CN111204717A - One-dimensional lithium/sodium ion battery cathode material and preparation method and application thereof - Google Patents
One-dimensional lithium/sodium ion battery cathode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a one-dimensional lithium/sodium ion battery cathode material, belonging to the technical field of battery cathode materials. The method comprises the following steps: dissolving trivalent ferric salt and organic acid in a solution of N, N-dimethylformamide, adding a NaOH solution, transferring the obtained mixed solution into a reaction kettle, carrying out heat preservation reaction at 110-120 ℃ for 5.5-6 hours, and cooling the productCooling, centrifuging and drying to obtain a one-dimensional iron-based metal organic framework compound; mixing the organic framework compound with elemental selenium powder, and then transferring the mixture into a tube furnace for high-temperature selenization reaction to obtain one-dimensional Fe3Se4the/C composite material is the one-dimensional lithium/sodium ion battery negative electrode material. The method is simple, safe and efficient, and the phase composition is controllable, and the lithium battery and the sodium battery assembled by using the composite material can simultaneously realize high capacity, high multiplying power and high cycle stability.
Description
Technical Field
The invention relates to the technical field of battery cathode materials, in particular to a one-dimensional lithium/sodium ion battery cathode material and a preparation method and application thereof.
Background
With the reduction of fossil fuels and the generation of climate change and other problems, sustainable development and environmental protection become important topics for people, and more researchers actively develop efficient and clean new energy. The lithium ion battery has light weight, high working voltage, large energy density and long cycle life, is a main force of a secondary energy market, and is widely applied to the energy storage fields of portable electronic products, electric vehicles, electric automobiles and the like. The rise of the emerging technology industries such as electric automobiles brings a wider platform for lithium ion batteries, and meanwhile, lithium is trapped in the resource shortage dilemma. As the same main group elements, the sodium element has rich resources, low price, good safety performance and similar physical and chemical properties with lithium ions, and if the sodium can replace the lithium element to enter the army energy storage field, the problem of lithium element resource shortage can be solved to a great extent. Therefore, sodium ion batteries based on approximate energy storage mechanism are also the hot spot of current research and are expected to realize industrialization.
The negative electrode material is an important component of a secondary lithium/sodium ion battery, the common negative electrode materials of the current lithium ion battery comprise carbon-based materials, transition metal oxides, metals, alloys thereof and the like, and because the ionic radius of sodium ions is larger than that of lithium ions, some common negative electrode materials of the lithium ion battery cannot meet the reversible deintercalation of the sodium ions. The negative electrode materials of the sodium ion battery researched at present mainly comprise: carbon-based negative electrodes, titanium-based oxide negative electrodes, alloy negative electrodes and transition metal phosphate negative electrodes. The transition metal chalcogenide is considered as a potential lithium/sodium cathode material with better conductivity due to the larger interlayer spacing. Among them, selenides are gradually becoming negative electrode materials with their optimal conductivity (relative to oxides and sulfides) and considerable interfacial lithium/sodium storage capacityIs one of the popular research directions. Selenides are of various types, and NiSe is commonx、FeSexAnd CoSexIn order to better improve the electrochemical performance of the selenide, how to controllably prepare the transition metal selenide with a specific composition and good structural characteristics becomes a technical problem which is urgently needed to be solved at present.
Disclosure of Invention
In order to solve the technical problems, the invention provides a one-dimensional lithium/sodium ion battery cathode material, and a preparation method and application thereof, wherein the one-dimensional lithium/sodium ion battery cathode material is one-dimensional Fe3Se4The method can effectively and controllably prepare Fe3Se4/C，Fe3Se4The nano-particle or single crystal nano-rod structure is presented and dispersed in carbon, and the electrochemical performance of the nano-particle or single crystal nano-rod structure as a negative electrode material is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the one-dimensional lithium/sodium ion battery negative electrode material comprises the following steps:
1) dissolving trivalent ferric salt and organic acid into a solution of N, N-dimethylformamide together, adding a NaOH solution after stirring uniformly, transferring the obtained mixed solution into a reaction kettle with polytetrafluoroethylene as a lining, carrying out heat preservation reaction at 110-120 ℃ for 5.5-6 hours, and cooling, centrifuging and drying the product to obtain a one-dimensional iron-based metal organic framework compound;
2) mixing the one-dimensional iron-based metal organic framework compound with elemental selenium powder, and then transferring the mixture into a tube furnace for high-temperature selenization reaction to obtain one-dimensional Fe3Se4the/C composite material is the one-dimensional lithium/sodium ion battery negative electrode material.
In the step 1), the ferric salt is ferric nitrate or ferric chloride.
In the step 1), the organic acid is fumaric acid or terephthalic acid.
In the step 1), the molar ratio of the trivalent ferric salt to the organic acid is 1:2-1: 6.
In step 2), to obtain Fe3Se4But not other selenides, the mass ratio of the one-dimensional iron-based metal organic framework compound to the elemental selenium powder is 1:2-1: 6.
In the step 2), the temperature of the high-temperature selenization reaction is 450-650 ℃ to realize Fe3Se4And inhibit its disproportionation or further combination with selenium.
Further, the high-temperature selenization reaction is specifically as follows: heating to 450-650 ℃ at the heating rate of 5 ℃/min in the argon environment, carrying out heat treatment at the temperature for 2-2.5h, then cooling to room temperature, pouring the powder material into an agate mortar, and grinding to obtain one-dimensional Fe3Se4a/C composite material.
The invention also provides the one-dimensional Fe3Se4The application of the/C composite material is used for preparing a battery cathode, and the preparation method comprises the following steps:
1) one-dimensional Fe3Se4Mixing the/C composite material, acetylene black and sodium alginate to obtain a mixture, wherein the one-dimensional Fe is3Se4The mass ratio of the/C composite material to the acetylene black to the sodium alginate is 5-9:0.5-2: 0.5-1;
2) and adding water into the mixture, stirring to obtain slurry, uniformly coating the slurry on a copper foil, transferring to a vacuum oven for drying, and preparing into an electrode plate by using a sheet punching machine to obtain the battery cathode.
Further, the one-dimensional Fe3Se4The mass ratio of the/C composite material to the acetylene black to the sodium alginate is 7:2:1, and the temperature of the vacuum oven is set to be 75-80 ℃.
By adopting the technical scheme, the invention provides one-dimensional Fe3Se4Preparation method of/C composite material, and Fe3Se4the/C composite material is used for the negative electrode of a lithium/sodium battery, due to Fe3Se4The nano-particle or single crystal nano-rod structure is presented and dispersed in carbon, which is beneficial to the exertion of the negative performance of the alkali ion secondary battery and can realize pure phase Fe3Se4Is controlled.
The invention firstly constructs one-dimensional iron-based metalOrganic frame compound, and Fe is directly obtained by a one-step selenization method with controlled process parameters3Se4The method is simple, safe and efficient, and realizes controllable phase composition.
The invention has the beneficial effects that: the lithium battery and the sodium battery assembled by the composite material realize high capacity, high multiplying power and high cycling stability. From Fe3Se4Lithium battery assembled by taking/C composite material as negative electrode and having current density of 0.2Ag-1At this time, the initial discharge/charge capacity was 1235.1/879.0mAh g-1And 709.5mAh g can be maintained after 100 cycles-1The capacity retention rate of (2) is 77.8%; current density 5Ag-1The discharge capacity can be as high as 566.7mAh g-1. From Fe3Se4Sodium battery assembled by taking/C composite material as negative electrode and having current density of 0.2Ag-1Initial discharge/charge capacity at 674.3/590.5mAh g-1And after 50 cycles, the discharge capacity was 417.3mAh g-1The capacity retention rate was 61.9%.
Drawings
FIG. 1 is Fe of example 13Se4X-ray diffraction (XRD) pattern of the/C composite;
FIG. 2 is Fe3Se4Scanning Electron Microscopy (SEM) image of/C composite wherein (a) and (b) are Fe of example 13Se4SEM pictures of/C-R, where (C) and (d) are Fe of example 23Se4SEM image of/C-T.
FIG. 3 is Fe3Se4Transmission Electron Microscopy (TEM) image of/C composite, wherein (a), (b) and (C) are Fe of example 13Se4TEM image of/C-R, (d), (e) and (f) are Fe of example 23Se4TEM image of/C-T.
FIG. 4 shows Fe of the present invention3Se4Thermogravimetric curve of the/C composite material under air atmosphere.
FIG. 5, (a) is Fe of the present invention3Se4A lithium battery charge and discharge performance curve diagram of the/C composite material; (b) is Fe of the invention3Se4A lithium battery cycle performance curve diagram of the/C composite material; (C) to be sent outMing Fe3Se4The lithium battery rate performance curve diagram of the/C composite material.
FIG. 6(a) shows Fe of the present invention3Se4A sodium battery charge-discharge performance curve diagram of the/C composite material; (b) is Fe in the invention3Se4A sodium battery cycle performance curve diagram of the/C composite material; (c) is Fe of the invention3Se4The sodium battery rate performance curve diagram of the/C composite material.
Detailed Description
Example 1
One-dimensional Fe3Se4The preparation method of the/C composite material comprises the following steps:
step (1): putting 0.4178g of fumaric acid and 1.6160g of ferric nitrate nonahydrate into a 100mL beaker, adding 80mL of N, N-dimethylformamide into the beaker, continuously stirring to form a uniform solution, transferring the solution into a 100mL reaction kettle with a polytetrafluoroethylene lining, carrying out heat preservation reaction at 110 ℃ for 6 hours, cooling, filtering and drying to obtain the one-dimensional iron-based metal framework compound.
Step (2): respectively placing 0.2g of one-dimensional iron-based metal frame compound and 1g of selenium powder in the step (1) in a corundum magnetic boat, and paving as flat as possible.
And (3): transferring the sample in the step (2) into a tube furnace for high-temperature selenization reaction, heating to 500 ℃ at the heating rate of 5 ℃/min in the argon environment, carrying out heat treatment at 500 ℃ for 2h, cooling to room temperature, pouring the powder material into an agate mortar, and grinding to obtain one-dimensional Fe3Se4the/C composite material is marked as Fe3Se4/C-R。
One-dimensional Fe prepared by the method3Se4The crystal structure of the/C composite material is shown in figure 1, and XRD diffraction peaks and Fe in the spectrogram3Se4The method is completely consistent, no obvious impure phase is found, and the diffraction peak is relatively sharp, which indicates that the material has better crystallinity.
Referring to fig. 2a and 2b, as can be seen from fig. 2a, the material has a distinct one-dimensional structural feature, and the length thereof is 1-2 μm; as can be seen from fig. 2b, these one-dimensional structures are aggregated from countless nanoparticles.
Referring to FIG. 3, FIG. 3a is a TEM photograph of a sample, from which it can be seen that Fe is one-dimensional3Se4The nanoparticles of/C have a plurality of voids therein; from fig. 3b, carbon structures can be found partially surrounding the nanoparticles, confirming that the prepared material is a carbon-based composite; fig. 3c is a high resolution TEM photograph of the prepared material, which exhibits a lattice spacing consistent with theoretical values.
Phase composition of materials referring to FIG. 4, one-dimensional Fe of materials can be obtained by calculation3Se4The mass fraction of carbon in the/C mixture was about 12.4%.
Example 2
One-dimensional Fe3Se4The preparation method of the/C composite material comprises the following steps:
step (1): placing 0.415g terephthalic acid and 0.675g ferric trichloride hexahydrate in a 100mL beaker, adding 27mL N, N-dimethylformamide into the beaker, continuously stirring to form a uniform solution, adding 3mL 0.4mol L of N, N-dimethylformamide into the solution-1And uniformly stirring the NaOH solution, transferring the solution into a 50mL reaction kettle with a polytetrafluoroethylene lining, carrying out heat preservation reaction at 110 ℃ for 6 hours, and cooling, centrifuging and drying to obtain the one-dimensional iron-based metal framework compound.
Step (2): respectively placing 0.2g of one-dimensional iron-based metal frame compound and 1g of selenium powder in the step (1) in a corundum magnetic boat, and paving as flat as possible.
And (3): transferring the sample in the step (2) into a tube furnace for high-temperature selenization reaction, heating to 500 ℃ at the heating rate of 5 ℃/min in the argon environment, carrying out heat treatment at 500 ℃ for 2h, cooling to room temperature, pouring the powder material into an agate mortar, and grinding to obtain one-dimensional Fe3Se4the/C composite material is marked as Fe3Se4/C-T。
Referring to fig. 2c and 2d for the morphology characteristics of the material, it can be seen from fig. 2c that a large number of particles exhibit a one-dimensional nanorod structure; as can be seen from FIG. 2d, the agglomeration between nanorods is more evident.
Referring to fig. 3 for the microscopic morphology characteristics of the material, fig. 3d is a TEM photograph of a sample, from which it can be seen that the nanorods have general uniformity and are very significantly agglomerated; from fig. 3e, it can be seen that a large number of nanorods are dispersed in the carbon framework, confirming that the prepared material is a carbon-based composite material; fig. 3f is a high resolution TEM photograph of the prepared material, which exhibits a lattice spacing consistent with theoretical values.
Phase composition of materials referring to FIG. 4, one-dimensional Fe of materials can be obtained by calculation3Se4The mass fraction of carbon in the/C mixture was about 23.4%.
Example 3
One-dimensional Fe3Se4The preparation method of the/C composite material comprises the following steps:
step (1): putting 0.4178g of fumaric acid and 1.6160g of ferric nitrate nonahydrate into a 100mL beaker, adding 80mL of N, N-dimethylformamide into the beaker, continuously stirring to form a uniform solution, transferring the solution into a 100mL reaction kettle with a polytetrafluoroethylene lining, carrying out heat preservation reaction at 110 ℃ for 6 hours, cooling, filtering and drying to obtain the one-dimensional iron-based metal framework compound.
Step (2): and (2) fully mixing 0.2g of the one-dimensional iron-based metal framework compound and 0.2g of selenium powder in the step (1) in a mortar to form a mixed phase.
And (3): transferring the sample in the step (2) into a tube furnace for high-temperature selenization reaction, heating to 500 ℃ at the heating rate of 5 ℃/min in the argon environment, carrying out heat treatment at 500 ℃ for 2h, cooling to room temperature, pouring the powder material into an agate mortar, and grinding to obtain one-dimensional Fe3Se4a/C composite material.
Example 4
One-dimensional Fe3Se4The method for preparing the lithium ion battery cathode by the aid of the/C composite material comprises the following steps:
step (1): with one-dimensional Fe prepared in example 13Se4the/C composite material is an active substance, acetylene black is a conductive agent, ethanol is an auxiliary grinding agent, sodium alginate is a binder, and the active substance, the conductive agent and the binder are mixed according to the ratio of 7:2:1Mixing the components according to the mass ratio, fully grinding the mixture, placing the mixture in a crucible, and taking water as a solvent to prepare slurry.
Step (2): and uniformly coating the slurry on a copper foil, transferring the copper foil to a vacuum oven, drying for 12h at the temperature of 80 ℃, preparing an electrode plate with the diameter of 14mm by using a sheet punching machine, taking commercial lithium ion electrolyte as electrolyte, taking a lithium sheet as a counter electrode and a reference electrode, and assembling the button cell in a glove box filled with argon atmosphere.
FIG. 4 shows one-dimensional Fe of this example3Se4Electrochemical performance diagram of lithium ion battery assembled by/C composite material, and the optimized composite material has current density of 0.2Ag-1At this time, the initial discharge/charge capacity was 1235.1/879.0mAh g-1And 709.5mAh g can be maintained after 100 cycles-1The capacity retention rate of (2) is 77.8%; current density 5Ag-1The discharge capacity can be as high as 566.7mAh g-1。
Example 5
One-dimensional Fe3Se4The method for preparing the negative electrode of the sodium-ion battery by the aid of the/C composite material comprises the following steps:
step (1): with Fe prepared in example 23Se4The preparation method comprises the following steps of mixing an active substance, a conductive agent and a sodium carboxymethylcellulose according to a mass ratio of 7:2:1, fully grinding the mixture, placing the mixture in a crucible, and mixing the mixture into slurry by using water as a solvent.
Step (2): and uniformly coating the slurry on a copper foil, transferring the copper foil to a vacuum oven, drying for 12h at the temperature of 80 ℃, preparing an electrode plate with the diameter of 14mm by using a sheet punching machine, taking a self-prepared electrolyte as an electrolyte and a sodium sheet as a counter electrode and a reference electrode, and assembling a battery in a glove box filled with argon atmosphere.
FIG. 5 shows one-dimensional Fe of this example3Se4Electrochemical performance diagram of sodium ion battery assembled by/C composite material, and current density of 0.2Ag can be seen from the diagram-1Initial discharge/charge capacity at 674.3/590.5mAh g-1And after 50 cycles, the discharge capacity was 417.3mAh g-1The capacity retention rate was 61.9%; meanwhile, the material also has good rate capability.
The above-described embodiments are disclosed as illustrative examples, and various changes and modifications can be made by those skilled in the art without departing from the scope of the present invention. The technical scope of the present invention is not limited to the embodiments described in the specification, but the above is only the preferred embodiments of the present invention, and the present invention is not limited thereto.
Claims (10)
1. The preparation method of the one-dimensional lithium/sodium ion battery cathode material is characterized by comprising the following steps: which comprises the following steps:
1) dissolving trivalent ferric salt and organic acid into a solution of N, N-dimethylformamide together, adding a NaOH solution after stirring uniformly, transferring the obtained mixed solution into a reaction kettle with polytetrafluoroethylene as a lining, carrying out heat preservation reaction at 110-120 ℃ for 5.5-6 hours, and cooling, centrifuging and drying the product to obtain a one-dimensional iron-based metal organic framework compound;
2) mixing the one-dimensional iron-based metal organic framework compound with elemental selenium powder, and then transferring the mixture into a tube furnace for high-temperature selenization reaction to obtain one-dimensional Fe3Se4the/C composite material is the one-dimensional lithium/sodium ion battery negative electrode material.
2. The preparation method of the one-dimensional lithium/sodium ion battery negative electrode material according to claim 1, characterized in that: in the step 1), the ferric salt is ferric nitrate or ferric chloride.
3. The preparation method of the one-dimensional lithium/sodium ion battery negative electrode material according to claim 1, characterized in that: in the step 1), the organic acid is fumaric acid or terephthalic acid.
4. The preparation method of the one-dimensional lithium/sodium ion battery negative electrode material according to claim 1, characterized in that: in the step 1), the molar ratio of the trivalent ferric salt to the organic acid is 1:2-1: 6.
5. The preparation method of the one-dimensional lithium/sodium ion battery negative electrode material according to claim 1, characterized in that: in the step 2), the mass ratio of the one-dimensional iron-based metal organic framework compound to the elemental selenium powder is 1:2-1: 6.
6. The preparation method of the one-dimensional lithium/sodium ion battery negative electrode material according to claim 1, characterized in that: in the step 2), the temperature of the high-temperature selenization reaction is 450-650 ℃.
7. The preparation method of the one-dimensional lithium/sodium ion battery negative electrode material according to claim 1, characterized in that: in the step 2), the high-temperature selenization reaction is as follows: heating to 450-650 ℃ at the heating rate of 5 ℃/min in the argon environment, carrying out heat treatment at the temperature for 2-2.5h, then cooling to room temperature, pouring the powder material into an agate mortar, and grinding to obtain one-dimensional Fe3Se4a/C composite material.
8. One-dimensional Fe obtained by the production method according to any one of claims 1 to 73Se4a/C composite material.
9. The one-dimensional Fe of claim 83Se4The application of the/C composite material is characterized in that: the composite material is used for preparing a battery cathode, and the preparation method comprises the following steps:
1) one-dimensional Fe3Se4Mixing the/C composite material, acetylene black and sodium alginate to obtain a mixture, wherein the one-dimensional Fe is3Se4The mass ratio of the/C composite material to the acetylene black to the sodium alginate is 5-9:0.5-2: 0.5-1;
2) and adding water into the mixture, stirring to obtain slurry, uniformly coating the slurry on a copper foil, transferring to a vacuum oven for drying, and preparing into an electrode plate by using a sheet punching machine to obtain the battery cathode.
10. The method of claim 9One-dimensional Fe3Se4The application of the/C composite material is characterized in that: the one-dimensional Fe3Se4The mass ratio of the/C composite material to the acetylene black to the sodium alginate is 7:2:1, and the temperature of the vacuum oven is set to be 75-80 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113178571A (en) * | 2021-03-17 | 2021-07-27 | 湖南理工学院 | Hierarchical porous Fe3Se4@ NC @ CNTs composite material and preparation method and application thereof |
| CN115000361A (en) * | 2022-04-25 | 2022-09-02 | 齐鲁工业大学 | Fe 3 Se 4 Graphene sodium battery negative electrode material and preparation method thereof |
| CN115207344A (en) * | 2021-04-12 | 2022-10-18 | 南京工业大学 | Fe x Se y Preparation of @ CN composite material and electrochemical energy storage application thereof |
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| CN115000361A (en) * | 2022-04-25 | 2022-09-02 | 齐鲁工业大学 | Fe 3 Se 4 Graphene sodium battery negative electrode material and preparation method thereof |
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