CN112467132A - Bimetal organic frame battery cathode material and preparation method thereof - Google Patents
Bimetal organic frame battery cathode material and preparation method thereof Download PDFInfo
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- CN112467132A CN112467132A CN202011193021.1A CN202011193021A CN112467132A CN 112467132 A CN112467132 A CN 112467132A CN 202011193021 A CN202011193021 A CN 202011193021A CN 112467132 A CN112467132 A CN 112467132A
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- 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
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The invention discloses a bimetal organic frame battery cathode material and a preparation method thereof, wherein the cathode material consists of a copper-nickel bimetal complex, conductive carbon black, a binder and a solvent, the copper-nickel bimetal complex in the cathode material is in dispersion distribution, and the method comprises the steps of preparing a bimetal mixed solution, heating the bimetal mixed solution and preparing an electrode. Compared with the existing metal organic framework such as cobalt which is applied to lithium batteries more, the copper-nickel bimetallic organic framework provided by the invention has the advantages that the price of the original material is low, the capacity contained in the material is large, and the cost performance is higher than that of the traditional product.
Description
Technical Field
The invention relates to the field of lithium ion electrode materials, in particular to a bimetallic organic frame battery cathode material.
Background
The lithium ion battery is one of the most widely used secondary batteries at present, but with the progress of science and technology and life, the lithium ion battery with low capacity can not meet the living needs of people. The theoretical specific capacity of the graphite serving as the current commercialized negative electrode material of the lithium ion battery is only 372mAh/g, so that a novel negative electrode material is urgently needed to replace the graphite.
The metal organic framework is mainly applied to the fields of catalysis, hydrogen storage and the like at present, and can be used as a template to prepare transition metal oxide and applied to energy storage. At present, most metal organic frameworks are difficult to be directly used as lithium ion battery cathode materials, and can only be used as precursors to prepare transition metal oxide cathodes. The transition metal oxide cathode prepared from the metal organic framework can inherit the advantages of large specific surface area, regular pore channels and the like of the metal organic framework material, but also has various defects of the transition metal oxide cathode, such as poor reversibility, low energy efficiency and the like. The metal organic framework material is directly used, so that compared with the corresponding oxide, the preparation method is simpler, energy-saving and more suitable for industrialization. Meanwhile, the current research shows that the bimetallic organic framework material has more advantages than a single-metal organic framework material due to the synergistic effect of two metal parts, and meanwhile, the specific capacity of the copper-nickel bimetallic organic framework is higher than that of other metals.
At present, few metal organic frameworks are directly used as lithium ion battery cathode materials, and most of the discovered metal organic frameworks cannot meet the requirements of the lithium ion battery cathode materials. The invention finds a bimetallic organic framework which can be directly used as a lithium ion battery cathode material, and the charge-discharge performance of the bimetallic organic framework can exceed that of the current commercial graphite cathode material. Compared with transition metal oxide prepared from the metal organic framework, the preparation process of the bimetal organic framework is simpler and energy-saving. Compared with a common single metal organic framework, the double metal organic framework has better cycle performance and higher charge-discharge capacity.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a bimetal organic frame battery cathode material.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention relates to a bimetal organic frame battery cathode material which is composed of a copper-nickel bimetal complex, conductive carbon black, a binder and a solvent, wherein the copper-nickel bimetal complex in the cathode material is in dispersion distribution.
As a preferable technical solution of the present invention, the nickel metal compound is one of nickel metal hydrochloride, nickel metal oxalate and nickel metal acetate, the solvent is one of DMF, methanol and ethanol, and the ligand is one of terephthalic acid, isophthalic acid and 2-methylimidazole.
The invention also provides a preparation method of the bimetal organic frame battery cathode material, which comprises the following steps: A. preparing a bimetal mixed solution;
weighing 0.01mol Cu (NO)3)2·xH2Dissolving O and 0.005mol of nickel metal compound in 30ml of solvent, magnetically stirring until the O and the 0.005mol of nickel metal compound are completely dissolved to obtain a metal salt solution, simultaneously weighing 0.01mol of ligand, dissolving in 30ml of solvent, magnetically stirring until the ligand is completely dissolved, then pouring the metal salt solution into the ligand solution, and stirring until the metal salt solution is completely dissolved to obtain a bimetal mixed solution;
B. carrying out solvent heat treatment on the bimetal mixed solution;
transferring the bimetal mixed solution into a polytetrafluoroethylene lining reaction kettle for sealing, carrying out solvothermal reaction for 24 hours at 120-150 ℃, carrying out suction filtration and collection on a product obtained by the reaction, carrying out vacuum drying for 12 hours at 80 ℃, and grinding into powder after drying to obtain powder D;
C. preparing an electrode;
uniformly mixing the powder D, the conductive carbon black and the binder according to the ratio of 7:2:1, adding a solvent NMP to prepare slurry, coating the slurry on one side of a copper foil, drying at the temperature of 80 ℃ for 8-12 h, and then cutting the copper foil into a circular pole piece with the diameter of 12mm to obtain the pole piece of the lithium ion battery.
As a preferred technical scheme of the invention, the nickel metal compound in the step A is NiCl2·6H2O、NiC2O4And Ni (CH)3COO)2·4H2One in OThe solvent is DMF, namely N, N-dimethylformamide, and the ligand is terephthalic acid.
Compared with the prior art, the invention has the following beneficial effects:
1: the preparation process of the organic metal frame is short and simple, and is favorable for directly forming a process production line for efficient production.
2: compared with the existing metal organic framework such as cobalt which is applied to lithium batteries more, the copper-nickel bimetallic organic framework provided by the invention has the advantages that the price of the original material is low, the capacity contained in the material is large, and the cost performance is higher than that of the traditional product.
3: compared with the transition metal oxide prepared by the metal organic framework, the metal organic framework is directly used, so that the calcining process is omitted, more greening and energy saving are realized in industrial production, and the emission of waste gas is reduced.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a graph of specific discharge capacity of a bimetallic organic framework material of the present invention;
FIG. 2 is a graph of the run cycle of the bimetallic organic framework material of the present invention;
FIG. 3 is a scanning electron micrograph of a bimetallic organic framework material of the present invention;
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
Example 1
The invention provides a bimetal organic frame battery cathode material, which consists of a copper-nickel bimetal complex, conductive carbon black, a binder and a solvent, wherein the copper-nickel bimetal complex in the cathode material is in dispersion distribution.
The preparation method of the cathode material of the bimetallic organic frame battery is characterized by comprising the following specific steps of:
A. preparing a bimetal mixed solution;
weighing 0.01mol Cu (NO)3)2·xH2O and 0.005mol NiCl2·6H2Dissolving O in 30ml of DMF, magnetically stirring until the solution is completely dissolved to obtain a metal salt solution, meanwhile, weighing 0.01mol of terephthalic acid, dissolving in 30ml of DMF, magnetically stirring until the solution is completely dissolved, then pouring the metal salt solution into the terephthalic acid solution, and stirring until the solution is completely dissolved to obtain a bimetal mixed solution;
B. carrying out solvent heat treatment on the bimetal mixed solution;
transferring the bimetal mixed solution into a polytetrafluoroethylene lining reaction kettle for sealing, carrying out solvothermal reaction for 24 hours at 120 ℃, carrying out suction filtration and collection on a product obtained by the reaction, carrying out vacuum drying for 12 hours at 80 ℃, and grinding into powder after drying to obtain powder D;
C. preparing an electrode;
uniformly mixing the powder D, the conductive carbon black and the binder according to the ratio of 7:2:1, adding a solvent NMP to prepare slurry, coating the slurry on one side of a copper foil, drying at the temperature of 80 ℃ for 8-12 h, and then cutting the copper foil into a circular pole piece with the diameter of 12mm to obtain the pole piece of the lithium ion battery.
Assembling the finally obtained battery pole piece into a lithium ion battery, testing the cycle performance of the lithium ion battery, activating the lithium ion battery 5 circles before the cycle under the current density of 50mA/g, and testing the cycle performance of the lithium ion battery in the subsequent cycle under the current density of 200mA/g, wherein the cycle performance is shown in figures 1 and 2;
as can be seen from figure 1, the first discharge specific capacity of the negative electrode material is 1985.4mAh/g, the first charge specific capacity is 909.5mAh/g, and the first coulombic efficiency is 45.81%. As can be seen from FIG. 2, after 90 cycles of cycling, the specific charge capacity is 771.1mAh/g, the capacity retention rate is 84.8%, and the specific charge capacity is still activated and improved as the cycling is advanced. Therefore, the lithium ion battery prepared by using the bimetallic organic frame cathode material has good cycle stability.
The characterization of the line Scanning Electron Microscope (SEM) of the bimetallic organic framework material prepared in this example can be seen from fig. 3, that the material prepared by the above experiment has a three-dimensional micro-flower structure, is a space group structure, and has formed uniform particles.
Example 2
Mixing NiCl2·6H2Changing O into NiC2O4Pole pieces were fabricated according to the method of example 1, steps a-C.
Example 3
Mixing NiCl2·6H2Changing O to Ni (CH)3COO)2·4H2O, the temperature of 120 ℃ solvothermal reaction for 24 hours in step B was changed to 150 ℃ solvothermal reaction for 24 hours, and the rest of the procedure was the same as in example 1.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. The cathode material is characterized by consisting of a copper-nickel bimetallic complex, conductive carbon black, a binder and a solvent, wherein the copper-nickel bimetallic complex in the cathode material is in dispersion distribution.
2. The bimetallic organic framework battery anode material as in claim 1, wherein the nickel metal compound is one of nickel metal hydrochloride, nickel metal oxalate and nickel metal acetate, the solvent is one of DMF, methanol and ethanol, and the ligand is one of terephthalic acid, isophthalic acid and 2-methylimidazole.
3. The preparation method of the bimetallic organic frame battery cathode material as claimed in claim 1, is characterized by comprising the following specific steps:
A. preparing a bimetal mixed solution;
weighing 0.01mol Cu (NO)3)2·xH2Dissolving O and 0.005mol of nickel metal compound in 30ml of solvent, magnetically stirring until the O and the 0.005mol of nickel metal compound are completely dissolved to obtain a metal salt solution, simultaneously weighing 0.01mol of ligand, dissolving in 30ml of solvent, magnetically stirring until the ligand is completely dissolved, then pouring the metal salt solution into the ligand solution, and stirring until the metal salt solution is completely dissolved to obtain a bimetal mixed solution;
B. carrying out solvent heat treatment on the bimetal mixed solution;
transferring the bimetal mixed solution into a polytetrafluoroethylene lining reaction kettle for sealing, carrying out solvothermal reaction for 24 hours at 120-150 ℃, carrying out suction filtration and collection on a product obtained by the reaction, carrying out vacuum drying for 12 hours at 80 ℃, and grinding into powder after drying to obtain powder D;
C. preparing an electrode;
uniformly mixing the powder D, the conductive carbon black and the binder according to the ratio of 7:2:1, adding a solvent NMP to prepare slurry, coating the slurry on one side of a copper foil, drying at the temperature of 80 ℃ for 8-12 h, and then cutting the copper foil into a circular pole piece with the diameter of 12mm to obtain the pole piece of the lithium ion battery.
4. The method of claim 3, wherein the nickel metal compound in step A is NiCl2·6H2O、NiC2O4And Ni (CH3COO)2·4H2And in O, the solvent is DMF (dimethyl formamide), namely N, N-dimethylformamide, and the ligand is terephthalic acid.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107732248A (en) * | 2017-11-21 | 2018-02-23 | 盐城工学院 | The MOF materials of negative electrode of lithium ion battery and its application |
| CN109817980A (en) * | 2019-03-21 | 2019-05-28 | 合肥华思系统有限公司 | The preparation method of secondary battery electrode active materials and secondary cell containing the material |
| KR101986247B1 (en) * | 2017-12-14 | 2019-06-07 | 한국과학기술연구원 | Process for preparation of Negative electrode active material comprising N-doped carbon-layer coated porous metal oxide and secondary battery using the same |
| CN111009421A (en) * | 2019-11-22 | 2020-04-14 | 中国矿业大学 | Lamellar bimetallic organic framework compound and preparation method and application thereof |
| CN111690147A (en) * | 2020-06-11 | 2020-09-22 | 上海大学 | Bimetal coordination polymer electrode material and preparation method thereof |
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- 2020-10-30 CN CN202011193021.1A patent/CN112467132A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107732248A (en) * | 2017-11-21 | 2018-02-23 | 盐城工学院 | The MOF materials of negative electrode of lithium ion battery and its application |
| KR101986247B1 (en) * | 2017-12-14 | 2019-06-07 | 한국과학기술연구원 | Process for preparation of Negative electrode active material comprising N-doped carbon-layer coated porous metal oxide and secondary battery using the same |
| CN109817980A (en) * | 2019-03-21 | 2019-05-28 | 合肥华思系统有限公司 | The preparation method of secondary battery electrode active materials and secondary cell containing the material |
| CN111009421A (en) * | 2019-11-22 | 2020-04-14 | 中国矿业大学 | Lamellar bimetallic organic framework compound and preparation method and application thereof |
| CN111690147A (en) * | 2020-06-11 | 2020-09-22 | 上海大学 | Bimetal coordination polymer electrode material and preparation method thereof |
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