CN113666343A - Organic metal frame structure nickel-cobalt selenide and preparation method and application thereof - Google Patents
Organic metal frame structure nickel-cobalt selenide and preparation method and application thereof Download PDFInfo
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- CN113666343A CN113666343A CN202110953306.9A CN202110953306A CN113666343A CN 113666343 A CN113666343 A CN 113666343A CN 202110953306 A CN202110953306 A CN 202110953306A CN 113666343 A CN113666343 A CN 113666343A
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- PYHYDDIOBZRCJU-UHFFFAOYSA-N [Ni]=[Se].[Co] Chemical compound [Ni]=[Se].[Co] PYHYDDIOBZRCJU-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 27
- 239000002184 metal Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 39
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 13
- 239000010941 cobalt Substances 0.000 claims abstract description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052786 argon Inorganic materials 0.000 claims abstract description 10
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 8
- 239000010431 corundum Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 13
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 12
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 7
- 238000003837 high-temperature calcination Methods 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- 229940078494 nickel acetate Drugs 0.000 claims description 7
- 229940011182 cobalt acetate Drugs 0.000 claims description 6
- 229940044175 cobalt sulfate Drugs 0.000 claims description 6
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 6
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 6
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims description 6
- 229960001826 dimethylphthalate Drugs 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 125000002524 organometallic group Chemical group 0.000 claims 8
- 239000007772 electrode material Substances 0.000 abstract description 13
- 239000011149 active material Substances 0.000 abstract description 6
- 230000008859 change Effects 0.000 abstract description 3
- 238000007599 discharging Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000004020 conductor Substances 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- QVYIMIJFGKEJDW-UHFFFAOYSA-N cobalt(ii) selenide Chemical compound [Se]=[Co] QVYIMIJFGKEJDW-UHFFFAOYSA-N 0.000 description 9
- 239000012621 metal-organic framework Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 8
- 239000011889 copper foil Substances 0.000 description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- WWECJGLXBSQKRF-UHFFFAOYSA-N n,n-dimethylformamide;methanol Chemical compound OC.CN(C)C=O WWECJGLXBSQKRF-UHFFFAOYSA-N 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 229910013872 LiPF Inorganic materials 0.000 description 4
- 101150058243 Lipf gene Proteins 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002932 luster Substances 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 239000011268 mixed slurry Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- -1 transition metal selenides Chemical class 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000003346 selenoethers Chemical class 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
-
- 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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
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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
- H01M4/58—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
- H01M4/581—Chalcogenides or intercalation compounds thereof
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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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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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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
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Abstract
The invention relates to the technical field of new energy electrode material preparation, in particular to an organic metal frame structure nickel-cobalt selenide and a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) dissolving a nickel source, a cobalt source and a carbon source in the mixed solution, uniformly stirring, transferring the mixture into a reaction container, and reacting at the temperature of 150-; after the reaction is finished, centrifuging, washing and drying the product to obtain a nickel-cobalt selenide precursor NiCo-MOF with an organic metal framework structure; 2) putting the precursor NiCo-MOF of the nickel cobalt selenide and selenium powder into a corundum ark, and calcining for a period of time at a high temperature in argon flow to obtain a target product. The product obtained by the method has larger specific surface area, the reaction interface is increased, and the volume change of the active material in the charging and discharging process can be effectively buffered by proper amount of carbon coating; compared with the prior art, the conductive material has the characteristics of high conductivity, long cycle life, environmental protection, simple preparation and excellent performance.
Description
Technical Field
The invention relates to the technical field of new energy electrode material preparation, in particular to an organic metal frame structure nickel-cobalt selenide and a preparation method and application thereof.
Background
Lithium ion batteries have a high energy density, good safety and stability, and a long cycle life, and are therefore of great interest. The negative electrode material composing the battery is a research hotspot in recent years, however, the negative electrode material has a series of problems of large volume change, low conductivity and the like in the charging and discharging processes. Therefore, in order to develop a suitable anode material suitable for a lithium ion battery, the anode material needs to be optimized. Binary transition metal selenides have higher conductivity and more electrochemically reactive active sites than monometallic selenides, and are therefore often used as negative electrode materials for lithium ion batteries for research.
With the continuous development of battery technology, the requirement on binary transition metal selenide is higher and higher, and the binary transition metal selenide needs to be modified, so that the conductivity and the comprehensive electrochemical performance of the binary transition metal selenide are further improved.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide the nickel-cobalt selenide with the organic metal framework structure and the preparation method and the application thereof.
In order to achieve the technical purpose and achieve the technical effect, the invention is realized by the following technical scheme:
a preparation method of nickel-cobalt selenide with an organic metal framework structure comprises the following steps:
1) preparing a nickel cobalt selenide precursor: dissolving a nickel source, a cobalt source and a carbon source in a mixed solution of dimethyl phthalate, deionized water, N-dimethylformamide methanol and ethylene glycol according to a certain proportion, uniformly stirring, transferring the mixture into a reaction container, and reacting at the temperature of 150 ℃ and 200 ℃ for 6-18 hours; after the reaction is finished, centrifuging, washing and drying the product to obtain a nickel-cobalt selenide precursor NiCo-MOF with an organic metal framework structure;
2) preparing nickel cobalt selenide: and placing a certain amount of nickel cobalt selenide precursor NiCo-MOF on one side of the corundum ark, placing a proper amount of selenium powder on the other side of the small ark, and calcining for a period of time at a high temperature in argon flow at a certain flow rate to obtain the target product nickel cobalt selenide/carbon composite material.
Further, in the preparation method of the organic metal framework structure nickel-cobalt selenide, in step 1), the nickel source is at least one of nickel acetate, nickel nitrate and nickel sulfate, the cobalt source is at least one of cobalt acetate, cobalt nitrate and cobalt sulfate, and the carbon source is at least one of 1,3, 5-benzenetricarboxylic acid, polyvinylpyrrolidone, sucrose and ascorbic acid.
Further, in the preparation method of the organic metal framework structure nickel cobalt selenide, in the step 1), the molar ratio of the nickel source to the cobalt source is 3-5:3-5, and the adding amount of the carbon source is 7-14 wt% of the total mass of the cobalt source and the nickel source.
Further, in the preparation method of the organic metal framework structure nickel cobalt selenide, in the step 1), the volume ratio of the dimethyl phthalate, the deionized water, the N, N-dimethylformamide methanol and the ethylene glycol in the mixed solution is 10-60:30-60:10-60: 10-60.
Further, in the preparation method of the nickel cobalt selenide with the organic metal framework structure, in the step 1), the mass ratio of the nickel cobalt selenide precursor NiCo-MOF to the selenium powder is 1-2: 3-6.
Further, in the preparation method of the organic metal framework structure nickel cobalt selenide, step 2), the flow rate of the argon gas is 25-60 mL/min.
Further, in the preparation method of the nickel-cobalt selenide with the organic metal framework structure, in the step 2), during the high-temperature calcination, the temperature is raised to 550-850 ℃ at the temperature rise rate of 3-5 ℃/min, and then the calcination is carried out for 5-8h at the temperature.
The nickel-cobalt selenide with the organic metal framework structure is prepared by the preparation method.
The nickel-cobalt selenide with the organic metal framework structure is applied to a lithium ion battery. According to the application, the prepared nickel cobalt selenide/carbon composite material is used as a negative electrode material. Meanwhile, the metal lithium sheet is a counter electrode and a reference electrode, and the button cell can be assembled for electrochemical performance test.
The invention has the beneficial effects that:
the method utilizes the characteristics of large specific surface area, high porosity, adjustable structure and function and the like of metal-organic frameworks (MOFs), adopts a method of combining solvothermal synthesis with high-temperature calcination heat treatment to prepare the nickel-cobalt selenide negative electrode material derived from the MOF, obtains a controllable preparation technology of the carbon-coated nickel-cobalt selenide, can effectively relieve the volume change of an active material in the charging and discharging process through carbon coating, improves the conductivity of the material, and increases the specific surface area of the electrode material, so that the cycle performance and the rate capability of the electrode material are improved, the structure of the modified material is optimized, the conductivity is improved, and the comprehensive electrochemical performance is improved. The invention firstly utilizes the metal organic framework structure to be compounded with the double metal selenide, and provides a brand new idea for the selenide serving as the lithium ion battery cathode material.
Of course, it is not necessary for any one product that embodies the invention to achieve all of the above advantages simultaneously.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is an SEM image of cobalt selenide/carbon as an electrode material in example 1;
FIG. 2 is an XRD pattern of cobalt selenide/carbon as an electrode material in example 1;
FIG. 3 is a graph of the charge and discharge curves of cobalt selenide/carbon as an electrode material in example 1;
FIG. 4 is a graph of the cycle curve for cobalt selenide/carbon as the electrode material in example 1;
fig. 5 is a graph of the rate capability of cobalt selenide/carbon as the electrode material in example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and 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.
A preparation method of nickel-cobalt selenide with an organic metal framework structure comprises the following steps:
1) preparing a nickel cobalt selenide precursor: dissolving a nickel source, a cobalt source and a carbon source in a mixed solution of dimethyl phthalate, deionized water, N-dimethylformamide methanol and ethylene glycol according to a certain proportion, and uniformly stirring.
Wherein the nickel source is at least one of nickel acetate, nickel nitrate and nickel sulfate, and the total amount is 0.015-0.025 mol. The cobalt source is at least one of cobalt acetate, cobalt nitrate and cobalt sulfate, and the total amount is 0.015-0.025 mol. The carbon source is at least one of 1,3, 5-benzenetricarboxylic acid, polyvinylpyrrolidone (PVP), sucrose and ascorbic acid, and the adding amount of the carbon source is 7-14 wt% of the total mass of the cobalt source and the nickel source.
In the mixed solution, the volume ratio of the dimethyl phthalate, the deionized water, the N, N-dimethylformamide methanol and the ethylene glycol is 10-60:30-60:10-60:10-60, and the total volume of the four mixed solutions is about 80 mL.
Transferring the mixture into the lining of a high-pressure reaction kettle, and reacting at 150-200 ℃ for 6-18 time; after the reaction is finished, centrifuging, washing and drying the product to obtain a nickel-cobalt selenide precursor NiCo-MOF with an organic metal framework structure;
2) preparing nickel cobalt selenide: 200-400mg of nickel cobalt selenide precursor NiCo-MOF is placed on one side of the corundum ark, and 600-1200mg of selenium powder is placed on the other side of the small ark. Heating to 550-850 ℃ in 25-60mL/min argon flow at the heating rate of 3-5 ℃/min, and then calcining for 5-8h at the temperature to obtain the target product nickel-cobalt selenide/carbon composite material.
The nickel-cobalt selenide with the grain diameter of about 2 mu m forms a unique organic metal framework structure, and the structure has the characteristics of high porosity, larger specific surface area, and adjustable structure and function. The material is used as a lithium ion battery cathode material, is assembled into a button cell for electrochemical performance test, and has the first-cycle discharge specific capacity of 780mAh/g under the current density of 50 mA/g. The invention adopts different nickel sources, cobalt sources and different organic solvents to be mixed and react in a high-pressure reaction kettle to obtain a precipitate, and then the product and selenium powder are further calcined at high temperature to obtain a target product. The specific embodiment of the invention is as follows:
example 1
2.63g of nickel sulfate, 1.244g of nickel acetate, 1.454g of nickel nitrate, 2.81g of cobalt sulfate and 0.53g of PVP are respectively weighed by an antenna balance. It was transferred into a beaker having a volume of 200mL, followed by addition of 30mL of deionized water, 20mL of DMP, 20mL of ethylene glycol, 10mL of N, N-dimethylformamide methanol, and magnetic stirring at a rotation speed of 120r/min for 30 min. The mixture was then transferred to a 100mL kettle liner and allowed to react at 180 ℃ for 10 h. And after the reaction is finished, standing the reaction kettle, removing upper-layer liquid, centrifugally washing the reaction kettle for 3 times by using deionized water and 2 times by using ethanol at the rotating speed of 8000r/min by using a centrifugal machine, and then drying the reaction kettle for 12 hours in a vacuum drying oven at the temperature of 80 ℃.
300mg of the above product was placed on one side of a corundum ark, and 800mg of selenium powder was placed on the other side of the canoe. In argon flow with the flow rate of 50mL/min, the heating rate is set to be 4 ℃/min at 850 ℃, after high-temperature calcination is carried out for 5 hours, the temperature is slowly reduced to the room temperature along with furnace cooling, and the target product nickel cobalt selenide/carbon composite material is obtained.
The synthesized nickel-cobalt selenide/carbon composite material is assembled into an electrode, 240mg of active material nickel-cobalt selenide/carbon, 30mg of conductive agent acetylene black and 30mg of binder polyvinylidene fluoride (PVDF) are uniformly mixed until the mixed slurry has metallic luster, the prepared electrode slurry is uniformly coated on a copper foil with the thickness of 5cm multiplied by 6cm, the copper foil is taken out after vacuum drying for 12 hours at the temperature of 60 ℃, and the electrode is punched into a pole piece with the diameter of 8 mm.
The prepared cobalt selenide/carbon electrode material is used as a negative electrode, a metal lithium sheet is used as a counter electrode and a reference electrode, and the electrolyte is LiPF with the concentration of 1.0mol/L6The solvent is ethylene carbonate, dimethyl carbonate and diethyl carbonate according to the proportion of 1: 1: 1, and forming the button cell in a glove box with the water oxygen content lower than 0.01 ppm. And (3) carrying out cycle and rate performance test on the battery by using a charge-discharge tester at 0.1-3V.
Example 2
1.244g of nickel acetate, 2.81g of cobalt sulfate, 1.455g of cobalt nitrate, 2.49g of cobalt acetate and 0.96g of sucrose were weighed respectively by using a balance. It was transferred into a beaker having a volume of 200mL, followed by addition of 40mL of deionized water, 10mL of DMP, 10mL of ethylene glycol, 20mL of N, N-dimethylformamide methanol, and magnetic stirring at a rotation speed of 150r/min for 20 min. The mixture was then transferred to a 100mL kettle liner and allowed to react at 150 ℃ for 18 h. And after the reaction is finished, standing the reaction kettle, removing upper-layer liquid, centrifugally washing the reaction kettle for 3 times by using deionized water and 2 times by using ethanol at the rotating speed of 8000r/min by using a centrifugal machine, and then drying the reaction kettle for 12 hours in a vacuum drying oven at the temperature of 80 ℃.
400mg of the above product was placed on one side of a corundum ark, and 1000mg of selenium powder was placed on the other side of the small ark. In argon flow with the flow rate of 25mL/min, the heating rate is set to be 4 ℃/min at the temperature of 750 ℃, after high-temperature calcination is carried out for 6 hours, the temperature is slowly reduced to the room temperature along with furnace cooling, and the target product nickel-cobalt selenide/carbon composite material is obtained.
The synthesized nickel-cobalt selenide/carbon composite material is assembled into an electrode, 240mg of active material nickel-cobalt selenide/carbon, 30mg of conductive agent acetylene black and 30mg of binder polyvinylidene fluoride (PVDF) are uniformly mixed until the mixed slurry has metallic luster, the prepared electrode slurry is uniformly coated on a copper foil with the thickness of 5cm multiplied by 6cm, the copper foil is taken out after vacuum drying for 12 hours at the temperature of 60 ℃, and the electrode is punched into a pole piece with the diameter of 8 mm.
The prepared cobalt selenide/carbon electrode material is used as a negative electrode, a metal lithium sheet is used as a counter electrode and a reference electrode, and the electrolyte is LiPF with the concentration of 1.0mol/L6The solvent is ethylene carbonate, dimethyl carbonate and diethyl carbonate according to the proportion of 1: 1: 1, and forming the button cell in a glove box with the water oxygen content lower than 0.01 ppm. And (3) carrying out cycle and rate performance test on the battery by using a charge-discharge tester at 0.1-3V.
Example 3
2.63g of nickel sulfate, 1.244g of nickel acetate, 2.81g of cobalt sulfate, 1.245g of cobalt acetate and 0.63g of ascorbic acid were weighed respectively by using a balance. It was transferred into a beaker having a volume of 200mL, followed by addition of 50mL of deionized water, 10mL of DMP, 10mL of ethylene glycol, 10mL of N, N-dimethylformamide methanol, and magnetic stirring at a rotation speed of 190r/min for 15 min. The mixture was then transferred to a 100mL reactor liner and reacted at 200 ℃ for 6 h. And after the reaction is finished, standing the reaction kettle, removing upper-layer liquid, centrifugally washing the reaction kettle for 3 times by using deionized water and 2 times by using ethanol at the rotating speed of 8000r/min by using a centrifugal machine, and then drying the reaction kettle for 12 hours in a vacuum drying oven at the temperature of 80 ℃.
400mg of the above product was placed on one side of a corundum ark, and 1200mg of selenium powder was placed on the other side of the small ark. In argon flow with the flow rate of 40mL/min, the heating rate is set to be 4 ℃/min at 650 ℃, after high-temperature calcination is carried out for 7h, the temperature is slowly reduced to the room temperature along with furnace cooling, and the target product nickel cobalt selenide/carbon composite material is obtained.
The synthesized nickel-cobalt selenide/carbon composite material is assembled into an electrode, 240mg of active material nickel-cobalt selenide/carbon, 30mg of conductive agent acetylene black and 30mg of binder polyvinylidene fluoride (PVDF) are uniformly mixed until the mixed slurry has metallic luster, the prepared electrode slurry is uniformly coated on a copper foil with the thickness of 5cm multiplied by 6cm, the copper foil is taken out after vacuum drying for 12 hours at the temperature of 60 ℃, and the electrode is punched into a pole piece with the diameter of 8 mm.
The prepared cobalt selenide/carbon electrode material is used as a negative electrode, a metal lithium sheet is used as a counter electrode and a reference electrode, and the electrolyte is LiPF with the concentration of 1.0mol/L6The solvent is ethylene carbonate or carbonic acidMethyl ester and diethyl carbonate as 1: 1: 1, and forming the button cell in a glove box with the water oxygen content lower than 0.01 ppm. And (3) carrying out cycle and rate performance test on the battery by using a charge-discharge tester at 0.1-3V.
Example 4
A balance was used to weigh 1.244g of nickel acetate, 1.454g of nickel nitrate, 1.455g of cobalt nitrate, 1.245g of cobalt acetate, and 0.38g of 1,3, 5-benzenetricarboxylic acid, respectively. It was transferred into a beaker having a volume of 200mL, followed by addition of 60mL of deionized water, 5mL of DMP, 10mL of ethylene glycol, 5mL of N, N-dimethylformamide methanol, and magnetic stirring at a rotational speed of 240r/min for 10 min. The mixture was then transferred to a 100mL kettle liner and allowed to react at 160 ℃ for 15 h. And after the reaction is finished, standing the reaction kettle, removing upper-layer liquid, centrifugally washing the reaction kettle for 3 times by using deionized water and 2 times by using ethanol at the rotating speed of 8000r/min by using a centrifugal machine, and then drying the reaction kettle for 12 hours in a vacuum drying oven at the temperature of 80 ℃.
200mg of the above product was placed on one side of a corundum ark, and 600mg of selenium powder was placed on the other side of the small ark. In argon flow with the flow rate of 60mL/min, the heating rate is set to be 4 ℃/min at 550 ℃, after high-temperature calcination is carried out for 8 hours, furnace cooling is carried out, and the temperature is slowly reduced to the room temperature, so that the target product nickel-cobalt selenide/carbon composite material is obtained.
The synthesized nickel-cobalt selenide/carbon composite material is assembled into an electrode, 240mg of active material nickel-cobalt selenide/carbon, 30mg of conductive agent acetylene black and 30mg of binder polyvinylidene fluoride (PVDF) are uniformly mixed until the mixed slurry has metallic luster, the prepared electrode slurry is uniformly coated on a copper foil with the thickness of 5cm multiplied by 6cm, the copper foil is taken out after vacuum drying for 12 hours at the temperature of 60 ℃, and the electrode is punched into a pole piece with the diameter of 8 mm.
The prepared cobalt selenide/carbon electrode material is used as a negative electrode, a metal lithium sheet is used as a counter electrode and a reference electrode, and the electrolyte is LiPF with the concentration of 1.0mol/L6The solvent is ethylene carbonate, dimethyl carbonate and diethyl carbonate according to the proportion of 1: 1: 1, and forming the button cell in a glove box with the water oxygen content lower than 0.01 ppm. And (3) carrying out cycle and rate performance test on the battery by using a charge-discharge tester at 0.1-3V.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (10)
1. The preparation method of the nickel-cobalt selenide with the organic metal framework structure is characterized by comprising the following steps:
1) preparing a nickel cobalt selenide precursor: dissolving a nickel source, a cobalt source and a carbon source in a mixed solution of dimethyl phthalate, deionized water, N-dimethylformamide methanol and ethylene glycol according to a certain proportion, uniformly stirring, transferring the mixture into a reaction container, and reacting at the temperature of 150 ℃ and 200 ℃ for 6-18 hours; after the reaction is finished, centrifuging, washing and drying the product to obtain a nickel-cobalt selenide precursor NiCo-MOF with an organic metal framework structure;
2) preparing nickel cobalt selenide: and placing a certain amount of nickel cobalt selenide precursor NiCo-MOF on one side of the corundum ark, placing a proper amount of selenium powder on the other side of the small ark, and calcining for a period of time at a high temperature in argon flow at a certain flow rate to obtain the target product nickel cobalt selenide/carbon composite material.
2. The method of claim 1, wherein the organometallic framework nickel cobalt selenide comprises: in the step 1), the nickel source is at least one of nickel acetate, nickel nitrate and nickel sulfate, the cobalt source is at least one of cobalt acetate, cobalt nitrate and cobalt sulfate, and the carbon source is at least one of 1,3, 5-benzenetricarboxylic acid, polyvinylpyrrolidone, sucrose and ascorbic acid.
3. The method of claim 1, wherein the organometallic framework nickel cobalt selenide comprises: in the step 1), the molar ratio of the nickel source to the cobalt source is 3-5:3-5, and the addition amount of the carbon source is 7-14 wt% of the total mass of the cobalt source and the nickel source.
4. The method of claim 1, wherein the organometallic framework nickel cobalt selenide comprises: in the step 1), the volume ratio of dimethyl phthalate, deionized water, N-dimethylformamide methanol and ethylene glycol in the mixed solution is 10-60:30-60:10-60: 10-60.
5. The method of claim 1, wherein the organometallic framework nickel cobalt selenide comprises: in the step 1), the mass ratio of the nickel cobalt selenide precursor NiCo-MOF to the selenium powder is 1-2: 3-6.
6. The method of claim 1, wherein the organometallic framework nickel cobalt selenide comprises: in step 2), the argon flow rate is 25-60 mL/min.
7. The method of claim 1, wherein the organometallic framework nickel cobalt selenide comprises: in the step 2), during the high-temperature calcination, the temperature is raised to 550-850 ℃ at the heating rate of 3-5 ℃/min, and then the calcination is carried out for 5-8h at the temperature.
8. The organometallic framework nickel cobalt selenide prepared by the preparation method described in any one of claims 1 to 7.
9. Use of the organo-metallic framed nickel cobalt selenide of claim 8 in a lithium ion battery.
10. Use according to claim 9, characterized in that: the prepared nickel cobalt selenide/carbon composite material is used as a negative electrode material.
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