CN111092212A - Preparation method of carbon nanotube penetrating type growth MOF composite electrode material - Google Patents
Preparation method of carbon nanotube penetrating type growth MOF composite electrode material Download PDFInfo
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- CN111092212A CN111092212A CN201911411035.3A CN201911411035A CN111092212A CN 111092212 A CN111092212 A CN 111092212A CN 201911411035 A CN201911411035 A CN 201911411035A CN 111092212 A CN111092212 A CN 111092212A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 47
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 47
- 239000007772 electrode material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000012924 metal-organic framework composite Substances 0.000 title claims abstract description 12
- 230000000149 penetrating effect Effects 0.000 title abstract description 12
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 238000002604 ultrasonography Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 26
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 238000004140 cleaning Methods 0.000 claims 1
- 238000007599 discharging Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 7
- 230000035515 penetration Effects 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 description 25
- 229910052799 carbon Inorganic materials 0.000 description 19
- 239000000463 material Substances 0.000 description 10
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- -1 cobalt Prussian blue analogue Chemical class 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- UCFIGPFUCRUDII-UHFFFAOYSA-N [Co](C#N)C#N.[K] Chemical compound [Co](C#N)C#N.[K] UCFIGPFUCRUDII-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- QVYIMIJFGKEJDW-UHFFFAOYSA-N cobalt(ii) selenide Chemical compound [Se]=[Co] QVYIMIJFGKEJDW-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- ZAPXGKVOIFARAC-UHFFFAOYSA-M sodium;acetate;tetrahydrate Chemical compound O.O.O.O.[Na+].CC([O-])=O ZAPXGKVOIFARAC-UHFFFAOYSA-M 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
Abstract
The invention belongs to the technical field of electrode material preparation, and particularly relates to a preparation method of a carbon nanotube through type growth MOF composite electrode material. And uniformly mixing the carbon nanotube solution and the precursor solution of the MOF, and then carrying out ultrasound. The invention uses simple ultrasonic method to make MOF grow on the carbon nano tube in a penetrating way, which is equivalent to the pinning effect, and improves the structural stability of the MOF derivative. Therefore, the penetration of the carbon nano tube can effectively relieve the structure collapse effect of the MOF derivative in the charging and discharging processes, and the cycle performance of the MOF derivative is obviously improved.
Description
The technical field is as follows:
the invention belongs to the technical field of electrode material preparation, and particularly relates to a preparation method of a carbon nanotube through type growth MOF composite electrode material.
Background art:
in recent years, metal organic framework Materials (MOFs) have been widely researched and applied in electrode materials of energy storage devices due to their advantages of large specific surface area, adjustable structure, many pores, and the like. Researchers often use MOFs as self-sacrificial templates to prepare various MOF-derived materials, which not only can retain their porous structures, but also can effectively improve their electrical conductivity, and when used as electrode materials, can significantly improve the energy density and power density of batteries.
The derivative materials of MOFs typically take two forms, one of which is MX (M ═ Fe, Co, Mn, Ni, etc.; X ═ O, S, Se, P, etc.); the other is MX @ Carbon composite material. However, MOF derivatives often suffer from the following problems when used as electrode materials: (1) as for the MX derivative, the microstructure is formed by assembling a plurality of small particles, the structure is unstable, the MX derivative is easy to collapse in the charging and discharging process, the active material falls off, the capacity and the cycle life of the battery are affected, and meanwhile, the problem of poor conductivity is also existed, and the rate capability of the battery is affected. (2) For MX @ Carbon derivative materials, because the Carbon content of a lot of MOFs is not high, the MX @ Carbon derivatives can not form a stable Carbon skeleton generally, the structure still collapses under the action of large stress in the process of lithium, sodium and other ions deintercalation, and the active materials fall off, so that the capacity and the cycle performance of the materials are influenced. The above disadvantages severely limit the practical application of MOF and its derivative materials.
The composition with carbon materials such as carbon nano tubes, graphene and the like is one of feasible ways for improving the electrochemical energy storage performance of the MOF derivative. However, most of the composites are limited to attaching the MOF derivatives to the surface of the carbon-based material, and the collapse of the structure of the MOF derivatives during the charging and discharging process cannot be effectively relieved.
The invention content is as follows:
the invention aims to solve the technical problem that most composite materials are only limited to attach the MOF derivatives on the surface of a carbon-based material, and the structural collapse phenomenon of the MOF derivatives in the charging and discharging processes cannot be effectively relieved.
In order to solve the problems, the MOF is grown on a single or a plurality of carbon nanotubes in a penetrating way by a simple ultrasonic method, or the carbon nanotubes are completely coated in the MOF to form an amber-like composite material, and the composite material can fully exert the characteristics of high active site and high specific capacity of the MOF derivative. The three-dimensional conductive network formed by the carbon nanotubes can improve the overall conductivity of the composite material, and can also preferentially relieve the volume expansion effect of the MOF derivative electrode material in the charging and discharging processes, thereby improving the rate capability and the cycle performance of the composite material.
In order to achieve the purpose, the invention is realized by the following technical scheme: a preparation method of a carbon nanotube penetrating type growth MOF composite electrode material comprises the steps of uniformly mixing a carbon nanotube solution and a precursor solution of MOF, and then carrying out ultrasound. The MOF grows on the carbon nano tube in a penetrating mode through a simple ultrasonic method, which is equivalent to a pinning effect, and the structural stability of the MOF derivative is improved. Therefore, the penetration of the carbon nano tube can effectively relieve the structure collapse effect of the MOF derivative in the charging and discharging processes, and the cycle performance of the MOF derivative is obviously improved.
Further, the ultrasonic time is 1-12 hours.
Furthermore, the preparation method of the carbon nano tube is that the carbon nano tube is ultrasonically treated in the water solution to be uniformly dispersed, and the type and the quality of the carbon tube have no fixed requirements. To facilitate the introduction of the synthesis procedure, the inventors configured the suspension with 40mg of carbon nanotubes.
Further, the method for preparing the precursor solution of the MOF comprises the following steps: precursor solutions of MOFs were configured in a dissolution process at room temperature. Any precursor solution of MOF is suitable. The synthesis method is described here by taking cobalt Prussian blue analogue Co-Co-PBA as an example. Dissolving 1.2mmol of sodium acetate tetrahydrate and 1.8mmol of sodium citrate in 20ml of water to form a solution A; dissolving 0.8mmol of potassium cobalt cyanide in 20ml of water to form a solution B; and (3) quickly pouring the solution A into the solution B to form a precursor solution of the Co-Co-PBA after stirring for 1 minute.
Further, after ultrasonic treatment, the mixed solution is centrifugally cleaned and then dried at 60-100 ℃. Preferably 60-80 deg.C. Drying in vacuum atmosphere can accelerate drying speed.
Further, the dried product is subjected to heat treatment under different atmospheres according to requirements. For example, a Co3O4@ CNT composite is formed at 300 degrees in air; sintering the Co-CNT @ CNT composite at 500-1000 ℃ under an inert atmosphere; in addition, the composite electrode material of cobalt sulfide, cobalt selenide, cobalt phosphide, cobalt nitride and carbon nano tubes can be formed by sulfurization, selenization, phosphorization and nitridation.
The composite electrode material prepared by the method also has the advantages that partial carbon tubes have no MOF growth, but the composite electrode material and other MOF growth carbon tubes jointly construct a three-dimensional conductive network. The amount of carbon tubes in the reaction is usually too much to ensure that each MOF penetrates or coats the carbon tubes after the reaction is finished, but cannot ensure that MOFs grow on each carbon tube. So there are two structures in the solution after the reaction: one is MOF that penetrates or coats the carbon tubes, and the other is individual carbon tubes. The periphery of the MOF grown in a penetrating way can also be penetrated by carbon tubes, the penetrated carbon tubes can be mutually wound with other carbon tubes without MOF grown to form a three-dimensional network, actually, redundant carbon tubes can form a three-dimensional conductive network, and all electrode materials can be integrally formed by winding the carbon tubes grown in the penetrating way and other carbon tubes, so that the integral stability of the structure is improved, and the cycle performance and the multiplying power performance of the material are further improved.
While the ultrasonic method is a necessary method for forming the structure and is a highlight of the invention, the inventor also adopts a stirring and standing method, and the MOF in the obtained material cannot grow on the carbon nano tubes in a penetrating way and is only simple mechanical mixing. The carbon tubes and the MOF solution are always in a suspension state by ultrasound and are uniformly dispersed in the solution, the growth of the MOF is a reaction of gradually sinking, the MOF is finally collected at the bottom of the bottle, and the carbon nanotubes are also sunk if the carbon nanotubes are static. The ultrasound provides external energy in the formation of the MOF, the MOF is always in a suspension state in the growth process, and the carbon nanotubes can be coated under the action of the ultrasound in the crystal nucleus growth process to realize the through growth.
In addition, the invention not only can coat the prepared material on the current collector by a slurry coating method, but also can form the self-supporting electrode material by a vacuum filtration method, thereby avoiding the use of a binder and a conductive agent and obviously improving the energy density.
The invention has the beneficial effects that:
(1) the composite material of the present invention has a three-dimensional conductive network. Unlike other composite structures of carbon materials and MOFs, the present invention grows MOFs on single or multiple carbon nanotubes throughout, or coats carbon nanotubes completely within MOFs to form amber-like composites. In addition, some carbon tubes were not MOF grown, but together with other MOF grown carbon tubes, a three-dimensional conductive network was constructed.
(2) The preparation method is simple, low in cost and capable of realizing large-scale preparation. The invention adopts a simple ultrasonic method to form a structure, and the MOF grows on the carbon nano tube in a penetrating way, which is equivalent to a pinning effect, and improves the structural stability of the MOF derivative. In contrast to the stirring and static methods, the MOF in the resulting material does not grow throughout the carbon nanotubes, but is simply mechanically mixed.
(3) The application range is wide. The structure method for the carbon nanotube penetrating type MOF growth is simple, has wide practicability, is suitable for all kinds of carbon nanotubes and MOFs, has no regulation on the amount of the carbon nanotubes, and is prepared according to personal requirements.
(4) The composite material can fully exert the characteristics of high active sites and high specific capacity of MOF derivatives. The three-dimensional conductive network formed by the carbon nanotubes can improve the overall conductivity of the composite material, and can also preferentially relieve the volume expansion effect of the MOF derivative electrode material in the charging and discharging processes, thereby improving the rate capability and the cycle performance of the composite material.
Drawings
FIG. 1 is a composite scanning electron microscope picture I of the present invention;
FIG. 2 is a composite scanning electron microscope picture II of the present invention;
FIG. 3 is a composite scanning electron microscope image III of the present invention;
FIG. 4 is a composite scanning electron micrograph IV of the present invention.
The specific implementation mode is as follows:
in order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a preparation method of a carbon nanotube through type growth MOF composite electrode material comprises the following steps:
(1) 40mg of carbon nanotubes were sonicated in an aqueous solution to disperse uniformly.
(2) Dissolving 1.2mmol of sodium acetate tetrahydrate and 1.8mmol of sodium citrate in 20ml of water to form a solution A; dissolving 0.8mmol of potassium cobalt cyanide in 20ml of water to form a solution B; and (3) quickly pouring the solution A into the solution B to form a precursor solution of the Co-Co-PBA after stirring for 1 minute.
(3) And (3) uniformly mixing the carbon nanotube solution in the step (1) with the precursor solution of the Co-Co-PBA in the step (2), and then putting into the mixture for ultrasonic treatment for 1 to 12 hours.
(4) After the ultrasonic treatment, the mixed solution was subjected to centrifugal washing and then dried under vacuum at 60 ℃.
(5) Carrying out heat treatment on Co-Co-PBA with carbon nanotubes growing in a penetrating way under different atmospheres according to requirements: generating a compound of Co3O4@ CNT at 300 ℃ in air; the Co-CNT @ CNT composite is sintered under an inert atmosphere at 500-1000 ℃.
In addition, the composite electrode material of cobalt sulfide, cobalt selenide, cobalt phosphide, cobalt nitride and carbon nano tubes can be formed by sulfurization, selenization, phosphorization and nitridation. The preparation method comprises the steps of vulcanizing, selenizing, phosphorizing and nitriding the MOF and carbon nano tube composite material by using elemental sulfur, elemental selenium, sodium dihydrogen hypophosphite and ammonia gas at the temperature of 350-500 ℃.
Claims (6)
1. A preparation method of a carbon nanotube through type growth MOF composite electrode material is characterized by comprising the following steps: and uniformly mixing the carbon nanotube solution and the precursor solution of the MOF, and then carrying out ultrasound.
2. A method of making a carbon nanotube through-growth MOF composite electrode material of claim 1, wherein: the ultrasonic time is 1-12 hours.
3. A method of making a carbon nanotube through-growth MOF composite electrode material of claim 1, wherein: the preparation method of the carbon nano tube comprises the step of carrying out ultrasonic treatment on the carbon nano tube in an aqueous solution until the carbon nano tube is uniformly dispersed.
4. A method of making a carbon nanotube through-growth MOF composite electrode material of claim 1, wherein: precursor solutions of MOFs were configured in a dissolution process at room temperature.
5. A method of making a carbon nanotube through-growth MOF composite electrode material of claim 1, wherein: and after ultrasonic treatment, centrifugally cleaning the mixed solution, and then drying at 60-100 ℃.
6. A method of making a carbon nanotube through-growth MOF composite electrode material of claim 1, wherein: and carrying out heat treatment on the dried product under different atmospheres according to requirements.
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| CN115180656A (en) * | 2022-07-06 | 2022-10-14 | 青海师范大学 | Multi-shell hollow spherical Co 3 O 4 -CNTs composite material, preparation method and application thereof |
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