CN106558689B - A kind of electrochemical in-situ method prepares the method and its application of two-arch tunnel mixed metal selenides - Google Patents
A kind of electrochemical in-situ method prepares the method and its application of two-arch tunnel mixed metal selenides Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 9
- 239000002184 metal Substances 0.000 title claims description 27
- 229910052751 metal Inorganic materials 0.000 title claims description 27
- 150000003346 selenoethers Chemical class 0.000 title claims description 22
- 239000002114 nanocomposite Substances 0.000 claims abstract description 44
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 14
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 13
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 11
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 239000006104 solid solution Substances 0.000 claims description 11
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000002848 electrochemical method Methods 0.000 claims description 2
- 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 abstract description 18
- 229910052708 sodium Inorganic materials 0.000 abstract description 18
- 239000011734 sodium Substances 0.000 abstract description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 12
- 239000010405 anode material Substances 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract description 7
- 238000003860 storage Methods 0.000 abstract description 4
- -1 it can be mass Substances 0.000 abstract 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 230000004087 circulation Effects 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 9
- 239000006230 acetylene black Substances 0.000 description 9
- 239000001768 carboxy methyl cellulose Substances 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 9
- 238000000227 grinding Methods 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 9
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 9
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 8
- 239000011669 selenium Substances 0.000 description 8
- 229910001415 sodium ion Inorganic materials 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- VPQBLCVGUWPDHV-UHFFFAOYSA-N sodium selenide Chemical group [Na+].[Na+].[Se-2] VPQBLCVGUWPDHV-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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
-
- 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
-
- 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
- C01B19/007—Tellurides or selenides of metals
-
- 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
- H01M4/58—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of co-continuous CoSe2/NiSe2Nanocomposite and preparation method and application.Co-continuous CoSe provided by the present invention2/NiSe2Nanocomposite has outstanding storage sodium performance, is an excellent anode material of lithium-ion battery.It is simple and novel for the preparation method of the nanocomposite, it can be mass, raw material is easy to get, and shows good application value.More importantly, presoma has reached the uniform compound of molecular level in this method, the nanocomposite of the compound and its uniform co-continuous formed in situ by electrochemical process again, so as to avoid compound uneven, the discontinuous disadvantage of two-phase in conventional composite object preparation process.Co-continuous CoSe2/NiSe2Nanocomposite illustrates outstanding high rate performance and cycle performance when being used as anode material of lithium-ion battery.
Description
Technical field
The invention belongs to nano materials and sodium-ion battery technical field, are related to a kind of two-arch tunnel mixed metal selenides
Electrochemical in-situ preparation method and its application in anode material of lithium-ion battery.
Background technique
Due to high-energy density, safety and stability, the advantages that green high-efficient, memory-less effect, becomes lithium ion battery
Energy storage device of greatest concern.Currently, having been widely used for all kinds of portable electronic devices, electric vehicle, storage
The fields such as energy equipment.But since the resource of lithium in the earth's crust is relatively limited, with power battery and extensive energy storage to lithium from
The demand of sub- battery increases considerably, following to face severe lithium resource shortage problem.For comparing, sodium is on earth
Reserves it is extremely abundant, and sodium-ion battery is similar to the energy storage mechnism of lithium ion battery, therefore causes the extensive of people
Concern, becomes most potential candidate after both lithium ion batteries.But since sodium ion radius is greater than lithium ion,
Cause the negative electrode material graphite of Current commercial not can be used directly in sodium-ion battery, therefore finds and be suitble to sodium-ion battery
Negative electrode material is extremely urgent.Metal selenide is due to theoretical specific capacity with higher, and tap density is very high, becomes one
The very promising anode material of lithium-ion battery of class.But the selenides limited capacity for the single metal usually studied, therefore send out
The composite material for opening up two kinds of metal selenides becomes can obtain the effective of outstanding storage sodium performance in conjunction with the advantages of two kinds of materials
Method.However, common complex method is often difficult to realize uniform compound, good effect is not achieved.So being badly in need of development
A method of it is uniformly compound that two kinds of selenides may be implemented.
Herein, we pass through the monodispersed CoNiSe that solvent thermal design has synthesized a kind of regular appearance first4Double gold
Belong to selenides solid-solution material (cube pattern, side length about 270nm, inside are spherical secondary structure, diameter 45-65nm), then
Such a co-continuous CoSe is obtained by electrochemical process (constant current charge-discharge) in situ2/NiSe2Metal nanometer composite material
(co-continuous metal selenide refers to that the two-phase of two kinds of different metal selenides is completely continuous).The bimetallic obtained by this method
In selenides composite material, two kinds of metals have reached the compound of molecular level, and very uniform, and regular appearance is controllable, are answered
High capacity, excellent cyclical stability and high rate performance are shown when negative electrode material for sodium-ion battery.
Summary of the invention
Realize that co-continuous metal selenide nanometer is multiple by electrochemical in-situ method the purpose of the present invention is to propose to a kind of
Condensation material (CoSe2/NiSe2) controllable preparation new approaches and have studied its application in sodium-ion battery.
Co-continuous metal selenide nanocomposite CoSe provided by the invention2/NiSe2, by CoNiSe4Bimetallic selenium
Compound solid-solution material (micro-nano compound structure) is obtained by electrochemical method in situ.
The specific method is as follows:
(1) certain mol proportion example is pressed by CoSO4·7H2O and NiSO4·6H2O is added to the water stirring to being completely dissolved.
(2) ethyl alcohol is added in the solution that step (1) obtains, adds selenium powder, is sufficiently stirred.
(3) hydrazine hydrate is added in the solution that step (2) obtains, ultrasonic agitation is uniform later.
(4) solution that step (3) obtains is transferred in the kettle of polytetrafluoroethyllining lining, carries out solvent thermal reaction.
(5) the reaction product solid powder that collection step (4) obtains, is washed and is dried.
(6) CoNiSe that will be obtained4Nanocomposite and acetylene black, sodium carboxymethylcellulose in 7:2:1 ratio, with
Water is that uniformly slurry is made in solvent grinding, is coated uniformly on copper foil.As the working electrode of battery after to be dried, with gold
Belong to sodium piece as after being assembled into button half-cell in glove box to electrode, constant current charge-discharge is carried out on LAND.Voltage range
For 0.01-2.8V.By the constant current charge-discharge circulation of a circle, that obtain is exactly co-continuous CoSe2/NiSe2Nanocomposite.
Wherein, CoSO described in step (1)4·7H2O and NiSO4The ratio of 6H2O can be 1:9-9:1.
Amount of alcohol added can be 5-15mL in step (2).
The time of solvent thermal reaction can be 6-24h in step (4), and the temperature of reaction can be 160-200 DEG C
Detailed description of the invention
Fig. 1 is CoNiSe in embodiment 54The XRD diagram of solid-solution material.
Fig. 2 is CoNiSe in embodiment 54The electron scanning micrograph of solid-solution material.
Fig. 3 is the CoNiSe in embodiment 54The pattern and its formation co-continuous CoSe of solid-solution material2/NiSe2Nanometer is multiple
The schematic diagram of condensation material.
Fig. 4 is the co-continuous CoSe in embodiment 52/NiSe2When nanocomposite is as anode material of lithium-ion battery
Charging and discharging curve figure.
Fig. 5 is the co-continuous CoSe in embodiment 52/NiSe2When nanocomposite is as anode material of lithium-ion battery
High rate performance.
Fig. 6 is co-continuous CoSe in embodiment 52/NiSe2When nanocomposite is as anode material of lithium-ion battery
Cycle performance.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but the present invention is not limited to following embodiments.
Embodiment 1
Prepare co-continuous metal selenide nanocomposite CoSe2/NiSe2
By CoSO4·7H2O and NiSO4·6H2O is added in 44mL water by 3:7 (0.6mmol:1.4mmol) molar ratio and is stirred
Mix to being completely dissolved, backward solution in 10mL ethyl alcohol is added, add 4mmol selenium powder, be sufficiently stirred.It is eventually adding 16mL water
Hydrazine is closed, 0.5h is stirred by ultrasonic.
Then obtained solution is transferred in the kettle of polytetrafluoroethyllining lining, solvent thermal reaction is carried out at 160 DEG C, instead
It is 6h between seasonable.It collects reaction and obtains solid powder (Co0.3Ni0.7Se4), it is washed and is dried.
The Co that will be obtained0.3Ni0.7Se4Nanocomposite and acetylene black, sodium carboxymethylcellulose in 7:2:1 ratio,
It takes water as a solvent grinding and slurry uniformly is made, be coated uniformly on copper foil.As the working electrode of battery after to be dried, with
Metallic sodium piece carries out constant current charge-discharge as after being assembled into button half-cell in glove box to electrode on blue electric tester.
Voltage range is 0.01-2.8V.By the circulation of a circle, that obtain is exactly co-continuous CoSe2/NiSe2Nanocomposite.
Embodiment 2
Prepare co-continuous metal selenide nanocomposite CoSe2/NiSe2
By CoSO4·7H2O and NiSO4·6H2O be added in 44mL water by 5:5 (1mmol:1mmol) molar ratio stir to
Be completely dissolved, backward solution in be added 10mL ethyl alcohol, add 4mmol selenium powder, be sufficiently stirred.It is eventually adding 16mL hydration
0.5h is stirred by ultrasonic in hydrazine.Then obtained solution is transferred in the kettle of polytetrafluoroethyllining lining, solvent is carried out at 160 DEG C
Thermal response, reaction time 6h.It collects reaction and obtains solid powder (CoNiSe4), it is washed and is dried.
The CoNiSe that will be obtained4Nanocomposite and acetylene black, sodium carboxymethylcellulose in 7:2:1 ratio, with water
Slurry uniformly is made for solvent grinding, is coated uniformly on copper foil.As the working electrode of battery after to be dried, with metal
Sodium piece carries out constant current charge-discharge as after being assembled into button half-cell in glove box to electrode on blue electric tester.Voltage
Section is 0.01-2.8V.By the circulation of a circle, that obtain is exactly co-continuous CoSe2/NiSe2Nanocomposite.
Embodiment 3
Prepare co-continuous metal selenide nanocomposite CoSe2/NiSe2
By CoSO4·7H2O and NiSO4·6H2O is added in 44mL water by 5:5 (0.2mmol:1.8mmol) molar ratio and is stirred
Mix to being completely dissolved, backward solution in 5mL ethyl alcohol is added, add 4mmol selenium powder, be sufficiently stirred.It is eventually adding 16mL water
Hydrazine is closed, 0.5h is stirred by ultrasonic.Then obtained solution is transferred in the kettle of polytetrafluoroethyllining lining, is carried out at 160 DEG C molten
Agent thermal response, reaction time 6h.It collects reaction and obtains solid powder (CoNiSe4), it is washed and is dried.
The CoNiSe that will be obtained4Nanocomposite and acetylene black, sodium carboxymethylcellulose in 7:2:1 ratio, with water
Slurry uniformly is made for solvent grinding, is coated uniformly on copper foil.As the working electrode of battery after to be dried, with metal
Sodium piece carries out constant current charge-discharge as after being assembled into button half-cell in glove box to electrode on blue electric tester.Voltage
Section is 0.01-2.8V.By the circulation of a circle, that obtain is exactly co-continuous CoSe2/NiSe2Nanocomposite.
Embodiment 4
Prepare co-continuous metal selenide nanocomposite CoSe2/NiSe2
By CoSO4·7H2O and NiSO4·6H2O be added in 44mL water by 5:5 (1mmol:1mmol) molar ratio stir to
Be completely dissolved, backward solution in be added 5mL ethyl alcohol, add 4mmol selenium powder, be sufficiently stirred.It is eventually adding 16mL hydrazine hydrate,
0.5h is stirred by ultrasonic.Then obtained solution is transferred in the kettle of polytetrafluoroethyllining lining, it is anti-that solvent heat is carried out at 180 DEG C
It answers, reaction time 6h.It collects reaction and obtains solid powder (CoNiSe4), it is washed and is dried.
The CoNiSe that will be obtained4Nanocomposite and acetylene black, sodium carboxymethylcellulose in 7:2:1 ratio, with water
Slurry uniformly is made for solvent grinding, is coated uniformly on copper foil.As the working electrode of battery after to be dried, with metal
Sodium piece carries out constant current charge-discharge as after being assembled into button half-cell in glove box to electrode on blue electric tester.Voltage
Section is 0.01-2.8V.By the circulation of a circle, that obtain is exactly co-continuous CoSe2/NiSe2Nanocomposite.
Embodiment 5
Prepare co-continuous metal selenide nanocomposite CoSe2/NiSe2
By CoSO4·7H2O and NiSO4·6H2O be added in 44mL water by 5:5 (1mmol:1mmol) molar ratio stir to
Be completely dissolved, backward solution in be added 5mL ethyl alcohol, add 4mmol selenium powder, be sufficiently stirred.It is eventually adding 16mL hydrazine hydrate,
0.5h is stirred by ultrasonic.Then obtained solution is transferred in the kettle of polytetrafluoroethyllining lining, it is anti-that solvent heat is carried out at 180 DEG C
It answers, reaction time 12h.It collects reaction and obtains solid powder (CoNiSe4), it is washed and is dried.
The CoNiSe that will be obtained4Nanocomposite and acetylene black, sodium carboxymethylcellulose in 7:2:1 ratio, with water
Slurry uniformly is made for solvent grinding, is coated uniformly on copper foil.As the working electrode of battery after to be dried, with metal
Sodium piece carries out constant current charge-discharge as after being assembled into button half-cell in glove box to electrode on blue electric tester.Voltage
Section is 0.01-2.8V.By the circulation of a circle, that obtain is exactly co-continuous CoSe2/NiSe2Nanocomposite.
Embodiment 6
Prepare co-continuous metal selenide nanocomposite CoSe2/NiSe2
By CoSO4·7H2O and NiSO4·6H2O is added in 44mL water by 7:3 (1.4mmol:0.6mmol) molar ratio and is stirred
Mix to being completely dissolved, backward solution in 5mL ethyl alcohol is added, add 4mmol selenium powder, be sufficiently stirred.It is eventually adding 16mL water
Hydrazine is closed, 0.5h is stirred by ultrasonic.Then obtained solution is transferred in the kettle of polytetrafluoroethyllining lining, is carried out at 180 DEG C molten
Agent thermal response, reaction time 12h.It collects reaction and obtains solid powder (Co0.7Ni0.3Se4), it is washed and is dried.
The Co that will be obtained0.7Ni0.3Se4Nanocomposite and acetylene black, sodium carboxymethylcellulose in 7:2:1 ratio,
It takes water as a solvent grinding and slurry uniformly is made, be coated uniformly on copper foil.As the working electrode of battery after to be dried, with
Metallic sodium piece carries out constant current charge-discharge as after being assembled into button half-cell in glove box to electrode on blue electric tester.
Voltage range is 0.01-2.8V.By the circulation of a circle, that obtain is exactly co-continuous CoSe2/NiSe2Nanocomposite.
Embodiment 7
Prepare co-continuous metal selenide nanocomposite CoSe2/NiSe2
By CoSO4·7H2O and NiSO4·6H2O is added in 44mL water by 7:3 (1.4mmol:0.6mmol) molar ratio and is stirred
Mix to being completely dissolved, backward solution in 5mL ethyl alcohol is added, add 4mmol selenium powder, be sufficiently stirred.It is eventually adding 16mL water
Hydrazine is closed, 0.5h is stirred by ultrasonic.Then obtained solution is transferred in the kettle of polytetrafluoroethyllining lining, is carried out at 180 DEG C molten
Agent thermal response, reaction time are for 24 hours.It collects reaction and obtains solid powder (Co0.7Ni0.3Se4), it is washed and is dried.
The Co that will be obtained0.7Ni0.3Se4Nanocomposite and acetylene black, sodium carboxymethylcellulose in 7:2:1 ratio,
It takes water as a solvent grinding and slurry uniformly is made, be coated uniformly on copper foil.As the working electrode of battery after to be dried, with
Metallic sodium piece carries out constant current charge-discharge as after being assembled into button half-cell in glove box to electrode on blue electric tester.
Voltage range is 0.01-2.8V.By the circulation of a circle, that obtain is exactly co-continuous CoSe2/NiSe2Nanocomposite.
Embodiment 8
Prepare co-continuous metal selenide nanocomposite CoSe2/NiSe2
By CoSO4·7H2O and NiSO4·6H2O is added in 44mL water by 1:9 (0.2mmol:1.8mmol) molar ratio and is stirred
Mix to being completely dissolved, backward solution in 5mL ethyl alcohol is added, add 4mmol selenium powder, be sufficiently stirred.It is eventually adding 16mL water
Hydrazine is closed, 0.5h is stirred by ultrasonic.Then obtained solution is transferred in the kettle of polytetrafluoroethyllining lining, is carried out at 180 DEG C molten
Agent thermal response, reaction time are for 24 hours.It collects reaction and obtains solid powder (Co0.1Ni0.9Se4), it is washed and is dried.
The Co that will be obtained0.1Ni0.9Se4Nanocomposite and acetylene black, sodium carboxymethylcellulose in 7:2:1 ratio,
It takes water as a solvent grinding and slurry uniformly is made, be coated uniformly on copper foil.As the working electrode of battery after to be dried, with
Metallic sodium piece carries out constant current charge-discharge as after being assembled into button half-cell in glove box to electrode on blue electric tester.
Voltage range is 0.01-2.8V.By the circulation of a circle, that obtain is exactly co-continuous CoSe2/NiSe2Nanocomposite.
As can be seen from the table, co-continuous CoSe prepared by the present invention2/NiSe2Nanocomposite has outstanding storage sodium
Performance, and method is simple.The composite material obtained using the present invention is compound and its uniform, has co-continuous characteristic.
The CoNiSe that example 5 is obtained4Solid-solution material carries out powder x-ray diffraction, and (Rigaku DmaxrB, CuK α are penetrated
Line) test, as a result as shown in Figure 1, the diffraction peak of material is in CoSe2With NiSe2Between, it was demonstrated that we successfully synthesize
CoNiSe4Solid-solution material.Fig. 2 (a, b) is the electron scanning micrograph of embodiment 5, and embodiment 5 can be found out from figure
Obtained CoNiSe4Solid-solution material is the square micro-nano structure being assembled by little particle, and of uniform size, square side length is about
For 270nm, their diameter of secondary structure particle is formed between 25-50nm.Fig. 3 is CoNiSe in embodiment 54Solid solution
Material forms co-continuous CoSe by electrochemical in-situ method2/NiSe2The change procedure schematic diagram of nanocomposite, first
When secondary sodium, CoNiSe4Solid solution combination sodium and electronics generate metal simple-substance Co, metal simple-substance Ni and Na2Se structure such as Fig. 3
(c) shown in, this process is irreversible, and when going sodium, sodium and electronics abjection have just obtained the co-continuous of Fig. 3 (d)
CoSe2/NiSe2Composite construction, this process are high reversibles, so reaction is only in Co/ in subsequent cyclic process
NaSe2The CoSe of/Ni and co-continuous2/NiSe2Between be repeated.Fig. 4 is co-continuous CoSe in embodiment 52/NiSe2Nanometer is multiple
Charging and discharging curve figure when condensation material is as anode material of lithium-ion battery, it can be seen that in addition to first lap discharge curve it
Outside, the charging and discharging curve of 2-5 circle is almost to be completely coincident, this also demonstrates the CoSe of co-continuous2/NiSe2Composite construction is outstanding
Invertibity and stability out.Fig. 5 and Fig. 6 is respectively the CoSe of co-continuous in embodiment 52/NiSe2It is negative as sodium-ion battery
High rate performance and cycle performance figure when the material of pole.As can be seen from the figure material specific capacity under the current density of 50mA/g reaches
To 443mAh/g, even if capacity is also up to 330mAh/g under the high current density of 5A, passed through under the current density of 600mA/g
After crossing 100 circulations, there are also 90% for capacity retention ratio.To sum up, the CoSe of co-continuous2/NiSe2Nanocomposite as sodium from
The cathode of sub- battery shows excellent high rate performance and cycle performance, and it is special that this has benefited from co-continuous special in its structure
Property.
Claims (9)
1. a kind of prepare co-continuous CoSe2/NiSe2The method of nanocomposite: it is characterized in that, with CoSO4·7H2O、
NiSO4·6H2O, selenium powder, water, ethyl alcohol, hydrazine hydrate are raw material, and the metal selenide of co-continuous is prepared in situ by electrochemical method
Nanocomposite；
The specific method is as follows:
(1) certain mol proportion example is pressed by CoSO4·7H2O and NiSO4·6H2O is added to the water stirring to being completely dissolved；
(2) ethyl alcohol is added in the solution that step (1) obtains, adds selenium powder, is sufficiently stirred；
(3) hydrazine hydrate is added in the solution that step (2) obtains, ultrasonic agitation is uniform later；
(4) solution that step (3) obtains is transferred in the kettle of polytetrafluoroethyllining lining, carries out solvent thermal reaction, obtains solid
Powder；
(5) the reaction product solid powder that collection step (4) obtains, is washed and is dried, obtain CoNiSe4Solid-solution material；
(6) to CoNiSe4Smear is carried out, constant current charge-discharge is carried out after packed battery and obtains co-continuous CoSe2/NiSe2Nano combined material
Material.
2. a kind of co-continuous CoSe is prepared according to claim 12/NiSe2The method of nanocomposite, feature exist
In CoSO described in step (1)4·7H2O and NiSO4·6H2The molar ratio of O is 1:9-9:1.
3. a kind of co-continuous CoSe is prepared according to claim 22/NiSe2The method of nanocomposite, feature exist
In CoSO described in step (1)4·7H2O and NiSO4·6H2The molar ratio of O is 5:5.
4. a kind of co-continuous CoSe is prepared according to claim 12/NiSe2The method of nanocomposite, feature exist
In amount of alcohol added is 5-15mL in step (2).
5. a kind of co-continuous CoSe is prepared according to claim 12/NiSe2The method of nanocomposite, feature exist
In amount of alcohol added is 5mL in step (2).
6. preparation method according to claim 1, which is characterized in that the time of solvent thermal reaction is 6- in step (4)
24h。
7. preparation method according to claim 6, which is characterized in that the time of solvent thermal reaction is 12h in step (4).
8. preparation method according to claim 1, which is characterized in that the temperature of solvent thermal reaction is 160- in step (4)
200℃。
9. preparation method according to claim 8, which is characterized in that the temperature of solvent thermal reaction is 180 in step (4)
℃。
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| CN108550806B (en) * | 2018-03-28 | 2020-10-09 | 中南大学 | MnSe/CoSe2Composite material and preparation method and application thereof |
| CN108554426B (en) * | 2018-03-30 | 2020-07-28 | 深圳华中科技大学研究院 | Difunctional cobalt diselenide material and preparation and application thereof |
| CN108892111B (en) * | 2018-06-22 | 2020-09-08 | 北京大学 | Bimetallic selenide Fe of porous structure2CoSe4Material, preparation method and application thereof |
| CN109768236B (en) * | 2019-02-22 | 2020-10-20 | 肇庆市华师大光电产业研究院 | Preparation method of sodium ion battery anode material of double-metal selenide |
| CN111939945A (en) * | 2020-08-20 | 2020-11-17 | 安阳师范学院 | CoSe2NiSe2Preparation of-CC composite material and application of electrolytic water hydrogen evolution performance thereof |
| CN112018361B (en) * | 2020-08-31 | 2021-10-15 | 华中科技大学 | Carbon cloth loaded carbon coated cobalt selenide nanosheet battery cathode material and preparation thereof |
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