, but also provides a firm supporting structure for the material, and improves the stability and durability of the material.
Co 2 The P nano particles are adhered in the amorphous carbon, and the amorphous carbon can effectively coat Co 2 And the P nano particles improve the conductivity and structural stability of the material. This advantage improves the cycling performance of the material, while also enhancing its performance during high current charge and discharge.
The carbon tentacles derived from amorphous carbon provide more reactive sites for the material, increase electron transport channels and improve the electrochemical activity of the material. This helps to increase the specific capacity of the material, thereby enhancing the energy density and performance of the battery.
Due to the optimized design of the composite material, co 2 The P nano particle@carbon@CNTs composite material shows better cycle performance and high-current charge and discharge performance in a lithium ion battery. This means that the battery has a higher stability in long-term use and high power requirements.
Drawings
FIG. 1 is an SEM photograph of ZIF-67@CNTs prepared in example 1;
FIG. 2 is Co prepared in example 1 2 SEM photograph of P nano particle@carbon@CNTs composite material;
FIG. 3 is Co prepared in example 1 2 TEM photograph of P nanoparticle@carbon@CNTs composite material;
FIG. 4 is Co prepared in example 1 2 P nano particle@carbon@CNTs composite material with current density of 0.5Ag -1 Is a cyclic performance graph of (2);
FIG. 5 is Co prepared in example 1 2 And (3) a multiplying power performance diagram of the P nano particle@carbon@CNTs composite material.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Co (cobalt) 2 The preparation method of the P nano particle@carbon@CNTs composite material comprises the following steps:
(1) Dispersing 0.5g of multi-wall carbon nanotubes (MWCNTs) in 20ml of concentrated nitric acid and 40ml of concentrated sulfuric acid, dispersing for 30 minutes by ultrasonic, heating and stirring for 3 hours in an oil bath at 90 ℃, washing for several times to neutrality, collecting, and finally drying the obtained product in a blast drying oven at 60 ℃ to obtain the MWCNTs-COOH.
(2) Dispersing 40mg MWCNTs-COOH in 100ml anhydrous methanol, adding 0.64g polyvinylpyrrolidone to uniformly disperse MWCNTs-COOH in the solution, and sequentially adding 0.4g CoCl 2 And 1.32g of 2-methylimidazole, stirring uniformly and aging for 12 hours to obtain a precursor solution. Finally, the product was washed with methanol and collected, and dried at 60 ℃ to give the precursor.
(3) The precursor is placed in a tube furnace, and 5% hydrogen/argon mixed gas is introduced to heat to 700 ℃ and keep the temperature for 2 hours. Finally, 0.1g of the obtained product is put in the downstream of a tube furnace, 1.5g of sodium hypophosphite is put in the upstream of the tube furnace, argon is introduced and the temperature is kept at 300 ℃ for 2 hours, thus obtaining Co 2 P nanoparticle @ carbon@CNTs composite material.
FIG. 1 is an SEM photograph of ZIF-67@CNTs. Due to the supporting effect of the multi-wall carbon nano tube, the synthesized ZIF-67 closely grows on the multi-wall carbon nano tube to form a sugar-like calabash-shaped structure; in addition, ZIF-67 has an average size of about 200nm. FIG. 2 is Co 2 SEM photograph of P nano particle @ carbon@CNTs composite material, and it can be seen that amorphous carbon is coupled on multi-wall carbon nanotubes, the amorphous carbon is derived into carbon tentacles, co 2 The P nano particles are attached in the amorphous carbon to form a sea cucumber-like structure. FIG. 3 is Co 2 TEM photograph of the P nanoparticle@carbon@CNTs composite material, co can be more clearly seen through TEM 2 The diameter of the P nano particles is between 20 and 80nm and uniformly adheres to the amorphous carbon; at the same time it can be seen that amorphous carbon is derivatisedA large number of carbon tentacles are shown, the diameter of which is about 10nm, forming a large number of electron transport channels. Thermogravimetric analysis showed Co 2 The mass content of P was 65%.
The material of the embodiment is adopted to manufacture the negative electrode of the lithium ion battery: co with the mass ratio of 8:1:1 is respectively weighed 2 The preparation method comprises the steps of dissolving PVDF in a proper amount of 1-methyl-2-pyrrolidone (NMP), stirring until the PVDF is completely dissolved, adding uniformly grinded active materials and acetylene black into the solution, and continuously stirring to ensure uniform slurry mixing. And then uniformly coating the slurry on a copper foil wafer (with the diameter of 12 mm), baking at 90 ℃ in a vacuum oven, and then annealing at 150 ℃ to obtain the electrode slice.
And assembling the prepared electrode plate, a metal lithium plate and a Celgard2500 diaphragm to form a CR2025 button type lithium ion battery, taking a dimethyl carbonate (DMC) -Ethylene Carbonate (EC) mixed solvent containing 1.0MLiPF6 as an electrolyte, and adopting a New Wei battery test system to test the charge and discharge performance and the cycle performance of the lithium ion battery.
FIG. 4 is Co 2 P nano particle@carbon@CNTs composite material with current density of 0.5Ag -1 And (3) performing cyclic charge and discharge test in a voltage range of 3-0.01V. 637.8mAhg remains after 100 cycles -1 The specific discharge capacity of (2) is about 95.6% of the capacity retention rate, and the coulombic efficiency is always above 98%, thus showing good reversibility.
FIG. 5 is Co 2 Multiplying power performance graphs of P nano particle@carbon@CNTs composite material at current densities of 0.25, 0.5, 1, 2 and 0.25Ag -1 The average specific discharge capacities were 704, 680, 569, 382 and 739mAhg, respectively -1 Excellent rate performance, when the current is reduced to 0.25Ag -1 When the discharge capacity is recovered to 739mAhg -1 And the reversibility is better.
Example 2
(1) Dispersing 0.5g of multi-wall carbon nanotubes (MWCNTs) in 20ml of concentrated nitric acid and 40ml of concentrated sulfuric acid, dispersing for 30 minutes by ultrasonic, heating and stirring for 3 hours in an oil bath at 90 ℃, washing for several times to neutrality, collecting, and finally drying the obtained product in a blast drying oven at 60 ℃ to obtain the MWCNTs-COOH.
(2) Dispersing 40mg MWCNTs-COOH in 100ml anhydrous methanol, adding 0.64g polyvinylpyrrolidone to uniformly disperse MWCNTs-COOH in the solution, and sequentially adding 0.4g CoCl 2 And 1.32g of 2-methylimidazole, stirring uniformly and aging for 12 hours to obtain a precursor solution. Finally, the product was washed with methanol and collected, and dried at 60 ℃ to give the precursor.
(3) The precursor is placed in a tube furnace, and 5% hydrogen/argon mixed gas is introduced to heat to 700 ℃ and keep the temperature for 2 hours. Finally, 0.1g of the obtained product is put in the downstream of a tube furnace, 1.5g of sodium hypophosphite is put in the upstream of the tube furnace, argon is introduced and the temperature is kept at 250 ℃ for 2 hours, thus obtaining Co 2 P nanoparticle @ carbon@CNTs composite material.
Product Co 2 The structure of the P nanoparticle @ carbon@CNTs composite is similar to that of example 1, with the main differences being incomplete phosphating, co 2 The content of P is reduced, and the simple substance of Co is generated.
The same process as in example 1 was used to fabricate a negative electrode for a lithium ion battery, assembled into a lithium ion battery, and the current density was 0.5Ag -1 And (3) performing cyclic charge and discharge test in a voltage range of 3-0.01V. 456mAhg after 100 cycles -1 The specific discharge capacity of (2) is about 93.8% of the capacity retention rate, and the coulomb efficiency is always above 98%, thus showing good reversibility.
Example 3
(1) Dispersing 0.5g of multi-wall carbon nanotubes (MWCNTs) in 20ml of concentrated nitric acid and 40ml of concentrated sulfuric acid, dispersing for 30min by ultrasonic, heating and stirring for 3h in an oil bath at 90 ℃, washing for several times to be neutral and collecting, and finally drying the obtained product in a blast drying oven at 60 ℃ to obtain the MWCNTs-COOH.
(2) Dispersing 40mg MWCNTs-COOH in 100ml anhydrous methanol, adding 0.64g polyvinylpyrrolidone to uniformly disperse MWCNTs-COOH in the solution, and sequentially adding 0.4g CoCl 2 And 1.32g of 2-methylimidazole, stirring uniformly and aging for 12 hours to obtain a precursor solution. Finally, the product is washed with methanol and collected, and dried at 60 ℃ to obtain the precursorA body.
(3) The precursor is placed in a tube furnace, and 5% hydrogen/argon mixed gas is introduced to heat to 700 ℃ and keep the temperature for 2 hours. Finally, 0.1g of the obtained product is put in the downstream of a tube furnace, 1.5g of sodium hypophosphite is put in the upstream of the tube furnace, argon is introduced and the temperature is kept at 350 ℃ for 2 hours, thus obtaining Co 2 P nanoparticle @ carbon@CNTs composite material.
Product Co 2 The structure of the P nanoparticle @ carbon@CNTs composite is similar to that of example 1, with the main difference being Co 2 The mass ratio of P is increased, and the thermogravimetric analysis shows that Co 2 The mass content of P was 71%.
The same process as in example 1 was used to fabricate a negative electrode for a lithium ion battery, assembled into a lithium ion battery, and the current density was 0.5Ag -1 And (3) performing cyclic charge and discharge test in a voltage range of 3-0.01V. 665.5mAhg remains after 100 cycles -1 The specific discharge capacity of (2) is about 94.3% of the capacity retention rate, and the coulombic efficiency is always above 98%, thus showing better reversibility.
The following is a detailed comparison table for three embodiments, including Co 2 Specific values of P content, specific discharge capacity, capacity retention and coulombic efficiency and performance evaluation:
| characteristics of | Example 1 | Example 2 | Example 3 |
| Co 2 P content (%) | 65％ | Less than 65% | 71％ |
| Specific discharge capacity (mAh/g) | 637.8 | 456 | 665.5 |
| Capacity retention (%) | 95.6％ | 93.8％ | 94.3％ |
| Coulombic efficiency (%) | >98％ | >98％ | >98％ |
Performance evaluation:
Co 2 p content: co of example 1 and example 3 2 The P content was higher, 65% and 71%, respectively, whereas Co of example 2 2 The P content is lower than 65%. Thus, example 1 and example 3 are in Co 2 The P content is better.
Specific discharge capacity: specific discharge capacities of example 1 and example 3 were 637.8mAh/g and 665.5mAh/g, respectively, while specific discharge capacity of example 2 was lower and 456mAh/g. Example 3 shows the highest specific discharge capacity.
Capacity retention rate: both example 1 and example 3 exhibited good performance in terms of capacity retention of 95.6% and 94.3%, respectively, while example 2 had a capacity retention of 93.8%.
Coulombic efficiency: the coulombic efficiency of all three examples remained above 98%, showing good reversibility.
In general, examples 1 and 3 are in Co 2 P content, specific discharge capacity and capacity retentionIn terms of better performance, example 2 although Co 2 The P content is lower, but still has better coulombic efficiency.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that it will be apparent to those skilled in the art that several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the scope of the invention.
Claims (10)
1. Co (cobalt) 2 The composite material is characterized by comprising multi-wall carbon nanotubes (MWCNTs) serving as main supporting structures, wherein the amorphous carbon is coupled to the multi-wall carbon nanotubes, a large number of carbon tentacles are derived from the amorphous carbon, and Co 2 The P nanoparticles are tightly adhered in amorphous carbon.
2. Co according to claim 1 2 The P nano particle@carbon@CNTs composite material is characterized in that the amorphous carbon is formed by carbonizing a metal organic framework material (ZIF-67), co 2 The P nano particle source is oxidized by Co nano particles, and Co 2 The particle diameter of the P nanometer particles is 20-80nm, the diameter of the multi-wall carbon nano tube is 50nm, the length of the multi-wall carbon nano tube is 1.5 mu m, the thickness of the amorphous carbon is 70nm, and the diameter of the derived carbon tentacle is 10nm.
3. Preparation of Co according to any one of claims 1 or 2 2 The preparation method of the P nano particle@carbon@CNTs composite material is characterized by comprising the following steps of:
(1) Dispersing multiwall carbon nanotubes (MWCNTs) in concentrated nitric acid (mass fraction 68%) and concentrated sulfuric acid (mass fraction 98%), performing ultrasonic dispersion for 30 minutes, heating and stirring in an oil bath, washing for several times to neutrality, collecting, and finally drying the obtained product in a blast drying oven at 60 ℃ to obtain MWCNTs-COOH;
(2) Dispersing MWCNTs-COOH into anhydrous methanol, adding into polyvinylpyrrolidone to uniformly disperse MWCNTs-COOH in the solution, and sequentially addingInto CoCl 2 And 2-methylimidazole, stirring uniformly and aging to obtain a precursor solution, and finally, washing and collecting a product by using methanol, and drying at 60 ℃ to obtain a precursor;
(3) Placing the precursor in a tube furnace, introducing 5% hydrogen/argon mixed gas at 700 ℃, preserving heat for 2 hours, and performing phosphating reaction on the obtained product to obtain Co 2 P nanoparticle @ carbon@CNTs composite material.
4. The Co according to claim 3 2 The preparation method of the P nano particle@carbon@CNTs composite material is characterized by comprising the step (1), wherein the volume ratio of concentrated nitric acid to concentrated sulfuric acid in the reaction is 1:2.
5. The Co according to claim 3 2 The preparation method of the P nano particle@carbon@CNTs composite material is characterized by comprising the step (1), wherein the molar mass ratio of the multiwall carbon nanotubes to the concentrated nitric acid to the concentrated sulfuric acid in the reaction is 2:15:37.
6. The Co according to claim 3 2 The preparation method of the P nano particle@carbon@CNTs composite material is characterized by comprising the step (1), wherein the heating reaction condition of an oil bath is 90 ℃ for 3 hours.
7. The Co according to claim 3 2 The preparation method of the P nano particle@carbon@CNTs composite material is characterized by comprising the step (2) of mixing MWCNTs-COOH with anhydrous methanol in a ratio of 2mg to 7.5ml.
8. The Co according to claim 3 2 The preparation method of the P nano particle@carbon@CNTs composite material is characterized by comprising the following steps of (2) MWCNTs-COOH, polyvinylpyrrolidone and CoCl 2 And 2-methylimidazole at a mass ratio of 1:16:10:33, aging conditions of 25℃for 12 hours.
9. The Co according to claim 3 2 P nano particle @ carbon@CNTs composite materialThe preparation method is characterized in that in the step (3), the phosphating reaction conditions are as follows: in a tube furnace, 0.1g of the obtained product was placed downstream and 1.5g of sodium hypophosphite was placed upstream, followed by argon and incubation at 300℃for 2 hours.
10. A Co according to any one of claims 1 or 2 2 The application of the P nano particle@carbon@CNTs composite material in the field of lithium ion battery anode materials.
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